Binuclear gold(i) compounds for photocatalytic applications

Abstract

Gold(I) complexes capable of absorbing light in the near-UV and / or visible region, and methods of making and using the same, are described. These gold(I) complexes have photochemical reactivity, such as strong absorption of near-UV and / or visible light, quenching rate constants of > 3.5 x 10 5 s ‑1 This enables them to catalyze photoredox reactions under near-UV and / or visible light, such as homocoupling of organic halides (e.g., alkyl halides and aryl halides), alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinolines, cyclization of indoles, reductive dehalogenation of aryl halides, and / or C-H bond cleavage, among others. The yields of products of photo-induced organic reactions catalyzed by the gold(I) complexes described herein can be higher than the yields of the same products formed from the same reactions under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3] at the same or higher loading than the loading of the one or more gold(I) complexes.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 223,468, filed July 19, 2021, the disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention generally belongs to the field of gold (I) complexes and their use as photocatalysts in organic reactions. Background Technology

[0004] Photo-redox catalysis has become an effective method for organic synthesis under mild reaction conditions. Photo-redox catalysis mainly employs d... 6 Transition metal compounds such as iridium(III) and ruthenium(II) compounds are used as photocatalysts. This is mainly due to their known excited-state properties and commercial availability. By tuning their structures, their excited-state properties can be tuned to activate different kinds of organic substrates for reactions. However, due to the octahedral coordination geometry of iridium(III) and ruthenium(II) photocatalysts, these photocatalysts can only catalyze photoinduced reactions through outer-shell electron transfer and / or energy transfer. They cannot participate in reactions that require substrate binding or radical capture via metal complexes (i.e., limited to outer-shell electron transfer). This limits the types of reactions that can be catalyzed.

[0005] d 8 and d 10 The application of transition metal compounds in photoredox catalysis for organic transformation has been less explored. One example is [Au2(μ-dppm)2]. 2+ (dppm = bis(diphenylphosphine)methane), which exhibits high energy 3 The [5dσ*6pσ] excited state readily undergoes substrate binding in solution at room temperature. However, high-energy UVA light (such as UV (365nm) light) is required to generate the triplet excited state and catalyze the photochemical reaction because the absorptivity of this gold complex is less than 1×10⁻⁶ at wavelengths above 330nm. 3 M -1 cm -1 This poses challenges to large-scale synthesis and limits the substrate range.

[0006] There is still a need to develop gold (I) complexes that can catalyze organic reactions under near-ultraviolet and / or visible light.

[0007] Therefore, the object of the present invention is to provide gold (I) complexes that catalyze organic reactions under near-ultraviolet and / or visible light.

[0008] Another object of the present invention is to provide a method for preparing gold (I) complexes.

[0009] Another object of the present invention is to provide a method for using gold (I) complexes in photocatalytic reactions. Summary of the Invention

[0010] Gold(I) complexes that can absorb light in the near-ultraviolet and / or visible light regions, as well as their preparation and use methods, are described. These gold(I) complexes are photochemically reactive, enabling them to catalyze photoredox reactions under near-ultraviolet and / or visible light.

[0011] Gold(I) complexes can have the structure of formula I:

[0012]

[0013] Wherein: (a) m can be 0, 1, or 2 positive charges; (b) n can be an integer between 0 and 2; (c) when present, each occurrence of A' can be an anion; (d) X1 to X4 can be P or N independently; (e) L1 and L2 can be absent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid, phosphoryl, or phosphonyl; (f) CY1 to CY8 can be substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted. (g) R1 to R8 may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (h) n1 to n8 can be independent integers between 0 and 10; (i) each ------ can be independent of being absent, a single bond, a double bond, or a triple bond; (j) Z1 and Z2 can be independent of being absent, a halide (fluoride, chloride, bromide, or iodide), trifluoromethanesulfonate, sulfonate, phosphonate, perchlorate, dicyanophosphate, cyano, nitrate, hydroxyl, oxalate, or carboxylate; (k) Z3 can be absent, a halide (fluoride, chloride, bromide, or iodide), oxygen, sulfur, oxalate, or carboxylate; (l) substituents can be independent of being substituted or Unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, aryloxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphoryl, phosphonyl or mercapto, or combinations thereof.

[0014] In some forms, when CY1 to CY8 of Formula I are independently substituted or unsubstituted aryl groups, at least one of R1 to R8 is not hydrogen. In some forms of Formula I, at least one of CY1 to CY8 is not an unsubstituted aryl group. In some forms, the gold(I) complexes disclosed herein are not [Au2(μ-dppm)2](Cl)2.

[0015] In some forms, gold (I) complexes can have the structure of formula Ia, formula Ib, or formula Ic:

[0016]

[0017]

[0018] Wherein: (a) A' in each occurrence can be an anion; (b) X1 to X4 can be P or N independently; (c) L1 and L2 can be absent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide, ether, polyether, thioether, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid, phosphoryl or phosphonyl; (d) CY1 to CY8 can be substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl or substituted or unsubstituted cycloalkynyl; (e) R1 to R8 can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted (a) aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto; (f) n1 to n8 may be independent integers between 0 and 10; (g) each ------ may be independent or be a single bond; (h) Z1 and Z2 may be independent halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonate, sulfonate, phosphate, perchlorate, dicyanophosphate, cyano, nitrate, hydroxyl, oxo, oxalate or carboxylate; (i) Z3 may be a halide (fluoride, chloride, bromide or iodide), oxygen, sulfur, oxalate or carboxylate; (j) substituents may be as defined above for Formula I.

[0019] In some forms of equations I, Ia, Ib, and / or Ic, L1 and L2 can be independent single bonds or R9 and R 10It can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n9 can be between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, or an integer of 1. In some forms of formula I, Ia, Ib, and / or Ic, X1 to X4 can be P. In some forms of formula I, Ia, Ib, and / or Ic, CY1 to CY8 can be independently substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted polyheteroaryl.

[0020] In some forms, gold(I) complexes can have the structure of formula IIa, IIb, or IIc:

[0021]

[0022] or

[0023]

[0024] Wherein: (a) n10 and n12 can be independently an integer between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, or 1; (b) R1 to R8 can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (c) n1 to n8 can be an integer between 0 and 5 independently; (d) each ------ can be either absent or a single bond independently; (e) Z1 and Z2 can be halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonates, sulfonates, phosphates, perchlorates, dicyanophosphates, cyano groups, nitrates, hydroxyl groups, oxalates, or carboxylates independently; (f) Z3 can be a halide (fluorides, chlorides, bromides or iodides), oxygen, sulfur, oxalates, or carboxylates; (g) each A' can be an anion; and (h) substituents can be as defined in Formula I.

[0025] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb, and / or IIc, R1 to R8 may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, or alkoxy. In some forms of formulas I, Ia, Ib, Ic, IIa, IIb, and / or IIc, R1 to R8 may independently be hydrogen, unsubstituted alkyl, haloalkyl, substituted or unsubstituted heterocyclic, or And R 13 and R 14 It can be independently hydrogen or a substituted or unsubstituted alkyl group, and n14 can be an integer from 0 to 5, from 0 to 4, from 0 to 3, from 0 to 2, or 0 or 1. In some forms, R 13 and R 14 Can be independently of unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0026] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, Z1 to Z3 can be halides independently, such as fluorides, chlorides, bromides, iodides or astatides, for example, chlorides or bromides.

[0027] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, each occurrence of A' may be a hydride, oxide, fluoride, sulfide, chloride, bromide, iodide, hydrogen phosphate, dihydrogen phosphate, hexafluorophosphate, trifluoromethanesulfonate, sulfate, nitrate, hydrogen sulfate, nitrite, thiosulfate, sulfite, chlorate, bromate, chlorite, hypochlorite, hypobromate, carbonate, chromate, bicarbonate, dichromate, perchlorate, acetate, formate, cyanide, amine, cyanate, peroxide, thiocyanate, oxalate, hydroxide or permanganate. In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, each occurrence of A' can be a halide (such as fluoride, bromide, iodide, etc.), perchlorate, hydrogen phosphate, dihydrogen phosphate, sulfate, nitrate, hydrogen sulfate, nitrite, chlorate, bromate, chlorite, hypochlorite or hypobromate, for example, a halide or perchlorate.

[0028] The gold (I) complexes described herein can be synthesized by reacting the corresponding ligand (optionally more than one corresponding ligand) with the gold precursor in a suitable solvent.

[0029] The gold (I) complexes described herein are suitable for photoredox catalysis, such as photoinduced organic reactions, including homocoupling of organohalides (e.g., alkyl halides and aryl halides), alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, cyclization of indole, reductive dehalogenation of aryl halides, and / or CH bond cleavage. In particular, these gold (I) complexes absorb light in the near-ultraviolet and / or visible wavelength range, such as light in the range of approximately 360 nm to approximately 450 nm or approximately 380 nm to approximately 450 nm, and therefore can catalyze photoredox reactions under near-ultraviolet and / or visible light.

[0030] Methods for catalyzing organic reactions using one or more gold (I) complexes disclosed herein may include: (i) exposing the reaction mixture to light at a certain temperature for a period of time sufficient to form a product. Typically, the light used to induce the organic reaction may have wavelengths in the following ranges: about 350 nm to about 450 nm, about 360 nm to about 450 nm, about 370 nm to about 450 nm, about 380 nm to about 450 nm, about 390 nm to about 450 nm, about 400 nm to about 450 nm, or about 405 nm to about 450 nm, such as about 405 nm or about 445 nm.

[0031] The reaction mixture may contain reactants (optionally more than one reactant), a solvent, and one or more gold (I) complexes. Optionally, the reaction mixture may further contain a suitable base, such as Et3N, iPr2NMe, iPr2NEt, 2,4,6-trimethylpyridine, imidazole, potassium carbonate or sodium carbonate, or combinations thereof.

[0032] Typically, the total amount of one or more gold (I) complexes in the reaction mixture can be up to 10 mol%, up to 5 mol%, up to 2 mol%, at least 0.05 mol%, at least 0.1 mol%, about 0.05 mol% to about 10 mol%, about 0.05 mol% to about 5 mol%, about 0.05 mol% to about 2 mol%, about 0.05 mol% to about 1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.1 mol% to about 10 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 2 mol%, about 0.1 mol% to about 1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.5 mol% to about 10 mol%, about 0.5 mol% to about 5 mol%, about 0.5 mol% to about 2 mol%, or about 0.5 mol% to about 1 mol%.

[0033] Typically, the products formed by organic reactions catalyzed by one or more gold (I) complexes disclosed herein can have yields of at least 12%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, up to 99%, up to 98%, up to 95%. %, about 15% to about 99%, about 20% to about 99%, about 40% to about 99%, about 50% to about 99%, about 15% to about 95%, about 20% to about 99%, about 40% to about 95%, about 50% to about 95%, about 15% to about 90%, about 20% to about 90%, about 40% to about 90%, about 50% to about 90%, about 15% to about 80%, about 20% to about 80%, about 40% to about 80%, or about 50% to about 80%.

[0034] The gold (I) complexes disclosed herein exhibit higher photocatalytic activity compared to known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3]. For example, the yield of products from photoinduced organic reactions using one or more of the gold (I) complexes described herein is higher than the yield of the same products formed by the same reaction under the same reaction conditions using the same or higher loadings of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3] compared to the loadings of one or more gold (I) complexes. Attached Figure Description

[0035] Figures 1A to 1D It is a coordination compound 2a ( Figure 1A ), 3a ( Figure 1B ), 4a ( Figure 1C ) and 5a( Figure 1D The ORTEP plot of the thermal ellipsoid is shown, with a probability level of 30%. For clarity, hydrogen atoms, solvent molecules, and perchlorate anions have been omitted.

[0036] Figures 2A to 2B This shows the absorption of complexes 1b, 2b, and / or 4a in degassed CH3CN at room temperature. Figure 2A ) and launch ( Figure 2B (A diagram of the spectrum.) Figures 2C to 2G It displays 1b ( Figure 2C ), 2b Figure 2D ), 3b Figure 2E ), 4a ( Figure 2F ) and 5a( Figure 2GEmission spectra at 77 K in solid and glassy media [DMF:EtOH:MeOH=1:1:4(V / V / V)].

[0037] Figure 3A It is displayed 4a after the laser flash in a position with n A nanosecond time-resolution absorption spectrum of Bu4NPF6 (0.1M) in CH3CN (time 0 of the laser flash occurs at 0.012 μs; the time shown in the figure refers to the time after the laser flash). Figure 3B This is a graph showing the femtosecond time-resolution transient absorption differential spectrum of 4a after excitation at 266 nm in CH3CN.

[0038] Figure 4A This is a graph showing the calculated absorption spectra of complexes 1b and 4a. Figure 4B This is a graph showing the calculated MO for 1b and 4a in state S0. Equivalent value = 0.03.

[0039] Figures 5A to 5C It displays 1b ( Figure 5A ), 1b-[ClO4]2( Figure 5B ), 4a-[ClO4]2( Figure 5C ) and 4a( Figure 5D The diagram shows the optimized T1 structure. Figure 5E This is a graph showing the calculated MO of the 1b and 1b-ClO4 complexes at the T1 state.

[0040] Figure 6A This is a graph showing the kinetics of solutions containing complex 4a [0.04 mM] and ISP / ISP+BEB [2 mM each] on the microsecond (top) and millisecond (bottom) timescales. ISP = 2-phenyl-1,2,3,4-tetrahydroisoquinoline, BEB = (2-bromoethyl)benzene. Figure 6B and 6C This is a graph showing the ns-TA spectrum of 4a at 100 μs in the presence of chlorobenzene [2 mM] [experimental in the presence of chlorobenzene]. n [The reaction was carried out in an acetonitrile solution of Bu4NPF6 (0.1M)]( Figure 6B ) and in having n A kinetic analysis diagram of selected absorption peaks in an acetonitrile solution containing Bu4NPF6 (0.1M) and chlorobenzene [2mM] for 4a. Figure 6C ). Detailed Implementation

[0041] I. Definition

[0042] It should be understood that, unless otherwise stated, the disclosed compounds, compositions, and methods are not limited to specific synthetic methods, specific analytical techniques, or specific reagents, and therefore can vary. It should also be understood that the terminology used herein is for the purpose of describing particular forms and embodiments only and is not intended to be limiting.

[0043] As used herein, “substituted” means all permitted substituents of the compounds or functional groups described herein. In the broadest sense, permitted substituents include acyclic and cyclic, branched and linear, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Exemplary substituents include, but are not limited to, halogens, hydroxyl groups, or any other organic groups containing any number of carbon atoms (preferably 1 to 14 carbon atoms), and optionally including one or more heteroatoms, such as oxygen, sulfur, or nitrogen groups, in linear, branched, or cyclic forms. Representative substituents include substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, halogen, hydroxyl, alkoxy, phenoxy, aryloxy, silyl, mercapto, alkylthio, substituted alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, substituted or unsubstituted carbonyl, carboxyl, amino, amide, oxo, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphoryl, phosphonyl, and amino acid groups. Such substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, halogen, hydroxyl, alkoxy, phenoxy, aryloxy, silyl, mercapto, alkylthio, substituted alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, substituted or unsubstituted carbonyl, carboxyl, amino, amide, oxo, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphoryl, phosphonyl and amino acid groups may be further substituted.

[0044] Heteroatoms such as nitrogen may have hydrogen substituents and / or any permitted substituents in the organic compounds described herein that satisfy the heteroatom valence. It should be understood that “substitution” or “substituted” includes the implicit precondition that such substitution occurs according to the permitted valence of the substituted atom and the substituent, and that the substitution yields a stable compound, i.e., a compound that does not spontaneously undergo transformation (e.g., transformation by rearrangement, cyclization, elimination, etc.).

[0045] As used herein, "alkyl" refers to a saturated aliphatic group, including straight-chain alkyl, branched-chain alkyl, and cycloalkyl (alicyclic). In some forms, straight-chain or branched alkyl groups have 30 or fewer carbon atoms in their main chain (e.g., C1-C for straight-chain alkyl groups). 30 For branched alkyl groups with C3-C 30 Alkyl groups have 20 or fewer, 15 or fewer, or 10 or fewer carbon atoms. Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. Similarly, cycloalkyl groups are non-aromatic carbonyl rings consisting of at least 3 carbon atoms (e.g., non-aromatic monocyclic or polycyclic rings containing 3 to 30, 3 to 20, or 3 to 10 carbon atoms in the ring structure), and have 5, 6, or 7 carbons in the ring structure. Cycloalkyl groups containing polycyclic systems may have two or more non-aromatic rings where two or more carbons are common to two adjacent rings (i.e., "fused cycloalkyl rings"). Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0046] The term "alkyl" as used throughout this specification, examples, and claims is intended to include both "unsubstituted alkyl" and "substituted alkyl," the latter referring to an alkyl moiety having a substituent for hydrogen on one or more carbons of a substituted hydrocarbon backbone. Such substituents may be any of the substituents listed above, such as halogens (e.g., fluorine, chlorine, bromine, or iodine), hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), aryl, alkoxy, aralkyl, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino, amide, amidine, imine, cyano, nitro, azide, oxo, thiohydrogen, mercapto, alkylthio, silyl, sulfinyl, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, aromatic, or heteroaromatic moiety. -NRR', where R and R' are independently hydrogen, alkyl, or aryl, and where the nitrogen atom is optionally quaternized; -SR, where R is phosphonoyl, sulfinyl, silyl, hydrogen, alkyl, or aryl; -CN; -NO2; -COOH; carboxylate; -COR, -COOR, or -CON(R)2, where R is hydrogen, alkyl, or aryl; imino, silyl, ether, haloalkyl (e.g., -CF3, -CH2-CF3, -CCl3, etc.); -CN; -NCOCOCH2CH2; -NCOCOCHCH; and -NCS; and combinations thereof. The term "alkyl" also includes "heteroalkyl".

[0047] Those skilled in the art will understand that, where appropriate, the substituted portion of the hydrocarbon chain can itself be substituted. For example, substituents of the substituted alkyl group can include halogens, hydroxyl groups, nitro groups, mercapto groups, amino groups, aralkyl groups, azide groups, imino groups, amide groups, phosphono groups, phosphoryl groups (including phosphonates and hypophosphonates), oxo groups, sulfonyl groups (including sulfates, sulfonamides, aminosulfonyls, and sulfonates), and silyl groups, as well as ethers, alkylthio groups, carbonyl groups (including ketones, aldehydes, carboxyl groups, and esters), haloalkyl groups, -CN groups, etc. Cycloalkyl groups can be substituted in the same manner.

[0048] Unless otherwise specified, “lower alkyl” as used herein refers to alkyl groups as defined above but having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, in their main chain structure. Similarly, “lower alkenyl” and “lower alkynyl” have similar chain lengths.

[0049] As used herein, “heteroalkyl” means a straight-chain, branched, or cyclic carbon-containing alkyl group or combination thereof containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P, and S, wherein nitrogen, phosphorus, and sulfur atoms are optionally oxidized, and nitrogen heteroatoms are optionally quaternized. For example, the term “heterocycloalkyl” is a cycloalkyl group as defined above in which at least one of the cyclic carbon atoms is substituted with a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus).

[0050] As used herein, the term "alkenyl" is a hydrocarbon group having 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon double bond. Alkenyl groups include straight-chain alkenyl, branched alkenyl, and cycloalkenyl. A cycloalkenyl is a non-aromatic carbonyl ring consisting of at least 3 carbon atoms and at least one carbon-carbon double bond, for example, a non-aromatic monocyclic or non-aromatic polycyclic ring containing 3 to 30 carbon atoms and at least one carbon-carbon double bond, 3 to 20 carbon atoms and at least one carbon-carbon double bond, or 3 to 10 carbon atoms and at least one carbon-carbon double bond, and having 5, 6, or 7 carbons and at least one carbon-carbon double bond in the ring structure. Cycloalkenyl groups containing polycyclic systems may have two or more non-aromatic rings in which two or more carbons are common to two adjacent rings (i.e., "fused cycloalkenyl rings") and contain at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(C'D) are intended to include both E and Z isomers. This can be assumed in the structural formula of the present invention, in which an asymmetric olefin is present, or it can be explicitly indicated by the bond symbol C. Throughout this specification, examples, and claims, the term "alkenyl" is intended to include both "unsubstituted alkenyl" and "substituted alkenyl," the latter referring to an alkenyl moiety having substituents on one or more carbons of a substituted hydrocarbon backbone. The term "alkenyl" also includes "heteroalkenyl."

[0051] The term "substituted alkenyl" refers to an alkenyl moiety having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, oxo, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0052] As used herein, “heteroalkenyl” refers to a straight-chain, branched, or cyclic carbon-containing alkenyl group or combination thereof containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P, and S, wherein nitrogen, phosphorus, and sulfur atoms are optionally oxidized, and nitrogen heteroatoms are optionally quaternized. For example, the term “heterocyclic alkenyl” is a cycloalkenyl group in which at least one of the cyclic carbon atoms is substituted by a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus).

[0053] As used herein, the term "alkynyl" is a hydrocarbon group having 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. Alynyl groups include straight-chain alkynyls, branched-chain alkynyls, and cycloalkynyls. A cycloalkynyl is a non-aromatic carbonyl ring consisting of at least three carbon atoms and at least one carbon-carbon triple bond, such as a non-aromatic monocyclic or non-aromatic polycyclic ring containing 3 to 30 carbon atoms and at least one carbon-carbon triple bond, 3 to 20 carbon atoms and at least one carbon-carbon triple bond, or 3 to 10 carbon atoms and at least one carbon-carbon triple bond, and having 5, 6, or 7 carbons and at least one carbon-carbon triple bond in its ring structure. Cycloalkynyl groups containing polycyclic systems may have two or more non-aromatic rings in which two or more carbons are common to two adjacent rings (i.e., "fused cycloalkynyl rings") and contain at least one carbon-carbon triple bond. For example... The asymmetric structure of the alkynes is intended to include E and Z isomers. This may be assumed in the structural formula herein in which an asymmetric alkyne is present, or it may be explicitly indicated by the bond symbol C. Throughout this specification, examples, and claims, the term "alkynyl" is intended to include both "unsubstituted alkynyl" and "substituted alkynyl," the latter referring to an alkynyl moiety having a substituent of hydrogen on one or more carbons of one or more substituted hydrocarbon backbones. The term "alkynyl" also includes "heterynyl."

[0054] The term "substituted alkynyl" refers to the alkynyl moiety having a substituent on one or more carbons of one or more substituted hydrocarbon backbones. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates, or thiocarbamates), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate esters, phosphonates, hypophosphonates, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0055] As used herein, “heteroyne” refers to a straight-chain, branched, or cyclic carbonaceous ynyl group or combination thereof containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P, and S, wherein nitrogen, phosphorus, and sulfur atoms are optionally oxidized, and nitrogen heteroatoms are optionally quaternized. For example, the term “heterocyclic ynyl” is a cyclic ynyl group in which at least one of the cyclic carbon atoms is substituted by a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus).

[0056] As used in this article, the term "aryl" refers to any C5-C 26 Carbon-based aromatic groups, heteroaromatic groups, fused aromatic groups, or fused heteroaromatic groups. For example, as used herein, "aryl" may include 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, 10-membered, 14-membered, 18-membered, and 24-membered monocyclic aromatic groups, including but not limited to benzene, naphthalene, anthracene, phenanthrene, etc. Examples of aryl groups include pyrene, cycloalkenes, and benzene. "Aryl" further includes polycyclic systems (i.e., "fused aromatic rings") having two or more rings shared by two adjacent rings, wherein at least one ring is aromatic; for example, the other one or more rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and / or heterocyclic. Aryl groups may be substituted with one or more groups, including but not limited to alkyl, alkynyl, alkenyl, aryl, halides, nitro, amino, esters, ketones, aldehydes, hydroxyl, carboxylic acids, or alkoxy groups.

[0057] The term "substituted aryl" refers to an aryl group in which one or more hydrogen atoms on one or more aromatic rings are replaced by one or more substituents. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (e.g., ketones, aldehydes, carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates, or thiocarbamates), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, imino, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl (e.g., CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0058] "Heterocycle" and "heterocyclic group" are used interchangeably and refer to a cyclic group consisting of 3 to 30, 3 to 20, 3 to 10, or 5 to 6 non-aromatic monocyclic or polycyclic carbon or nitrogen atoms linked together, wherein each ring contains carbon and 1 to 4 atoms selected from non-peroxide oxygen, sulfur, and N(Y) (where Y is absent or is H, O, Cl-C). 10 The heterocycle (alkyl, phenyl, or benzyl) contains one to three double bonds, which are optionally substituted with one or more substituents. By definition, a heterocyclic group is distinct from a heteroaryl group. The heterocycle can be a heterocyclic alkyl, heterocyclic alkenyl, heterocyclic alkynyl, etc., such as piperazinyl, piperidinyl, piperidinoneyl, 4-piperidinoneyl, dihydrofurano[2,3-b]tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidinoneyl, 4-piperidinoneyl, piperinyl, pyranyl, 2H-pyrroleyl, 4H-quinazinyl, quininecycloyl, tetrahydrofuranyl, 6H-1,2,5-thiadiazinyl. The heterocyclic group may optionally be substituted with one or more substituents defined above for alkyl and aryl groups.

[0059] The term "heteroaryl" refers to C5-C 30A heteroaryl group is a monocyclic aromatic ring, a fused aromatic ring, a bicyclic aromatic ring system, or a combination thereof, wherein one or more carbon atoms in one or more aromatic ring structures have been replaced by heteroatoms. Suitable heteroatoms include, but are not limited to, oxygen, sulfur, and nitrogen. As used herein, "heteroaryl" in a broad sense includes 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, 10-membered, 14-membered, 18-membered, and 24-membered monocyclic aryl groups, which may include 1 to 4 heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetraazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine. Heteroaryl groups may also be referred to as "aryl heterocycles" or "heteroaromatic groups." "Heteroaryl" further includes polycyclic systems (i.e., "fused rings") having two or more rings shared by two adjacent rings, wherein at least one ring is heteroaromatic, for example, the other ring or rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic, or a combination thereof. Examples of heteroaryl rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophene, benzooxazolyl, benzooxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazole, benzoisooxazolyl, benzoisothiazolyl, benzimidazolinyl, carbazole, 4aH-carbazole, carbolinyl, chromanyl, chromenyl, cenyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, furanyl, and furazonyl. Imidazolyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indololinyl, indolazinyl, indolyl, 3H-indolyl, sinapicoyl, isobenzofuranyl, isochoryl, isoindololinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthidyl, octahydroisoquinolinyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl 1,3,4-oxadiazolyl, oxazolyl, oxazolyl, hydroxyindole, pyrimidinyl, phenanthridine, phenanthroline, phenazinyl, phenthiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, pteridinyl, purine, pyrazinyl, pyrazolylalkyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazolyl, pyridoimidazolyl, pyridothiazolyl, pyridinyl The compounds include pyridyl, pyrimidinyl, pyrrolylyl, pyrrolinyl, pyrroloyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thienyl, and xanthonyl. One or more rings may be substituted as defined below for "substituted heteroaryl".

[0060] The term "substituted heteroaryl" refers to a heteroaryl group in which one or more hydrogen atoms on one or more heteroaryl rings are replaced by one or more substituents. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (e.g., ketones, aldehydes, carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates, or thiocarbamates), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, imino, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl (e.g., CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0061] The term "polyaryl" refers to a chemical moiety comprising two or more aryl, heteroaryl, and combinations thereof. Aryl, heteroaryl, and combinations thereof are fused or linked by single bonds, ethers, esters, carbonyl groups, amides, sulfonyl groups, sulfonamides, alkyl groups, azo groups, and combinations thereof. For example, "polyaryl" can be a polycyclic system having two or more rings shared by two adjacent rings (i.e., a "fused aromatic ring"), wherein the two or more rings are aromatic. When two or more heteroaryl groups are involved, the chemical moiety may be called "polyheteroaryl".

[0062] The term "substituted polyaryl" refers to a polyaryl group in which one or more aryl or heteroaryl groups are replaced by one or more substituents. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof. When two or more heteroaryl groups are involved, the chemical motif may be referred to as "substituted polyheteroaryl".

[0063] The term "cycle" refers to a substituted or unsubstituted monocyclic or polycyclic (e.g., those formed from monocyclic or fused-ring systems), such as substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted cycloynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted polyheteroaryl, having 3 to 30 carbon atoms when geometric constraints permit. The substituted cycloalkyl, cycloalkenyl, cycloynyl, and heterocyclic groups are substituted as defined above for alkyl, alkenyl, ynyl, heterocyclic, aryl, heteroaryl, polyaryl, and polyheteroaryl, respectively.

[0064] As used herein, the term "aralkyl" is an aryl or heteroaryl group having an alkyl, ynyl, or alkenyl group as defined above attached to an aromatic group (such as aryl, heteroaryl, polyaryl, or polyheteroaryl). An example of an aralkyl group is benzyl.

[0065] The terms "alkyloxy" or "alkoxy", "aryloxy" or "aryloxy" are generally described by the formula -OR v The compound represented by R v This includes, but is not limited to, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocyclic alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, phosphonyl, phosphonyl, sulfinyl, silyl, mercapto, amide, and amino. Exemplary alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy, etc. A “lower alkoxy” is an alkoxy group containing 1 to 6 carbon atoms. An “ether” is two functional groups covalently linked by oxygen as defined below. Therefore, the alkyl substituent that makes an alkyl group an ether is or is similar to an alkoxy group, and may be represented by one of the following: -O-alkyl, -O-alkenyl, -O-alkynyl, -O-aryl, -O-heteroaryl, -O-polyaryl, -O-polyheteroaryl, -O-heterocyclic, etc.

[0066] The term "substituted alkoxy" refers to an alkoxy group having one or more hydrogen atoms on one or more carbons of one or more substituted alkoxy backbones. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates, or thiocarbamates), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, oxo, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0067] As used herein, the term "ether" is derived from formula A. 2 OA 1 It means that A 2 and A 1 It may be independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, phosphonium, phosphonyl, sulfinyl, silyl, mercapto, substituted or unsubstituted carbonyl, alkoxy, amide, or amino, as described above.

[0068] As used herein, the term "polyether" is represented by the following formula:

[0069]

[0070] Where A 3 A 2 and A 1 It can be independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, phosphonyl, substituted or unsubstituted carbonyl, alkoxy, amide, or amino, as described above; g can be a positive integer between 1 and 30.

[0071] The term "phenoxy" is recognized in the art and refers to the formula -OR v The compound in which R v Yes (i.e., -O-C6H5). Those skilled in the art will recognize that phenoxy is a species of the aryloxy group.

[0072] The term "substituted phenoxy" refers to a phenoxy group as defined above, having a substituent having one or more hydrogen atoms on one or more carbons of one or more substituted benzene rings. Such substituents include, but are not limited to, halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0073] As may be used interchangeably herein, the terms “aryloxy” and “aryloxy” are represented by -O-aryl or -O-heteroaryl, where aryl and heteroaryl are as defined herein.

[0074] As may be used interchangeably herein, the terms “substituted aryloxy” and “substituted aryloxy” refer to a -O-aryl or -O-heteroaryl group having a substituent on one or more hydrogen atoms on one or more ring atoms of one or more substituted aryl and heteroaryl groups, as defined herein. Such substituents can be any of the substituents mentioned above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0075] As used herein, the term "amino" includes groups.

[0076]

[0077] Wherein, E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, wherein, independent of E, R x R xi and R xiiEach of these groups independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., substituted or unsubstituted alkylaryl group, substituted or unsubstituted arylalkyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphono group, a phosphonyl group, a sulfinyl group, a silyl group, a mercapto group, an amide group, an amino group, or -(CH2). m -R”'; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is 0 or an integer from 1 to 8. The term "quaternary amino" also includes groups in which nitrogen, R x R xi and R xii N connected to them + It consists of heterocyclic or heteroaryl groups having 3 to 14 atoms in a ring structure.

[0078] The terms "amide" or "amide group" are used interchangeably and refer to both "unsubstituted amide group" and "substituted amide group," and are represented by the following general formula:

[0079]

[0080] Wherein, E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, or substituted or unsubstituted heterocyclic group, wherein independently of E, R and R' each independently represent hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclic group, hydroxyl, alkoxy, phosphonium, phosphonyl, sulfinyl, silyl, mercapto, amide, amino, or -(CH2). m-R”', or R and R' together with the N atom they are attached to form a heterocycle having 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is 0 or an integer from 1 to 8. In some forms, when E is oxygen, a carbamate is formed.

[0081] As used herein, "carbonyl" is generally accepted in the art and includes, for example, portions that can be represented by the following general formula:

[0082]

[0083] Where X is a bond, or represents oxygen or sulfur, and R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphine, amide, amino, or -(CH2). m -R” or a pharmaceutically acceptable salt; E” is absent, or E” is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, or substituted or unsubstituted heterocyclic group; R' represents hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclic group, hydroxyl, alkoxy, phosphonium, phosphine, amide, amino, or -(CH2). m-R”; R” represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyhexaaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is 0 or an integer from 1 to 8. When X is oxygen and R is as defined above, this part is also called a carboxyl group. When X is oxygen and R is hydrogen, the formula represents a “carboxylic acid.” When X is oxygen and R’ is hydrogen, the formula represents a “formate ester.” When X is oxygen and R or R’ is not hydrogen, the formula represents an “ester.” Generally, when the oxygen atom in the above formula is replaced by a sulfur atom, the formula represents a “thiocarbonyl.” When X is sulfur and R or R’ is not hydrogen, the formula represents a “thioester.” When X is sulfur and R is hydrogen, the formula represents a “thiocarboxylic acid.” When X is sulfur and R' is hydrogen, the formula represents "thiocarbamate". When X is a bond and R is not hydrogen, the formula represents "ketone". When X is a bond and R is hydrogen, the formula represents "aldehyde".

[0084] The term "substituted carbonyl" refers to R, R', or a group with the following parts:

[0085]

[0086] A carbonyl group as defined above in which one or more hydrogen atoms in the linked group are independently substituted. Such substituents may be any of the substituents described above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0087] The term "carboxyl group" is as defined above for the carbonyl group, and more specifically by formula -R iv COOH is defined, where R iv It is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, or a substituted or unsubstituted heteroaryl.

[0088] The term "substituted carboxyl group" refers to the group in which R... iva carboxyl group as defined above, wherein one or more hydrogen atoms are substituted. Such substituents may be any of the above substituents, for example, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thioformate), alkoxy, phosphonium, phosphino, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g., quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0089] The term "phosphino" is represented by the following formula

[0090]

[0091] wherein E is absent, or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclyl, wherein independently of E, R vi and R vii each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclyl, hydroxyl, alkoxy, phosphonium, phosphino, phosphonyl, sulfinyl, silyl, mercapto, amido, amino, or -(CH2) m -R''', or R vi and R vii together with the P atom to which they are attached form a heterocycle having 3 to 14 atoms in the ring structure; R''' represents hydroxyl, substituted or unsubstituted carbonyl, substituted or unsubstituted aryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, alkoxy, phosphonium, phosphino, amido or amino; m is 0 or an integer from 1 to 8.

[0092] The term "phosphonium" is represented by the following formula

[0093]

[0094] Wherein, E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, wherein, independent of E, R vi R vii and R viii Each of these groups independently represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphonyl, sulfinyl, silyl, mercapto, amide, amino, or -(CH2). m -R”', or R vi R vii and R viii P connected to them + The atoms together form a heterocycle having 3 to 14 atoms in a ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is an integer from 0 to 8.

[0095] The term "phosphonoyl" is represented by the following formula.

[0096]

[0097] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, oxygen, alkoxy, aryloxy, or substituted alkoxy or substituted aryloxy, wherein independent of E, R vi and R viiIndependently, it can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphonyl, sulfinyl, silyl, mercapto, amide, amino, or -(CH2). m -R”', or R vi and R vii Together with the P atoms they are attached to, they form a heterocycle with 3 to 14 atoms in the ring structure; R”' represents hydroxyl, substituted or unsubstituted carbonyl, substituted or unsubstituted aryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, alkoxy, phosphonyl, amide, or amino; m is an integer from 0 to 8.

[0098] The term "substituted phosphonoyl group" indicates that E and R are substituted. vi and R vii Independently substituted phosphonoyl groups. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates, or thiocarbamates), alkoxy, phosphoryl, phosphates, phosphonates, hypophosphonates, amino (e.g., quaternized amino), amides, amidines, imines, cyano, nitro, azide, mercapto, alkylthio, sulfates, sulfonates, aminosulfonyl, sulfonamides, sulfonyl groups, heterocyclic groups, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0099] The term "phosphonyl" is defined as a phosphonyl group in which E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy, as defined above, and independent of E, R vi and R vii Independently, it can be a hydroxyl, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy group, as defined above. When E is oxygen, the phosphoryl group cannot attach to another chemical substance to form, for example, an oxygen-oxygen bond or other unstable bonds as understood by one of ordinary skill in the art. When E, R vi and R viiWhen substituted, the substituents include, but are not limited to, halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof.

[0100] The term "sulfinyl" is represented by the following formula.

[0101]

[0102] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, wherein, independently of E, R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted... Alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphonyl, silyl, mercapto, amide, amino, or -(CH2). m -R”', or E and R together with the S atom to which they are attached, form a heterocycle with 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is 0 or an integer from 1 to 8.

[0103] The term "sulfonyl" is represented by the following formula.

[0104]

[0105] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, wherein, independently of E, R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphine, amide, amino, or -(CH2). m -R”', or E and R together with the S atom to which they are attached, form a heterocycle with 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is 0 or an integer from 1 to 8.

[0106] The term "substituted sulfonyl" refers to a sulfonyl group in which E, R, or both are independently substituted. Such substituents can be any of the substituents listed above, such as halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0107] The term "sulfonic acid" refers to a sulfonyl group as defined above in which R is a hydroxyl group and E is absent or is a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, or substituted or unsubstituted heteroaryl.

[0108] The term "sulfate ester" refers to a sulfonyl group as defined above in which E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy as defined above, and R is independently hydroxyl, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy as defined above. When E is oxygen, the sulfate ester cannot be attached to another chemical substance to form, for example, an oxygen-oxygen bond or other unstable bonds as understood by one of ordinary skill in the art.

[0109] The term "sulfonate" refers to a sulfonyl group as defined above, wherein E is, as defined above, oxygen, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy, and R is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amino, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, -(CH2). m -R”' (R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocyclic ring, an amide group, an amino group, or a polycyclic ring); m is 0 or an integer from 1 to 8. When E is oxygen, the sulfonate ester cannot be attached to another chemical substance to form, for example, an oxygen-oxygen bond or other unstable bonds as understood by those skilled in the art.

[0110] The term "aminosulfonyl" refers to sulfonamides or sulfonamides represented by the following formula:

[0111]

[0112] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted cycloalkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, wherein independently of E, R and R' each independently represent hydrogen, substituted or unsubstituted alkane. Alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxyl, alkoxy, phosphonium, phosphine, amide, amino, or -(CH2). m-R”', or R and R' together with the N atom to which they are attached, constitute a heterocycle having 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonyl group, an amide group, or an amino group; m is an integer from 0 to 8.

[0113] As used herein, the term "silyl" is represented by the formula -SiRR'R" where R, R', and R" can independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted carbonyl, phosphonium, phosphonyl, sulfinyl, mercapto, amide, amino, alkoxy, or oxo, as described above.

[0114] The term "thiol" is used interchangeably and is represented by -SR, where R can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted carbonyl, phosphonium, phosphonyl, amide, amino, alkoxy, oxo, phosphonyl, sulfinyl, or silyl, as described above.

[0115] The term "alkathio" refers to an alkyl group as defined above, having a sulfur group attached to it. The "alkathio" part is represented by -S-alkyl. Representative alkathio groups include methylthio, ethylthio, etc. The term "alkathio" also includes cycloalkyl groups having a sulfur group attached to them.

[0116] The term "substituted alkathio" refers to an alkathio group having one or more hydrogen atoms on one or more carbon atoms of one or more substituted alkathio backbones. Such substituents include, but are not limited to, halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkathio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0117] The term "phenylthio" is recognized in the art and refers to -SC6H5, i.e., a phenyl group bonded to a sulfur atom.

[0118] The term "substituted phenylthio" refers to a phenylthio group as defined above, having hydrogen atoms on one or more carbons of a substituted benzene ring. Such substituents include, but are not limited to, halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0119] "Arylthio" refers to -S-aryl or -S-heteroaryl, where aryl and heteroaryl are as defined herein.

[0120] The term "substituted arylthio" refers to a -S-aryl or -S-heteroaryl group having a substituent having one or more hydrogen atoms on one or more ring atoms that substitute for aryl and heteroaryl rings as defined herein. Such substituents include, but are not limited to, halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphonium, phosphonyl, phosphoryl, phosphate, phosphonate, hypophosphonate, amino (e.g., quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0121] The terms “hydroxyl” and “hydroxyl” are used interchangeably and are represented by -OH.

[0122] The term "oxo" refers to the =O atom bonded to a carbon atom.

[0123] The terms “cyano” and “nitrile” are used interchangeably to refer to -CN.

[0124] The term "nitro" refers to -NO2.

[0125] The term "phosphate" refers to -O-PO3.

[0126] The terms “azide” or “azidation” are used interchangeably to refer to -N3.

[0127] The disclosed compounds and substituents may independently have two or more of the listed groups. For example, if the compound or substituent is a straight-chain alkyl group, one of the hydrogen atoms of the alkyl group may be replaced by a hydroxyl, alkoxy, etc. Depending on the chosen groups, the first group may be incorporated into the second group, or alternatively, the first group may be side-attached (i.e., connected) to the second group. For example, for the phrase "alkyl group containing an ester group," the ester group may be incorporated into the backbone of the alkyl group. Alternatively, the ester may be attached to the backbone of the alkyl group. The nature of the chosen groups will determine whether the first group is inserted into or attached to the second group.

[0128] Compounds and substituents can be substituted independently by substituents as described in the definition of "substitution" above.

[0129] II. Gold (I) Complexes

[0130] Gold(I) complexes capable of catalyzing organic reactions under near-UV and / or visible light have been developed. Typically, the gold(I) complexes disclosed herein comprise diphosphine ligands with functionalized ring structures. Without being bound by any theory, these gold(I) complexes possess empty coordination sites, which can promote substrate binding and radical capture. The electronic and steric properties of the bridging ligands in these gold(I) complexes allow for metal-metal bonding... 3 The [5dσ*6pσ] excited state is reactive in capturing incoming substrate / carbon center radicals and improves light absorption in the visible spectral region.

[0131] These gold (I) complexes possess excellent photochemical reactivity (e.g., strong absorption in near-ultraviolet and / or visible wavelengths, large quenching rate constants, and large radiative attenuation rates), and should be suitable for photoredox catalysis, such as homocoupling of organohalides (e.g., alkyl halides and aryl halides), alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, cyclization of indole, reductive dehalogenation of aryl halides, and / or CH bond cleavage. In particular, these gold (I) complexes can absorb in the near-ultraviolet and / or visible wavelength range, such as from 360 nm to approximately 450 nm or from approximately 380 nm to approximately 450 nm, and therefore can catalyze photoredox reactions under near-ultraviolet and / or visible light. For example, these gold (I) complexes can act as near-ultraviolet and / or visible light-activated carbon-halide cleaving agents under mild reaction conditions (e.g., room temperature).

[0132] These gold (I) complexes exhibit higher photocatalytic activity compared to known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3]. For example, the yield of products from photoinduced organic reactions using one or more of the gold (I) complexes described herein (such as those mentioned above) is higher than the yield of the same products from the same reaction using the same or higher loadings of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3] under the same reaction conditions (e.g., the same amounts of reactants, bases, and solvents, the same wavelength of light, the same temperature, pressure, gas environment, humidity, and reaction time, etc.).

[0133] A. Structure of gold(I) complex

[0134] Gold(I) complexes can have the structure of formula I:

[0135]

[0136] Wherein: (a) m can be 0, 1, or 2 positive charges; (b) n can be an integer between 0 and 2; (c) when present, each occurrence of A' can be an anion; (d) X1 to X4 can be P or N independently; (e) L1 and L2 can be absent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid, phosphoryl, or phosphonyl; (f) CY1 to CY8 can be substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl. (g) R1 to R8 may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto; (h) n1 to n8 (i) Each can be an integer between 0 and 10; (j) Z1 and Z2 can be an integer between 0 and 10; (i) each can be an integer between 0 and 10; (j) each can be an integer between 0 and 10; (i) each can be an integer between 0 and 10; (j) each can be an integer between 0 and 10; (i) each can be an integer between 0 and 10; (ii) each can be an integer between 0 and 10; (iii) each can be an integer between 0 and 10; (iv) each can be an integer between 0 and 10; (v) each can be an integer between 0 and 10; (vi) each can be an integer between 0 and 10; (v) each can be an integer between 0 and 10; (vi) each can be an integer between 0 and 10; (vii) each can be an integer between 0 and 10; (vii) each can be an integer between 0 and 10; (v ... Or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, haloalkyl (e.g., -CF3), phenoxy, aryloxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto or combinations thereof.

[0137] In some forms, when CY1 to CY8 of Formula I are independently substituted or unsubstituted aryl groups, at least one of R1 to R8 is not hydrogen. In some forms of Formula I, at least one of CY1 to CY8 is not an unsubstituted aryl group. In some forms, the gold(I) complexes disclosed herein are not [Au2(μ-dppm)2](Cl)2.

[0138] In some forms, gold (I) complexes can have the structure of formula Ia, formula Ib, or formula Ic:

[0139]

[0140] Wherein: (a) A' in each occurrence can be an anion; (b) X1 to X4 can be P or N independently; (c) L1 and L2 can be absent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide, ether, polyether, thioether, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid, phosphoryl or phosphonyl; (d) CY1 to CY8 can be substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl or substituted or unsubstituted cycloalkynyl; (e) R1 to R8 can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted (i) aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto; (f) n1 to n8 may be independent integers between 0 and 10; (g) each ------ may be independent or be a single bond; (h) Z1 and Z2 may be independent halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonate, sulfonate, phosphate, perchlorate, dicyanophosphate, cyano, nitrate, hydroxyl, oxo, oxalate or carboxylate; (i) Z3 may be a halide (fluoride, chloride, bromide or iodide), oxygen, sulfur, oxalate or carboxylate; (j) substituents may be as defined above for Formula I.

[0141] In some forms of equations I, Ia, Ib, and / or Ic, L1 and L2 can be independent single bonds or R9 and R 10 It can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n9 can be an integer between 1 and 10, 1 and 8, 1 and 6, 1 and 4, 1 and 3, 1 and 2, or 1.

[0142] In some forms of equations I, Ia, Ib and / or Ic, X1 to X4 can be P.

[0143] In some forms of formulas I, Ia, Ib, and / or Ic, CY1 to CY8 can independently be substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted polyheteroaryl. In some forms of formulas I, Ia, Ib, and / or Ic, CY1 to CY8 can independently be:

[0144]

[0145] Among them: (a)R 60 To R 66 (a) can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (b) n60 to n66 can be independently an integer from 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0, or 1; (c) Q1 and Q2 can be independently oxygen, sulfur, NR 67 or CR 68 R 69 And R 67 To R 69 It can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (d) substituents can be as defined above for Formula I. In some forms, R 67 To R 69 It may be hydrogen or a substituted or unsubstituted alkyl group, such as a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C1-C2 alkyl group, an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C3 alkyl group, or an unsubstituted C1-C2 alkyl group.

[0146] In some forms, R 60 To R 66The substituent may be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, fatty alcohol, haloalkyl (e.g., -CF3), amino, or alkoxy; and the substituent may be independently unsubstituted alkyl, unsubstituted alkenyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, oxo, alkoxy, halogen, hydroxyl, haloalkyl (e.g., -CF3), or amino, or a combination thereof.

[0147] In some forms, R 60 To R 66 The substituent may be independently hydrogen, haloalkyl (e.g., -CF3), alkoxy (e.g., -O-alkyl, e.g., -OMe), substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, amino, substituted or unsubstituted polyaryl, hydroxyl, fatty alcohol, substituted or unsubstituted alkyl or unsubstituted alkenyl; and the substituent may be independently unsubstituted alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.), unsubstituted alkenyl (methylene, ethylene, propylene, butene, pentene, hexene, etc.), unsubstituted heterocyclic group, phenyl, unsubstituted polyaryl, alkoxy (e.g., -O-alkyl, e.g., -OMe), halogen, hydroxyl or haloalkyl (e.g., -CF3) or combinations thereof.

[0148] In some forms, gold(I) complexes can have the structure of formula IIa, IIb, or IIc:

[0149] or

[0150]

[0151] Wherein: (a) n10 and n12 can be independently an integer between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, or 1; (b) R1 to R8 can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (c) n1 to n8 can be an integer between 0 and 5 independently; (d) each ------ can be either absent or a single bond independently; (e) Z1 and Z2 can be halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonates, sulfonates, phosphates, perchlorates, dicyanophosphates, cyano groups, nitrates, hydroxyl groups, oxalates, or carboxylates independently; (f) Z3 can be a halide (fluorides, chlorides, bromides or iodides), oxygen, sulfur, oxalates, or carboxylates; (g) each A' can be an anion; and (h) substituents can be as defined in Formula I.

[0152] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, R1 to R8 may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, haloalkyl (e.g. -CF3), oxo, amino or alkoxy.

[0153] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, R1 to R8 may be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo or alkoxy.

[0154] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, R1 to 8 may be independently hydrogen, haloalkyl (e.g. -CF3), alkoxy (e.g. -O-alkyl, e.g. -OMe), substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl group, amino group, substituted or unsubstituted polyaryl group, hydroxyl group, substituted or unsubstituted alkyl group or unsubstituted alkenyl group.

[0155] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, R1 to R8 may independently be hydrogen, hydroxyl, unsubstituted alkyl (e.g., unsubstituted C1-C6 alkyl), unsubstituted alkenyl (e.g., unsubstituted C1-C6 alkenyl), haloalkyl (e.g., -CF3), fatty alcohol, -NR 70 R 71 Substituted or unsubstituted polyaryl groups, substituted or unsubstituted heterocyclic groups, or R 13 and R 14 It can be independently a halogen, hydrogen, hydroxyl, haloalkyl (e.g., -CF3), alkoxy (e.g., -O-alkyl, such as -OMe, etc.), unsubstituted alkenyl, or substituted or unsubstituted alkyl, and n14 can be an integer from 0 to 5, 0 to 4, 0 to 3, 0 to 2, such as 0, 1, or 2, and R 70 and R 71 It can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, amino, alkoxy, or carbonyl. In some forms, R 70 and R 71 It can be independently hydrogen, an unsubstituted alkyl group (e.g., an unsubstituted C1-C6 alkyl group), or an unsubstituted phenyl group. When R1 to R8 are all trifluoromethyl and n14 is 2, at least one of R1 to R8 is not In some forms, R 13 and R 14 Can be independently of unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl, such as methyl, ethyl, propyl, butyl (e.g., n-butyl or tert-butyl), pentyl, hexyl, etc. When any one of R1 to R8 in formulas I, Ia, Ib, Ic, IIa, IIb, and / or IIc is a substituted or unsubstituted heterocyclic or polyaryl group, the heterocyclic or polyaryl group may have the following structure:

[0156]

[0157] Among them, CY9 to CY 12 It can be an aryl group that is absent, substituted, or unsubstituted; and Q3 to Q7 can be oxygen, sulfur, or NR independently. 72 or CR 73 R 74 And R 72 To R 74It can independently be absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; the substituent can be as defined above for Formula I. In some forms, R 72 To R 74 It can be independently absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, amino, alkoxy, or carbonyl. In some forms, R 72 To R 74 It can be independently absent, hydrogen-rich, or substituted or unsubstituted alkyl groups. In some forms, R 72 To R 74 It can exist independently or be hydrogen.

[0158] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, Z1 to Z3 can be halides independently, such as fluorides, chlorides, bromides or iodides, for example chlorides or bromides.

[0159] In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, each occurrence of A' may be a hydride, oxide, fluoride, sulfide, chloride, bromide, iodide, hydrogen phosphate, dihydrogen phosphate, hexafluorophosphate, trifluoromethanesulfonate, sulfate, nitrate, hydrogen sulfate, nitrite, thiosulfate, sulfite, chlorate, bromate, chlorite, hypochlorite, hypobromate, carbonate, chromate, bicarbonate, dichromate, perchlorate, acetate, formate, cyanide, amine, cyanate, peroxide, thiocyanate, oxalate, hydroxide or permanganate. In some forms of formulas I, Ia, Ib, Ic, IIa, IIb and / or IIc, each occurrence of A' can be a halide (e.g., fluoride, bromide, iodide), perchlorate, hydrogen phosphate, dihydrogen phosphate, sulfate, nitrate, hydrogen sulfate, nitrite, chlorate, bromate, chlorite, hypochlorite or hypobromate, such as a halide or perchlorate.

[0160] For any one of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, a haloalkyl (e.g., -CF3), cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0161] For any one of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the substituent may be independently an unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted heterocyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted polyaryl, unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, haloalkyl (e.g., -CF3), cyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0162] For any one of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the substituent may be an unsubstituted alkyl, an unsubstituted alkenyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, an oxo, an alkoxy, a halogen, a hydroxyl, a haloalkyl (e.g., -CF3), an amino, a cyano, or a carbonyl, or a combination thereof.

[0163] For any one of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the substituent may be independently an unsubstituted alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.), an unsubstituted alkenyl group (methylene, ethylene, propylene, butylene, pentylene, hexylene, etc.), an unsubstituted heterocyclic group, a phenyl group, an unsubstituted polyaryl group, an alkoxy group (e.g., -O-alkyl, such as -OMe, etc.), a halogen, a hydroxyl group, or a haloalkyl group (e.g., -CF3), or a combination thereof.

[0164] For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the alkyl group may be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group (monocyclic or polycyclic). The terms "cyclic alkyl group" and "cycloalkyl group" are used interchangeably herein. Exemplary alkyl groups include straight-chain C1-C1 alkyl groups. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10 Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10 Alkyl, C1-C9 alkyl, C1-C8, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl. Cyclic alkyl groups can be polycyclic alkyl groups, such as C4-C6 alkyl. 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C 18 Polycyclic alkyl, C4-C 16 Polycyclic alkyl, C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0165] For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the alkenyl group may be a straight-chain alkenyl, a branched alkenyl, or a cyclic alkenyl (monocyclic or polycyclic). The terms "cyclic alkenyl" and "cycloalkenyl" are used interchangeably herein. Exemplary alkenyl groups include straight-chain C2-C... 30 Alkenyl, branched C4-C 30 Alkenyl, cyclic C3-C 30 Alkenyl, straight-chain C2-C 20 Alkenyl, branched C4-C 20 Alkenyl, cyclic C3-C 20 Alkenyl, straight-chain C2-C 10 Alkenyl, branched C4-C 10 Alkenyl, cyclic C3-C 10 Alkenyl, straight-chain C2-C6 alkenyl, branched-chain C4-C6 alkenyl, cyclic C3-C6 alkenyl, straight-chain C2-C4 alkenyl, cyclic C3-C4 alkenyl, such as straight-chain C2-C6 alkenyl. 10Alkenyl, C2-C9 alkenyl, C2-C8 alkenyl, C2-C7 alkenyl, C2-C6 alkenyl, C2-C5 alkenyl, C2-C4 alkenyl, C2-C3 alkenyl, C2 alkenyl; branched C3-C9 alkenyl, C3-C9 alkenyl, C3-C8 alkenyl, C3-C7 alkenyl, C3-C6 alkenyl, C3-C5 alkenyl, C3-C4 alkenyl; or cyclic C3-C9 alkenyl, C3-C9 alkenyl, C3-C8 alkenyl, C3-C7 alkenyl, C3-C6 alkenyl, C3-C5 alkenyl, C3-C4 alkenyl. Cyclic alkenyl groups can be polycyclic alkenyl groups, such as C4-C6 alkenyl. 30 Polycyclic alkenyl, C4-C 25 Polycyclic alkenyl, C4-C 20 Polycyclic alkenyl, C4-C 18 Polycyclic alkenyl, C4-C 16 Polycyclic alkenyl, C4-C 15 Polycyclic alkenyl, C4-C 14 Polycyclic alkenyl, C4-C 13 Polycyclic alkenyl, C4-C 12 Polycyclic alkenyl, C4-C 10 Polycyclic alkenyl, C4-C9 polycyclic alkenyl, C4-C8 polycyclic alkenyl, C4-C7 polycyclic alkenyl, C4-C6 polycyclic alkenyl or C4-C5 polycyclic alkenyl.

[0166] For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the alkynyl group may be a straight-chain alkynyl, a branched-chain alkynyl, or a cyclic alkynyl (monocyclic or polycyclic). The terms "cyclic alkynyl" and "cycloalkynyl" are used interchangeably herein. Exemplary alkynyl groups include straight-chain C2-C... 30 Alkyne group, branched C4-C 30 Alkyne group, cyclic C3-C 30 Alkyne group, straight-chain C2-C 20 Alkyne group, branched C4-C 20 Alkyne group, cyclic C3-C 20 Alkyne group, straight-chain C2-C 10 Alkyne group, branched C4-C 10 Alkyne group, cyclic C3-C 10 Alkynyl, straight-chain C2-C6 alkynyl, branched-chain C4-C6 alkynyl, cyclic C3-C6 alkynyl, straight-chain C2-C4 alkynyl, cyclic C3-C4 alkynyl, such as straight-chain C2-C 10The alkynyl group can be C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, or C2-C4. It can also be branched, including C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 alkynyl groups, or cyclic alkynyl groups such as C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 alkynyl groups. Cyclic alkynyl groups can be polycyclic, such as C4-C6. 30 Polycyclic alkyne group, C4-C 25 Polycyclic alkyne group, C4-C 20 Polycyclic alkyne group, C4-C 18 Polycyclic alkyne group, C4-C 16 Polycyclic alkyne group, C4-C 15 Polycyclic alkyne group, C4-C 14 Polycyclic alkyne group, C4-C 13 Polycyclic alkyne group, C4-C 12 Polycyclic alkyne group, C4-C 10 Polycyclic alkyne, C4-C9 polycyclic alkyne, C4-C8 polycyclic alkyne, C4-C7 polycyclic alkyne, C4-C6 polycyclic alkyne, or C4-C5 polycyclic alkyne.

[0167] It should be understood that any exemplary alkyl, alkenyl, and ynyl group can be heteroalkyl, heteroalkenyl, and heteroynyl, respectively. For example, an alkyl group can be a straight-chain C2-C group. 30 Heteroalkyl, branched C4-C 30 Heteroalkyl, cyclic C3-C 30 Heteroalkyl (i.e., monocyclic or polycyclic heteroalkyl), straight-chain C2-C 20 Heteroalkyl, branched C4-C 20 Heteroalkyl, cyclic C3-C 20 Heteroalkyl, straight-chain C2-C 10 Heteroalkyl, branched C4-C 10 Heteroalkyl, cyclic C3-C 10 Heteroalkyl, straight-chain C2-C6 heteroalkyl, branched-chain C4-C6 heteroalkyl, cyclic C3-C6 heteroalkyl, straight-chain C2-C4 heteroalkyl, cyclic C3-C4 heteroalkyl, such as straight-chain C2-C6 heteroalkyl. 10Heteroalkyl groups include C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, and C2 heteroalkyl groups; branched C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 heteroalkyl groups; or cyclic C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 heteroalkyl groups. Cyclic heteroalkyl groups can be polycyclic, such as C4-C6. 30 Polycyclic heteroalkyl, C4-C 25 Polycyclic heteroalkyl, C4-C 20 Polycyclic heteroalkyl, C4-C 18 Polycyclic heteroalkyl, C4-C 16 Polycyclic heteroalkyl, C4-C 15 Polycyclic heteroalkyl, C4-C 14 Polycyclic heteroalkyl, C4-C 13 Polycyclic heteroalkyl, C4-C 12 Polycyclic heteroalkyl, C4-C 10 Polycyclic heteroalkyl, C4-C9 polycyclic heteroalkyl, C4-C8 polycyclic heteroalkyl, C4-C7 polycyclic heteroalkyl, C4-C6 polycyclic heteroalkyl or C4-C5 polycyclic heteroalkyl.

[0168] For any one of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the alkenyl group can be a straight-chain C2-C. 30 Heteroalkenyl, branched C4-C 30 Heteroalkenyl, cyclic C3-C 30 Heterene groups (i.e., monocyclic or polycyclic heteroene groups), straight-chain C2-C 20 Heteroalkenyl, branched C4-C 20 Heteroalkenyl, cyclic C3-C 20 Heteroalkenyl, straight-chain C2-C 10 Heteroalkenyl, branched C4-C 10 Heteroalkenyl, cyclic C3-C 10 heteroalkenyl, straight-chain C2-C6 heteroalkenyl, branched-chain C4-C6 heteroalkenyl, cyclic C3-C6 heteroalkenyl, straight-chain C2-C4 heteroalkenyl, cyclic C3-C4 heteroalkenyl, such as straight-chain C2-C6 heteroalkenyl. 10Heterenyl groups include C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, and C2-C5 heteroenyl groups; branched C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 heteroenyl groups; and cyclic C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4 heteroenyl groups. Cyclic heteroenyl groups can be polycyclic, such as C4-C5. 30 Polycyclic heteroenes, C4-C 25 Polycyclic heteroenes, C4-C 20 Polycyclic heteroenes, C4-C 18 Polycyclic heteroenes, C4-C 16 Polycyclic heteroenes, C4-C 15 Polycyclic heteroenes, C4-C 14 Polycyclic heteroenes, C4-C 13 Polycyclic heteroenes, C4-C 12 Polycyclic heteroenes, C4-C 10 Polycyclic heteroene, C4-C9 polycyclic heteroene, C4-C8 polycyclic heteroene, C4-C7 polycyclic heteroene, C4-C6 polycyclic heteroene, or C4-C5 polycyclic heteroene.

[0169] For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the alkynyl group can be a straight-chain C2-C group. 30 Heterynyl group, branched C4-C 30 Heterynyl, cyclic C3-C 30 heteroyne group (i.e., monocyclic or polycyclic heteroyne group), straight-chain C2-C 20 Heterynyl group, branched C4-C 20 Heterynyl, cyclic C3-C 20 Heteryne group, straight-chain C2-C 10 Heterynyl group, branched C4-C 10 Heterynyl, cyclic C3-C 10 Xyrynyl, straight-chain C2-C6 xyrynyl, branched-chain C4-C6 xyrynyl, cyclic C3-C6 xyrynyl, straight-chain C2-C4 xyrynyl, cyclic C3-C4 xyrynyl, such as straight-chain C2-C 10The following are types of heteroynyl groups: C2-C9 heteroynyl, C2-C8 heteroynyl, C2-C7 heteroynyl, C2-C6 heteroynyl, C2-C5 heteroynyl, C2-C4 heteroynyl, C2-C3 heteroynyl, C2 heteroynyl; branched C3-C9 heteroynyl, C3-C9 heteroynyl, C3-C8 heteroynyl, C3-C7 heteroynyl, C3-C6 heteroynyl, C3-C5 heteroynyl, C3-C4 heteroynyl; or cyclic C3-C9 heteroynyl, C3-C9 heteroynyl, C3-C8 heteroynyl, C3-C7 heteroynyl, C3-C6 heteroynyl, C3-C5 heteroynyl, C3-C4 heteroynyl. Cyclic heteroynyl groups can be polycyclic, such as C4-C6. 30 Polycyclic heteroyne group, C4-C 25 Polycyclic heteroyne group, C4-C 20 Polycyclic heteroyne group, C4-C 18 Polycyclic heteroyne group, C4-C 16 Polycyclic heteroyne group, C4-C 15 Polycyclic heteroyne group, C4-C 14 Polycyclic heteroyne group, C4-C 13 Polycyclic heteroyne group, C4-C 12 Polycyclic heteroyne group, C4-C 10 Polycyclic heteroyne group, C4-C9 polycyclic heteroyne group, C4-C8 polycyclic heteroyne group, C4-C7 polycyclic heteroyne group, C4-C6 polycyclic heteroyne group, or C4-C5 polycyclic heteroyne group.

[0170] For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the aryl group can be C5-C. 30 Aryl, C5-C 20 Aryl, C5-C 12 Aryl, C5-C 11 Aryl, C5-C9 aryl, C6-C 20 Aryl, C6-C 12 Aryl, C6-C 11 Aryl or C6-C9 aryl. It should be understood that aryl can be heteroaryl, such as C5-C9. 30 heteroaryl, C5-C 20 heteroaryl, C5-C 12 heteroaryl, C5-C 11 heteroaryl, C5-C9 heteroaryl, C6-C 30 heteroaryl, C6-C 20 heteroaryl, C6-C 12 heteroaryl, C6-C 11 Heteroaryl or C6-C9 heteroaryl. For any of formulas I, Ia, Ib, Ic, IIa, IIb, and IIc, the polyaryl group can be C6-C9. 10 -C 30 Polyaryl, C10 -C 20 Polyaryl, C 10 -C 12 Polyaryl, C 10 -C 11 Polyaryl or C 12 -C 20 Polyaryl. It should be understood that aryl groups can be poly-heteroaryl, such as C. 10 -C 30 Polyarylene, C 10 -C 20 Polyarylene, C 10 -C 12 Polyarylene, C 10 -C 11 Polyarylene or C 12 -C 20 Multi-aryl aromatics.

[0171] In some forms, the gold(I) complexes disclosed herein are neither [Au2(μ-dppm)2](Cl)2 having the 1a structure nor [Au2(μ-dppm)2](ClO4)2 having the 1b structure:

[0172]

[0173] Gold (I) complexes may contain one or more chiral centers or may otherwise exist as multiple stereoisomers. These may be pure (single) stereoisomers or mixtures of stereoisomers, such as enantiomers, diastereomers, and mixtures of enantiomers or diastereomers in excess. These compounds can exist in the form of geometric isomers. Therefore, it should be understood that the present invention includes pure geometric isomers or mixtures of geometric isomers.

[0174] 1. Exemplary gold (I) complexes

[0175] An example gold (I) complex is shown below.

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] B. Properties of gold(I) complexes

[0182] The gold(I) complexes disclosed herein possess excellent photochemical reactivity suitable for photo-redox catalysis (e.g., strong absorption in near-ultraviolet and / or visible wavelengths, large quenching rate constants, large radiative attenuation rates, etc.). In particular, the gold(I) complexes disclosed herein can absorb in the near-ultraviolet and / or visible wavelength range, for example, from about 360 nm to about 450 nm or from about 380 nm to about 450 nm, and therefore can catalyze photo-redox reactions under near-ultraviolet and / or visible light.

[0183] The photochemical reactivity of the gold(I) complexes disclosed herein can be determined by absorption wavelength, extinction coefficient (“ε”), and radiative attenuation rate (“k”). r ), diffusion-corrected bimolecular quenching rate constant ("k") q '”) and / or reduction potential (“E”) c The absorption wavelengths, ε, and k-values ​​of these gold (I) complexes were measured to evaluate them. r k q 'and E c The techniques are known. For example, the absorption wavelength, ε, and k can be obtained by measuring the absorption and / or emission spectra and / or emission lifetimes of the gold(I) complexes disclosed herein. r For example, the absorption wavelength of the disclosed gold(I) complex in solution or as a powder can be directly obtained by absolute measurement using a UV-Vis spectrophotometer (such as the HP 8453 UV-Vis spectrophotometer).

[0184] For example, the ε of the disclosed gold(I) complex can be obtained based on measured absorption spectra. For instance, ε is obtained using the equation ε = A / (c × l), where A is the measured absorbance, c is the concentration of the gold(I) complex in a solvent (e.g., acetonitrile or N,N-dimethylformamide or combinations thereof), and l is the path length of the solution being measured, which is 1 cm. In these measurements, the concentration of the gold(I) complex can be approximately 5 × 10⁻⁶. -6 M to approximately 3 × 10 -5 Within the range of M.

[0185] For example, the disclosed gold(I) complex k r Equation k can be used r =Φ / τ, where Φ is the emission quantum yield and τ is the emission lifetime. The emission quantum yield can be obtained using, for example, [Ru(bpy)3](PF6)2 in degassed acetonitrile as a standard (Φ = 0.062) or quinine sulfate in 1N H2SO4 as a standard (Φ = 0.546). The emission lifetime can be obtained by: (1) measuring the emission intensity with an oscilloscope to obtain the current intensity (I(t)) as a function of time; (2) by using the equation I(t) = A + B × (e-t / τ The initial current and the current measured at time t in equation (1) are fitted to obtain the value of τ.

[0186] For example, the disclosed gold(I) complex k q The emission lifetime τ of the gold (I) complex in the presence of different concentrations of quencher can be obtained by the following methods: (1) measuring the emission lifetime τ of the gold (I) complex in the presence of different concentrations of quencher; (2) fitting the τ obtained at different quencher concentrations with equation (1) to obtain k. q Value, where [Q] is the quencher concentration, and τ0 is the emission lifetime of the gold (I) complex in the absence of quencher; (3) Fit k in equation (2) q The value of kq' is obtained by taking k. D =1.0×10 10 M -1 s -1 (This is the diffusion-limiting rate constant in acetonitrile.)

[0187] τ0 / τ=1+kq[τ0][Q] Equation (1)

[0188] (k q ') -1 =k q -1 -k D -1 Equation (2)

[0189] Suitable for measuring the k of the gold(I) complexes disclosed above. q Examples of quenchers include, but are not limited to, pyridinium salts and neutral organic compounds, such as those described in Table 2 of the following examples, 1,4-cyclohexadiene, benzyl alcohol, and 1-phenylethanol.

[0190] The disclosed gold(I) complex E c Measurements can be taken using voltammetry methods, such as cyclic voltammetry, linear sweep voltammetry, or pulse voltammetry (e.g., differential pulse voltammetry, square wave voltammetry, etc.).

[0191] In some forms, the gold (I) complexes disclosed herein, in solution or as powder, can absorb light of the following wavelengths: up to 520 nm, up to 500 nm, up to 480 nm, up to 450 nm, up to 420 nm, about 250 nm to about 520 nm, about 250 nm to about 500 nm, about 250 nm to about 480 nm, about 250 nm to about 450 nm, about 250 nm to about 420 nm, about 280 nm to about 520 nm, about 280 nm to about 500 nm, about 280 nm to about 480 nm, about 280 nm to about 450 nm, about 280 nm to about 420 nm, about 300 nm to about 520 nm, about 300 nm to about 500 nm, about 300 nm to about 480 nm, about 300 nm to about 450 nm, about 300 nm to about 420 nm, about 320 nm m to about 520 nm, about 320 nm to about 500 nm, about 320 nm to about 480 nm, about 320 nm to about 450 nm, about 320 nm to about 420 nm, about 350 nm to about 520 nm, about 350 nm to about 500 nm, about 350 nm to about 480 nm, about 350 nm to about 450 nm, about 350 nm to about 420 nm, about 360 nm to about 520 nm, about 360 nm to about 500 nm, about 360 nm to about 480 nm, about 360 nm to about 450 nm, about 360 nm to about 420 nm, about 380 nm to about 520 nm, about 380 nm to about 500 nm, about 380 nm to about 480 nm, about 380 nm to about 450 nm, or about 380 nm to about 420 nm, for example, determined using the absorption spectrum of a gold (I) complex.

[0192] In some forms, the gold(I) complexes disclosed herein may have an extinction coefficient (“ε”) of at least 0.1 × 10⁻⁶ in solutions with wavelengths > 250 nm or as powders. 4 M -1 cm -1 At least 0.5 × 10 4 M -1 cm -1 At least 1.0 × 10 4 M -1 cm -1 At least 2.0 × 10 4 M -1 cm -1 At least 3.0 × 10 4 M -1 cm -1 At least 5.0 × 10 4 M -1 cm -1 At least 8.0 × 10 4 M-1 cm -1 Or at least 10.0 × 10 4 M -1 cm -1 For example, as described above, the absorption spectrum of the gold(I) complex was used to determine this.

[0193] In some forms, the gold(I) complexes disclosed herein, in solution or as powder, can exhibit the following radiation attenuation rates (“k”). r "): At least 0.45 × 10 4 s -1 At least 0.80×10 4 s -1 At least 1.00 × 10 4 s -1 At least 2.00 × 10 4 s -1 At least 4.00 × 10 4 s -1 At least 8.00×10 4 s -1 At least 1.00 × 10 5 s -1 At least 1.50 × 10 5 s -1 At least 2.00 × 10 5 s -1 At least 2.50 × 10 5 s -1 Or at least 2.80 × 10 5 s -1 For example, approximately 2.95 × 10 5 s -1 For example, the emission quantum yield and emission lifetime were determined using gold (I) complexes as described above.

[0194] In some forms, the gold(I) complexes disclosed herein can possess the following diffusion-corrected bimolecular quenching rate constant (“k q' "): At least 3.5 × 10 5 M -1 s -1 At least 5.0 × 10 5 M -1 s -1 At least 1.0 × 10 6 M -1 s -1 At least 5.0 × 10 6 M -1 s -1 At least 1.0 × 10 7 M -1 s -1At least 5.0 × 10 7 M -1 s -1 At least 1.0 × 10 8 M -1 s -1 At least 3.5 × 10 8 M -1 s -1 At least 5.0 × 10 8 M -1 s -1 At least 8.0 × 10 8 M -1 s -1 Or at least 1.0 × 10 9 M -1 s -1 For example, at approximately 3.5 × 10 8 M -1 s -1 To approximately 1.5 × 10 9 M -1 s -1 Within a range, such as that determined using a quencher as described above.

[0195] In some forms, the gold (I) complexes disclosed herein may have reduction potentials relative to a saturated calomel electrode (“SCE”) of less than -1.46 V, less than -1.50 V, less than -1.55 V, or less than -1.60 V, for example, a reduction potential of less than -1.50 V relative to the SCE, which are determined by appropriate methods, such as cyclic voltammetry.

[0196] In some forms, the gold(I) complexes disclosed herein may have absorption wavelengths, ε, and k-values ​​within any of the ranges described above. r k q 'and / or E c For example, gold(I) complexes, in solution or as powder, can absorb light at wavelengths up to 520 nm, up to 480 nm, up to 450 nm, about 280 nm to about 520 nm, about 280 nm to about 480 nm, about 280 nm to about 450 nm, about 360 nm to about 520 nm, about 360 nm to about 480 nm, about 360 nm to about 450 nm, about 380 nm to about 520 nm, about 380 nm to about 480 nm, or about 380 nm to about 450 nm, as determined using the absorption spectrum of the gold(I) complex; the gold(I) complex, in solution or as powder, has a light intensity of at least 1.0 × 10⁻⁶ nm. 4 M -1 cm -1The ε, as determined using the absorption spectrum of the gold(I) complex; the gold(I) complex in solution or as a powder has a ε of at least 2.50 × 10⁻⁶. 5 s -1 k r The emission quantum yield and emission lifetime, as determined using gold (I) complexes, are at least 1.0 × 10⁻⁶. 8 s -1 k q ', as determined using a quencher; and / or having an E value less than -1.46V, less than -1.50V, less than -1.55V, or less than -1.60V relative to SCE. c For example, determined by the cyclic voltammetry method.

[0197] Suitable for measuring the absorption wavelength, ε, and k of gold(I) complexes. r k q 'and / or E c Exemplary solutions include those containing organic solvents. Suitable exemplary organic solvents for forming the measurement solution include, but are not limited to, acetonitrile, methylcyclopropane, dichloromethane, and toluene, and combinations thereof. Optionally, the absorption wavelength, ε, and kJ of the gold (I) complex are used for measurement. r k q 'and / or E c The solution is degassed using an inert gas (such as nitrogen, argon, or helium, or a combination thereof) or by a freeze-pump-thaw cycle.

[0198] III. Preparation Method

[0199] The gold(I) complexes and ligands forming the gold(I) complexes described herein can be synthesized using methods known in the field of organic chemical synthesis. The target gold(I) complex can be synthesized by reacting a corresponding ligand (optionally more than one corresponding ligand) with a gold precursor in a suitable solvent. Exemplary solvents include organic solvents, such as dichloromethane. The corresponding ligands can be prepared using methods known in the art, such as those described in the examples. The reaction solution containing one or more corresponding ligands and a gold precursor can be stirred at room temperature and optionally under an inert gas atmosphere (such as nitrogen) for a suitable time to form a product containing the target gold(I) complex. The product containing the target gold(I) complex can be purified and optionally recrystallized to provide the target gold(I) complex. More specific reagents, reaction conditions, and formed gold(I) complexes are described in the examples.

[0200] IV. Usage Method

[0201] The gold (I) complexes disclosed herein are suitable for photoredox catalysis, such as photoinduced organic reactions, including homocoupling of organohalides (e.g., alkyl halides and aryl halides), alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, cyclization of indole, reductive dehalogenation of aryl halides, and / or CH bond cleavage. In particular, these gold (I) complexes absorb light in the near-ultraviolet and / or visible wavelength range, for example, from about 360 nm to about 450 nm or from about 380 nm to about 450 nm, and therefore can catalyze photoredox reactions under near-ultraviolet and / or visible light.

[0202] Typically, methods for catalyzing organic reactions using one or more gold (I) complexes disclosed herein include: (i) exposing the reaction mixture to light at a certain temperature for a period of time sufficient to form a product. Typically, the wavelength range of the light used to induce the organic reaction is about 350 nm to about 450 nm, about 360 nm to about 450 nm, about 370 nm to about 450 nm, about 380 nm to about 450 nm, about 390 nm to about 450 nm, about 400 nm to about 450 nm, or about 405 nm to about 450 nm, such as about 405 nm or about 445 nm.

[0203] The reaction mixture may contain reactants (optionally more than one reactant), a solvent, and one or more gold (I) complexes, wherein at least one of the reactants is a substrate. The term "substrate" refers to a reactant in the reaction mixture that is transformed in the chemical reaction. Optionally, the reaction mixture may further contain a suitable base, such as Et3N, iPr2NMe, iPr2NEt, 2,4,6-trimethylpyridine, imidazole, potassium carbonate, or sodium carbonate, or combinations thereof. Without being bound by any theory, the base in the reaction mixture may act as an electron donor to provide electrons to the gold complex and / or to neutralize hydrogen halides generated during the reaction. For example, the base in the reaction mixture may: (1) provide electrons to the gold (I) complex upon photoexcitation (i.e., reduction quenching); (2) provide electrons to any gold (II) complex generated during the reaction to regenerate the gold (I) complex; and / or (3) neutralize hydrogen halides generated during the reaction.

[0204] Optionally, the method disclosed herein further includes the step of mixing reactants (optionally more than one reactant) with one or more gold (I) complexes and optional bases in a suitable solvent prior to step (i) to form a reaction mixture.

[0205] Exemplary solvents suitable for forming the reaction mixture include those containing organic solvents. Exemplary organic solvents suitable for forming the reaction mixture include, but are not limited to, acetonitrile and alcohols or combinations thereof. For example, the organic solvent for forming the reaction mixture is acetonitrile or a mixture of acetonitrile and alcohols, such as a mixture of acetonitrile and methanol, a mixture of acetonitrile and ethanol, or a mixture of acetonitrile, methanol, and ethanol, etc. When two or more solvents are used to form the reaction mixture, the volume ratio between the solvents depends on the solubility of the particular reactant. For example, when two solvents (i.e., a first solvent and a second solvent) are used to form the reaction mixture, the volume ratio between the first solvent and the second solvent can be in the range of: 1:100 to 100:1, 1:50 to 50:1, or 1:10 to 10:1, such as about 1:100, about 1:50, about 1:20, about 1:10, about 1:5, about 1:2, about 1:1, about 100:1, about 50:1, about 20:1, about 10:1, or about 5:1, etc.

[0206] Typically, the total amount of one or more gold (I) complexes in the reaction mixture can be up to 10 mol%, up to 5 mol%, up to 2 mol%, at least 0.05 mol%, at least 0.1 mol%, about 0.05 mol% to about 10 mol%, about 0.05 mol% to about 5 mol%, about 0.05 mol% to about 2 mol%, about 0.05 mol% to about 1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.1 mol% to about 10 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 2 mol%, about 0.1 mol% to about 1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.5 mol% to about 10 mol%, about 0.5 mol% to about 5 mol%, about 0.5 mol% to about 2 mol%, or about 0.5 mol% to about 1 mol%. The total amount of one or more gold (I) complexes in the reaction mixture can be calculated using the following formula: mol% of one or more gold complexes = [(sum of the moles of one or more gold complexes) / (sum of the moles of the substrate)] × 100%.

[0207] The reaction conditions for carrying out organic reactions, such as reaction temperature, time, gas environment, and stirring, depend on the specific type of reaction. For example, organic reactions catalyzed by one or more gold (I) complexes disclosed herein may be carried out at room temperature (i.e., 20°C to 22°C at 1 atm) for a time of about 2 hours to about 20 hours, about 4 hours to about 16 hours, about 4 hours to about 14 hours, or about 6 hours to about 12 hours, such as about 6 hours or about 12 hours, and optionally in an inert gas environment, such as nitrogen, helium, or argon, and / or under stirring.

[0208] Typically, the products formed by organic reactions catalyzed by one or more gold (I) complexes disclosed herein can have yields of at least 12%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, up to 99%, up to 98%, up to 95%. %, about 15% to about 99%, about 20% to about 99%, about 40% to about 99%, about 50% to about 99%, about 15% to about 95%, about 20% to about 99%, about 40% to about 95%, about 50% to about 95%, about 15% to about 90%, about 20% to about 90%, about 40% to about 90%, about 50% to about 90%, about 15% to about 80%, about 20% to about 80%, about 40% to about 80%, or about 50% to about 80%. The yield of the product can be calculated using the following formula: Product yield = (number of moles of product obtained experimentally) / (number of moles of product theoretically) × 100%. The number of moles of product obtained experimentally can be determined using known methods, such as using NMR with a known amount of internal standard (e.g., 1 H NMR, 13 C NMR, 19 F NMR and / or 31 Determined by P NMR spectroscopy.

[0209] The gold (I) complexes disclosed herein exhibit higher photocatalytic activity compared to known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3]. For example, the yield of products from photoinduced organic reactions using one or more of the gold (I) complexes described herein (such as those mentioned above) is higher than the yield of the same products from the same reactions under the same reaction conditions using the same or higher loadings of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3] compared to the loadings of the gold (I) complexes disclosed herein. The term "under the same reaction conditions" means that the reaction catalyzed by each of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2 and [fac-Ir(ppy)3] is carried out under the following conditions: using the same amount of reactants, the same base (if any), the same solvent, under the same wavelength of light, at the same temperature, at the same pressure, under the same gaseous environment, at the same humidity, at the same time, etc.

[0210] A. Homocoupling of catalytic organohalides

[0211] In some forms, one or more gold (I) complexes can be used to catalyze the homocoupling of organohalides. The method may include exposing the reaction mixture to light at a temperature for a time sufficient to form a product. The light used to induce the homocoupling of the organohalides may have a wavelength in the range of about 380 nm to about 450 nm or about 400 nm to about 450 nm (e.g., about 405 nm).

[0212] The reaction mixture may contain an organohalide (such as an alkyl halide or an aryl halide, optionally more than one organohalide), a solvent, and one or more gold (I) complexes disclosed herein, wherein the organohalide is a substrate. In some forms, the reaction mixture may further contain a suitable base, such as Et3N, iPr2NMe, iPr2NEt, 2,4,6-trimethylpyridine, imidazole, potassium carbonate or sodium carbonate, or combinations thereof.

[0213] Typically, the total amount of one or more gold (I) complexes in the reaction mixture used for the homologous coupling of organohalides can range from about 0.1 mol% to about 5 mol%, about 0.5 mol% to about 5 mol%, or about 1 mol% to about 5 mol%, such as about 1 mol%, about 2 mol%, or about 5 mol%. The total amount of one or more gold (I) complexes in the reaction mixture used for the homologous coupling of organohalides can be calculated using the following formula: mol% of gold complexes = [(sum of the moles of one or more gold complexes) / (sum of the moles of one or more organohalides)] × 100%.

[0214] Optionally, the method disclosed herein for catalytic homologous coupling of organohalides further includes the step of mixing one or more organohalides with one or more gold (I) complexes and optionally a base in a suitable solvent to form a reaction mixture prior to the reaction.

[0215] Exemplary solvents suitable for forming reaction mixtures containing one or more organohalides and one or more gold (I) complexes and optionally a base include, but are not limited to, acetonitrile, methanol, ethanol, or N,N-dimethylformamide or mixtures thereof, such as a mixture of acetonitrile and methanol. When a mixture of two solvents is used to form the reaction mixture, such as a mixture of acetonitrile and methanol, the volume ratio between the first and second solvents, such as the volume ratio between acetonitrile and methanol, may be in the range of about 1:5 to 5:1, such as about 1:1.

[0216] Homologous coupling reactions of organohalides using one or more gold (I) complexes disclosed herein as photocatalysts can be carried out at room temperature for a time of about 2 hours to about 20 hours, about 4 hours to about 16 hours, or about 6 hours to about 14 hours, such as about 12 hours.

[0217] 1. Reactants

[0218] In some forms, the organohalides contained in the reaction mixture may have the structure of Formula III:

[0219]

[0220] Wherein: (a) A1' may be a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl, or a substituted or unsubstituted heterocyclic group; (b) L3 may be a bond or R 15 and R 16 Independently, it can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto, and n16 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.; (c) Z4 can be a halogen, such as fluorine, chlorine or bromine, etc. (d) The substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyhexaaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0221] 2. Products

[0222] In some forms, the products formed by homologous coupling of organohalides of formula III catalyzed by one or more gold (I) complexes disclosed herein can have the structure of formula IV:

[0223]

[0224] Wherein A1' and L3 can be defined as in Formula III above. In some forms, homocoupling of an organohalide of Formula III catalyzed by one or more gold (I) complexes disclosed herein can form two products, wherein the first product has the structure of Formula IV (also referred to herein as the homocoupling product) and the second product has the structure of Formula IV' (also referred to herein as the hydrodehalogenation product):

[0225]

[0226] A1' and L3 can be defined as in Formula III above. The ratio of homologous coupling product to hydrogenation dehalogenation product depends on the specific reaction conditions.

[0227] In some forms of Formula III, Formula IV and / or Formula IV', A1' may be a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted polyheteroaryl.

[0228] In some forms of Formula III, Formula IV and / or Formula IV', the substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0229] In some forms of Formula III, Formula IV and / or Formula IV', the substituent may be independently an unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted heterocyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted polyaryl, unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0230] In some forms of formula III, formula IV and / or formula IV', the substituent may be an unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano or carbonyl or a combination thereof.

[0231] In some forms of Formula III, Formula IV and / or Formula IV', A1' may be an unsubstituted alkyl group or have the following structures:

[0232] or

[0233]

[0234] Among them: (a)R 17 To R 20 (a) can be hydrogen, unsubstituted alkyl, haloalkyl, alkoxy, halogen, cyano or carbonyl; (b) n17 to n20 can be integers between 0 and 5, between 0 and 4, between 0 and 3, or between 0 and 2.

[0235] In some forms, when L3 of equations III and / or IV is At that time, R 15 and R 16 It can be independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0236] The alkyl, alkenyl, alkynyl, and aryl groups of formulas III, IV, V, VI, and / or VII may be any of the alkyl, alkenyl, alkynyl, and aryl groups described above for formulas I, Ia, Ib, Ic, IIa, IIb, and IIc. For example, the alkyl groups of formulas III, V, VI, and / or VII may be straight-chain alkyl, branched alkyl, or cyclic alkyl (monocyclic or polycyclic), such as straight-chain C1-C1. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C 10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10 Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or C4-C 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C18 Polycyclic alkyl, C4-C 16 Polycyclic alkyl, C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0237] 3. Product yield

[0238] In some forms, the yield of products formed by homologous coupling of one or more gold (I) complexes disclosed herein can be in the range of about 15% to about 99%, about 30% to about 99%, about 50% to about 99%, about 30% to about 55%, or about 70% to about 99%.

[0239] In some forms, homocoupling of organohalides catalyzed by one or more gold (I) complexes disclosed herein can form more than one product, such as two products (e.g., the homocoupling product of formula IV and the hydrodehalogenation product of formula IV'), and each product can have a yield in the range of about 15% to about 55% or about 30% to about 55%.

[0240] In some forms, the yield of the product formed by homologous coupling of one or more gold (I) complexes disclosed herein catalyzed by the gold (I) complexes can be at least 2, at least 5, at least 10, at least 12, at least 20, at least 30, at least 40, at least 50, or at least 60 times the yield of the same product formed under the same reaction conditions using the same reaction with [Au2(μ-dppm)2](Cl)2, the same reaction with [Ru(bpy)3](Cl)2, and / or the same reaction with [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]. The amount of each of Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and [fac-Ir(ppy)3] used for catalyzing the homologous coupling of organohalides in the reaction mixture can be calculated by the following formula: mol% of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] = [(number of moles of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] / (sum of the moles of one or more organohalides)] × 100%.

[0241] For example, the yield of a product of formula IV formed by homologous coupling of an organohalide of formula III catalyzed by one or more gold (I) complexes disclosed herein can be at least 2, at least 5, at least 10, at least 12, at least 20, at least 30, at least 40, at least 50, or at least 60 times the yield of the same product formed under the same reaction conditions using the same reaction using [Au2(μ-dppm)2](Cl)2, the same reaction using [Ru(bpy)3](Cl)2, and / or the same reaction using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0242] The following examples describe specific exemplary organohalides, products, and their corresponding yields, as well as the yields of the same products formed by the same homologous coupling reaction of organohalides using known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3].

[0243] B. Catalytic alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline

[0244] In some forms, one or more gold (I) complexes can be used to catalyze the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline. The method may include exposing the reaction mixture to light at a certain temperature for a time sufficient to form the product. The light used to induce the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline may have a wavelength in the range of about 380 nm to about 450 nm or about 400 nm to about 450 nm, such as about 405 nm or about 442 nm.

[0245] The reaction mixture may comprise 2-phenyl-1,2,3,4-tetrahydroisoquinoline and an organohalide (e.g., an alkyl halide or an aryl halide), a solvent, and one or more gold (I) complexes disclosed herein, wherein 2-phenyl-1,2,3,4-tetrahydroisoquinoline is the substrate. In some forms, the reaction mixture may further comprise a suitable base, such as 2,4,6-trimethylpyridine, imidazole, potassium carbonate, or sodium carbonate, or combinations thereof.

[0246] Typically, the total amount of one or more gold (I) complexes in the reaction mixture used for the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline can be from about 0.1 mol% to about 2 mol%, from about 0.5 mol% to about 2 mol%, or from about 1 mol% to about 2 mol%, such as about 1 mol% or about 2 mol%. The total amount of one or more gold (I) complexes in the reaction mixture used for the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline can be calculated using the following formula: mol% of one or more gold complexes = [(sum of the moles of one or more gold complexes) / (moles of 2-phenyl-1,2,3,4-tetrahydroisoquinoline) × 100%.

[0247] Optionally, the method for catalytic alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline disclosed herein further includes the following steps: mixing 2-phenyl-1,2,3,4-tetrahydroisoquinoline, one or more organohalides and one or more gold (I) complexes and optionally a base in a suitable solvent to form a reaction mixture prior to the reaction.

[0248] Exemplary solvents suitable for forming a reaction mixture containing 2-phenyl-1,2,3,4-tetrahydroisoquinoline, one or more organohalides and one or more gold (I) complexes and optional solvents are acetonitrile, methanol or N,N-dimethylformamide or combinations thereof.

[0249] Alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline using one or more gold (I) complexes disclosed herein as photocatalysts can be carried out at room temperature for a time of about 2 to about 20 hours, about 4 to about 16 hours, or about 6 to about 14 hours, such as about 12 hours, and optionally in an inert gas environment (such as nitrogen).

[0250] 1. Reactants

[0251] In some forms, the organohalides contained in the reaction mixture that can react with 2-phenyl-1,2,3,4-tetrahydroisoquinoline may have the structure of formula VIII:

[0252]

[0253] Wherein: (a) A” may be a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl, or a substituted or unsubstituted heterocyclic group; (b) L4 may be a bond or R 21 and R 22 It can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n22 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.; (c) Z5 can be a halogen, such as fluorine, chlorine, bromine, or iodine. (d) The substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0254] 2. Products

[0255] In some forms, the products formed by the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline with an organohalide of formula VIII, catalyzed by one or more gold (I) complexes disclosed herein, can have the structure of formula IX:

[0256]

[0257] A” and L4 can be defined as in equation VIII above.

[0258] In some forms of Formula VIII and / or Formula IX, A” may be a substituted or unsubstituted straight-chain alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted polyaryl group.

[0259] In some forms of Formula VIII and / or Formula IX, A” may be an unsubstituted straight-chain alkyl, an unsubstituted branched alkyl, a substituted or unsubstituted polycyclic alkyl, or have a structure of Formula X, Formula XI, or Formula XII:

[0260]

[0261] Among them: (a)R 23 To R 26 (a) can be independently hydrogen, unsubstituted alkyl, haloalkyl, oxo, amino, alkoxy, halogen, cyano, or carbonyl; (b) n23 to n26 can be independently integers between 0 and 5, between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1; (c) Y” can be O, S, CR 27 or NR 28 And R 27 and R 28 (d) The substituent may be absent independently, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro or carbonyl;

[0262] In some forms of formulas VIII, IX, X, XI and / or XII, the substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0263] In some forms of formulas VIII, IX, X, XI and / or XII, the substituent may be independently an unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted heterocyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted polyaryl, unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0264] In some forms of formulas VIII, IX, X, XI and / or XII, the substituents may be unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano or carbonyl or combinations thereof.

[0265] In some forms of equation VIII and / or IX, L4 may be a bond or Where R 21 and R 22 It can be independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0266] The alkyl, alkenyl, alkynyl, and aryl groups of formulas VIII, IX, X, XI, and / or XII may be any of the alkyl, alkenyl, alkynyl, and aryl groups described above with respect to formulas I, Ia, Ib, Ic, IIa, IIb, and IIc. For example, the alkyl groups of formulas VIII, IX, X, XI, and / or XII may be straight-chain alkyl, branched-chain alkyl, or cyclic alkyl (monocyclic or polycyclic), such as straight-chain C1-C1. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C 10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10 Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or C4-C 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C 18 Polycyclic alkyl, C4-C 16 Polycyclic alkyl, C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0267] 3. Product yield

[0268] In some forms, the products formed by alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline catalyzed by one or more gold (I) complexes disclosed herein can have yields in the range of: about 40% to about 90%, about 40% to about 85%, about 50% to about 90%, about 50% to about 85%, about 60% to about 90%, and about 60% to about 85%.

[0269] In some forms, the yield of the product formed by the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline catalyzed by one or more gold (I) complexes disclosed herein can be at least 1.2 times, at least 1.5 times, at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 8 times, or at least 10 times that of the same product formed under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]. The amount of each of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and [fac-Ir(ppy)3] used in the reaction mixture for catalyzing the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline can be calculated by the following formula: mol% of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] = [(moles of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] / (moles of 2-phenyl-1,2,3,4-tetrahydroisoquinoline)] × 100%.

[0270] For example, the yield of the product of formula IX formed by the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline with an organohalide of formula VIII by one or more gold (I) complexes disclosed herein can be at least 1.2 times, at least 1.5 times, at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 8 times, or at least 10 times that of the same product formed under the same reaction conditions using the same reaction using [Au2(μ-dppm)2](Cl)2, the same reaction using [Ru(bpy)3](Cl)2, and / or the same reaction using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0271] The following examples describe specific exemplary organohalides, products, and their corresponding yields, as well as the yields of the same products formed by the same alkylation reaction of 2-phenyl-1,2,3,4-tetrahydroisoquinoline using known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3].

[0272] C. Catalytic cyclization of indole

[0273] In some forms, one or more gold (I) complexes can be used to catalyze the cyclization of indole. The method may include exposing the reaction mixture to light at a temperature for a time sufficient to form the product. The light used to induce the cyclization of indole may have a wavelength in the range of about 380 nm to about 450 nm or about 400 nm to about 450 nm, for example, about 405 nm.

[0274] The reaction mixture may contain indole (optionally more than one indole) and one or more gold (I) complexes disclosed herein, wherein the indole is the substrate. In some forms, the reaction mixture may further contain a suitable base, such as sodium carbonate.

[0275] Typically, the total amount of one or more gold (I) complexes used to catalyze the cyclization of indole in the reaction mixture can be from about 0.1 mol% to about 1 mol% or from about 0.5 mol% to about 1 mol%, such as about 0.5 mol% or about 1 mol%. The total amount of one or more gold (I) complexes used to catalyze the cyclization of indole in the reaction mixture can be calculated using the following formula: mol% of gold complexes = [(sum of the moles of one or more gold complexes) / (sum of the moles of one or more indole] × 100%.

[0276] Optionally, the method disclosed herein for catalytic cyclization of indole further includes the step of mixing one or more indole with one or more gold (I) complexes and optionally a base in a suitable solvent to form a reaction mixture prior to the reaction.

[0277] Exemplary solvents suitable for forming a reaction mixture containing one or more indoles and one or more gold (I) complexes and optional solvents are acetonitrile, methanol, or N,N-dimethylformamide or combinations thereof.

[0278] Indole cyclization reactions using one or more gold (I) complexes disclosed herein as photocatalysts can be carried out at room temperature for a time of about 2 to about 10 hours, about 2 to about 8 hours, or about 4 to about 8 hours, such as about 6 hours, and optionally in an inert gas environment (such as nitrogen).

[0279] 1. Reactants

[0280] In some forms, the indole contained in the reaction mixture can have the structure of formula XIII:

[0281]

[0282] Among them: (a)R 29 and R 30 (a) can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; (b) n30 can be an integer between 2 and 10, between 2 and 8, between 2 and 6, or between 2 and 4, such as 3 or 4; (c) R 31 and R 32 (d) n31 and n32 can be independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or combinations thereof; (e) Z6 can be a halogen, such as fluorine, chlorine, etc. (f) Substituents may be independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or combinations thereof.

[0283] In some forms, the indole contained in the reaction mixture can have the structure of formula XIV:

[0284]

[0285] Where: (a) n33 can be an integer between 0 and 8, between 0 and 6, between 0 and 4, or between 0 and 2, such as 1 or 2; (b) each occurrence of R 31 and R 32(c) Z6 may be a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof; (d) Z6 may be a halogen; and (e) substituents may be as defined in Formula XIII.

[0286] 2. Products

[0287] In some forms, the products formed by the cyclization of indole of formula XIII catalyzed by one or more gold(I) complexes disclosed herein can have the structure of formula XV:

[0288]

[0289] Where R 29 To R 32 n30 to n32 can be defined as in equation XIII.

[0290] In some forms, the products formed by the cyclization of indole of formula XIII or XIV catalyzed by one or more gold(I) complexes disclosed herein can have the structure of formula XVI:

[0291]

[0292] Among them, n33, R 31 and R 32 It can be defined as XIV.

[0293] In some forms of formula XIII, XIV, XV and / or XVI, the substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0294] In some forms of formula XIII, XIV, XV and / or XVI, the substituent may be independently an unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted heterocyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted polyaryl, unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0295] In some forms of formula XIII, XIV, XV and / or XVI, the substituent may be an unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano or carbonyl or a combination thereof.

[0296] In some forms of equations XIII, XIV, XV, and / or XVI, each occurrence of R 31 and R 32 It can be independently an unsubstituted alkyl, haloalkyl, oxo, amino, alkoxy, halogen, cyano, or carbonyl group.

[0297] In some forms of equations XIII, XIV, XV, and / or XVI, each occurrence of R 31 and R 32 It can be used independently for halogens, or And R 33 and R 34 It can be independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0298] The alkyl, alkenyl, alkynyl, and aryl groups of formulas XIII, XIV, XV, and / or XVI can be any of the alkyl, alkenyl, alkynyl, and aryl groups described above with respect to formulas I, Ia, Ib, Ic, IIa, IIb, and IIc. For example, the alkyl groups of formulas XIII, XIV, XV, and / or XVI can be straight-chain alkyl, branched alkyl, or cyclic alkyl (monocyclic or polycyclic), such as straight-chain C1-C1. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C 10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or C4-C 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C 18 Polycyclic alkyl, C4-C 16 C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0299] 3. Product yield

[0300] In some forms, the product formed by the cyclization of indole catalyzed by one or more gold (I) complexes disclosed herein can have yields of at least 90%, at least 92%, about 90% to about 99%, about 92% to about 98%, or about 94% to about 96%.

[0301] In some forms, the yield of the product formed by the cyclization of indole catalyzed by one or more gold (I) complexes disclosed herein can be at least 1.5, 2, 3, 4, 5, 6, 7, or at least 8 times the yield of the same product formed under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]. The amount of each of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and [fac-Ir(ppy)3] used to catalyze the cyclization of indole in the reaction mixture can be calculated by the following formula: mol% of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] = [(number of moles of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] / (sum of the number of moles of one or more indole)] × 100%.

[0302] For example, the yield of the product of formula XV or XVI formed by the cyclization of indole of formula XIII or XIV catalyzed by one or more gold (I) complexes disclosed herein can be at least 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, or at least 8 times that of the same product formed under the same reaction conditions using the same reaction using [Au2(μ-dppm)2](Cl)2, the same reaction using [Ru(bpy)3](Cl)2, and / or the same reaction using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0303] The following examples describe specific exemplary indoles, products, and their corresponding yields, as well as the yields of the same products formed by the same cyclization reaction of indoles using known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3].

[0304] D. Catalytic reductive dehalogenation of aryl halides

[0305] In some forms, one or more gold (I) complexes can be used to catalyze the reductive dehalogenation of aryl halides. The method may include exposing the reaction mixture to light at a temperature for a time sufficient to form a product. The light used to induce the reductive dehalogenation of the aryl halides may have wavelengths in the range of about 380 nm to about 450 nm or about 400 nm to about 450 nm, such as about 405 nm or about 442 nm.

[0306] The reaction mixture may contain an aryl halide (optionally more than one) and one or more gold (I) complexes disclosed herein, wherein the aryl halide is the substrate. In some forms, the reaction mixture may further contain a suitable base, such as Et3N, iPr2NMe, or iPr2NEt, or combinations thereof.

[0307] Typically, the total amount of one or more gold (I) complexes used to catalyze the reductive dehalogenation of aryl halides in the reaction mixture can be about 0.05 mol% to about 5 mol%, about 0.05 mol% to about 2 mol%, about 0.05 mol% to about 1 mol%, about 0.05 mol% to about 0.5 mol%, or about 0.05 mol% to about 0.25 mol%, such as about 0.05 mol%, about 0.25 mol%, about 2 mol%, or about 5 mol%. The total amount of one or more gold (I) complexes used to catalyze the reductive dehalogenation of aryl halides in the reaction mixture can be calculated using the following formula: mol% of gold complexes = [(sum of the moles of one or more gold complexes) / (sum of the moles of one or more aryl halides)] × 100%.

[0308] Optionally, the method disclosed herein for catalytic reductive dehalogenation of aryl halides further includes the step of mixing one or more aryl halides and one or more gold (I) complexes and optionally a base in a suitable solvent to form a reaction mixture prior to the reaction.

[0309] Exemplary solvents suitable for forming reaction mixtures containing one or more aryl halides and one or more gold (I) complexes and optionally a base include, but are not limited to, acetonitrile, methanol, or N,N-dimethylformamide or mixtures thereof, such as a mixture of acetonitrile and methanol. When a mixture of two solvents is used to form the reaction mixture, such as a mixture of acetonitrile and methanol, the volume ratio between the first solvent and the second solvent (e.g., the volume ratio between acetonitrile and methanol) can be from about 1:5 to 5:1, for example, about 1:1.

[0310] The reductive dehalogenation reaction of aryl halides using one or more gold (I) complexes disclosed herein as photocatalysts can be carried out at room temperature for a time of about 2 to about 20 hours, about 4 to about 16 hours, or about 6 to about 14 hours, such as about 12 hours, and optionally in an inert gas environment (such as nitrogen).

[0311] 1. Reactants

[0312] In some forms, the aryl halide contained in the reaction mixture can have the structure of formula XVII:

[0313]

[0314] Wherein: (a) A”' can be a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted polyheteroaryl; (b) Z7 can be a halogen, such as fluorine, chlorine, bromine, or iodine; (c) the substituent can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphoryl, phosphonyl or mercapto or a combination thereof.

[0315] 2. Products

[0316] In some forms, the products formed by the reductive dehalogenation of aryl halides of formula XVII catalyzed by one or more gold (I) complexes disclosed herein can have the structure of formula XVIII:

[0317]

[0318] Where A”' can be defined as in the above description of equation XVII.

[0319] In some forms of equation XVII and / or XVIII, A”' can have the structure of equation XIX, XX, or XXI:

[0320]

[0321] or

[0322]

[0323] Among them: (a)R 35 To R39 (a) can independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or combinations thereof; (b) n35 to n39 can independently be an integer between 0 and 5, between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1; (c) R 40 and R 41 (d) can be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto; (e) n40 can be an integer between 0 and 10, between 0 and 8, between 0 and 6, between 0 and 4, between 0 and 3, between 0 and 2, such as 1 or 2; (e) ------ can be absent or a bond, and L5 can be absent, substituted or unsubstituted alkylene, ether, polyether or thioether; (f) substituents can be as defined in formula XVII.

[0324] In some forms of equations XIX, XX, and / or XXI, R 35 To R 39 Can be independently of unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, oxo, alkoxy, halogen, cyano or carbonyl.

[0325] In some forms of equation XXI, R 40 and R 41 It can be independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl, oxo, alkoxy, or carbonyl.

[0326] In some forms of formula XIX, XX and / or XXI, the ----- may be absent or a bond, and L5 may be absent or an unsubstituted alkylene group.

[0327] In some forms of formulas XVII, XVIII, XIX, XX and / or XXI, the substituent may be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0328] In some forms of formula XVII, XVIII, XIX, XX and / or XXI, the substituent may be independently an unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted heterocyclic, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted polyaryl, unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0329] In some forms of formulas XVII, XVIII, XIX, XX and / or XXI, the substituents may be unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano or carbonyl or combinations thereof.

[0330] The alkyl, alkenyl, alkynyl, and aryl groups of formulas XVII, XVIII, XIX, XX, and / or XXI can be any of the alkyl, alkenyl, alkynyl, and aryl groups described above with respect to formulas I, Ia, Ib, Ic, IIa, IIb, and IIc. For example, the alkyl groups of formulas XVII, XVIII, XIX, XX, and / or XXI can be straight-chain alkyl, branched alkyl, or cyclic alkyl (monocyclic or polycyclic), such as straight-chain C1-C1. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C 10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10 Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or C4-C 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C 18 Polycyclic alkyl, C4-C 16 Polycyclic alkyl, C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0331] 3. Product yield

[0332] In some forms, the products formed by the reductive dehalogenation of aryl halides catalyzed by one or more gold (I) complexes disclosed herein can have yields in the range of about 25% to about 99%, about 25% to about 70%, or about 55% to about 99%.

[0333] In some forms, the yield of the product formed by the reductive dehalogenation of aryl halides catalyzed by one or more gold (I) complexes disclosed herein can be at least 1.5 times, at least 2 times, at least 2.5 times, at least 3 times, at least 4 times, at least 5 times, at least 8 times, at least 10 times, at least 15 times, at least 20 times, or at least 25 times that of the same product formed under the same reaction conditions using the same reaction with [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]. The amount of each of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and [fac-Ir(ppy)3] used in the reaction mixture for catalyzing the reductive dehalogenation of aryl halides can be calculated by the following formula: mol% of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] = [(number of moles of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] / (sum of the moles of one or more aryl halides)] × 100%.

[0334] For example, the yield of the product of formula XVIII formed by the reductive dehalogenation of an aryl halide of formula XVII catalyzed by one or more gold (I) complexes disclosed herein can be at least 1.5 times, at least 2 times, at least 2.5 times, at least 3 times, at least 4 times, at least 5 times, at least 8 times, at least 10 times, at least 15 times, at least 20 times, or at least 25 times that of the same product formed under the same reaction conditions using the same reaction using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3]. The total amount of one or more gold (I) complexes in the reaction mixture is equal to or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0335] The following examples describe specific exemplary aryl halides, products, and their corresponding yields, as well as the yields of the same products formed by the same reductive dehalogenation reaction of aryl halides using known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or [fac-Ir(ppy)3].

[0336] E. Catalytic breaking of CH bonds

[0337] In some forms, one or more gold (I) complexes (such as exemplary gold (I) complex 5a) can be used to catalyze the breaking of CH bonds in organic compounds. The method may include the step of exposing the reaction mixture to light at a temperature for a time sufficient to form a product. The light used to induce the breaking of CH bonds in the organic compound may have wavelengths in the following ranges: about 350 nm to about 450 nm, about 360 nm to about 450 nm, about 380 nm to about 450 nm, about 350 nm to about 420 nm, about 380 nm to about 420 nm, or about 400 nm to about 420 nm, such as about 405 nm.

[0338] The reaction mixture may comprise an organic compound having at least one CH bond (optionally more than one organic compound, wherein each organic compound has at least one CH bond) and one or more gold (I) complexes disclosed herein, wherein the organic compound having at least one CH bond is a substrate.

[0339] Typically, the total amount of one or more gold (I) complexes in the reaction mixture used to catalyze the cleavage of CH bonds can be from about 0.1 mol% to about 5 mol%, from about 0.5 mol% to about 5 mol%, or from about 1 mol% to about 5 mol%, such as about 5 mol%. The total amount of one or more gold (I) complexes in the reaction mixture used to catalyze the cleavage of CH bonds in organic compounds can be calculated using the following formula: mol% of gold complexes = [(sum of the moles of one or more gold complexes) / (sum of the moles of one or more organic compounds having at least one CH bond)] × 100%.

[0340] Optionally, the method disclosed herein for catalytic CH bond cleavage further includes the step of mixing one or more organic compounds and one or more gold (I) complexes in a suitable solvent to form a reaction mixture prior to the reaction.

[0341] Exemplary solvents suitable for forming reaction mixtures containing one or more organic compounds and one or more gold (I) complexes include, but are not limited to, acetonitrile and alcohols (e.g., methanol, ethanol, isopropanol, etc.) and combinations thereof, such as acetonitrile or isopropanol.

[0342] The reaction catalyzing the breaking of CH bonds using one or more gold (I) complexes disclosed herein as photocatalysts can be carried out at room temperature for a time of about 2 to about 20 hours, about 4 to about 16 hours, or about 6 to about 14 hours, such as about 12 hours, and optionally in an inert gas environment (such as nitrogen).

[0343] In some forms, for catalytic cleavage of the CH bonds in organic compounds, one or more gold (I) complexes disclosed herein may have a turnover number of at least 10, at least 20, at least 30, or at least 40. The turnover number of a gold (I) complex can be calculated by dividing the molar number of the product by the sum of the molar numbers of the gold complexes. For example, to determine the turnover number, an excess of substrate is used, such as 1000 or 10000 times the amount of the gold (I) complex (i.e., the amount of the gold (I) complex in the reaction mixture is approximately 0.1 mol% or 0.01 mol%), and the reaction is carried out for a long time, such as at least 12 hours.

[0344] 1. Reactants

[0345] In some forms, organic compounds containing at least one CH bond in the reaction mixture may have the structure of formula XXII, XXIII, or XXIV:

[0346]

[0347] Among them: (a)R 42 To R 49 and R 54 It can independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof, or two adjacent R groups forming a substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted polyheteroaryl, and R 42 and R 43 At least one of them and R 46 and R 47 One of them is hydrogen; (b) n54 can be an integer between 0 and 4; (c) R 50 To R 53 (d) n50 and n52 can be independent integers between 0 and 6; (e) Y”' can be O, S, CR 27 or NR 28 And R 27 and R28 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro, or carbonyl; (f)R 55 and R 56 (g) The substituent may independently be hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, or substituted or unsubstituted aralkyl; Substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphoryl, phosphonyl or mercapto, or combinations thereof.

[0348] 2. Products

[0349] The products formed by the cleavage of the CH bonds of organic compounds of formulas XXII, XXIII, and XXIV catalyzed by one or more gold (I) complexes disclosed herein can have structures of formulas XXV, XXVI, and XXVII or XXVII', respectively:

[0350]

[0351] Where R 42 R 44 To R 46 R 48 R 49 To R 56 、n54、n50、n52、------、Y”' can be defined as XXII、XXIII and XXIV.

[0352] In some forms, the R of organic compounds of formula XXIV 56 The product formed by the cleavage of the CH bond of such organic compounds catalyzed by one or more gold (I) complexes disclosed herein can have the structure of formula XXVII or XXVII' or a combination thereof described above:

[0353]

[0354] Where R55 The definition can be as shown in formula XXIV.

[0355] In some forms, the R of organic compounds of formula XXIV 56 The compound can be hydrogen, and the cleavage of the CH bond in such organic compounds catalyzed by one or more gold (I) complexes disclosed herein can form two products, wherein the first product can have the structure of formula XXVII and the second product can have the structure of formula XXVII'. The ratio of the first product to the second product depends on the specific reaction conditions (e.g., the choice of solvent). In some forms, when R... 56 When it is hydrogen, R in formulas XXIV, XXVII and / or XXVII' 55 It can be a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, or a substituted or unsubstituted aralkyl group, such as a substituted or unsubstituted aryl group.

[0356] In some forms, the products formed by the cleavage of the CH bonds of an organic compound of formula XXIII catalyzed by one or more gold (I) complexes disclosed herein can have the structure of formula XXVIII or XXIX:

[0357]

[0358] Among them (a)R 54 、n54、Y”' can be defined as above for equation XXIII; (b)R 57 To R 64 (c) Each of the following can be absent or a bond; (d) Substituents can be as defined above for Formula XXIII.

[0359] In some forms of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII and / or XXIX, the substituent may independently be a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof.

[0360] In some forms of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII and / or XXIX, the substituent may independently be an unsubstituted alkyl, an unsubstituted alkenyl, an unsubstituted alkynyl, an unsubstituted heterocyclic, an unsubstituted aryl, an unsubstituted heteroaryl, an unsubstituted polyaryl, an unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, an alkoxy, a halogen, a hydroxyl, a cyano, a nitro, an amino, an amide, an oxo, a sulfonyl, a phosphono, or a mercapto, or a combination thereof.

[0361] In some forms of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII and / or XXIX, the substituent may be an unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano, or carbonyl or a combination thereof.

[0362] In some forms of equations XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII and / or XXIX, R 42 To R 49 and R 54 It can be independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0363] The alkyl, alkenyl, alkynyl, and aryl groups of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII, and / or XXIX may be any one of the alkyl, alkenyl, alkynyl, and aryl groups described above for formulas I, Ia, Ib, Ic, IIa, IIb, and IIc. For example, the alkyl groups of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVII', XXVIII, and / or XXIX may be straight-chain alkyl, branched-chain alkyl, or cyclic alkyl (monocyclic or polycyclic), such as straight-chain C1-C1. 30 Alkyl, branched C4-C 30 Alkyl, cyclic C3-C 30 Alkyl, straight-chain C1-C 20 Alkyl, branched C4-C 20 Alkyl, cyclic C3-C 20 Alkyl, straight-chain C1-C 10 Alkyl, branched C4-C 10 Alkyl, cyclic C3-C 10 Alkyl, straight-chain C1-C6 alkyl, branched-chain C4-C6 alkyl, cyclic C3-C6 alkyl, straight-chain C1-C4 alkyl, cyclic C3-C4 alkyl, such as straight-chain C1-C6 alkyl. 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl; branched C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; cyclic C3-C9 alkyl, C3-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, or C3-C4 alkyl; or C4-C 30 Polycyclic alkyl, C4-C 25 Polycyclic alkyl, C4-C 20 Polycyclic alkyl, C4-C 18 Polycyclic alkyl, C4-C 16 Polycyclic alkyl, C4-C 15 Polycyclic alkyl, C4-C 14 Polycyclic alkyl, C4-C 13 Polycyclic alkyl, C4-C 12 Polycyclic alkyl, C4-C 10 Polycyclic alkyl, C4-C9 polycyclic alkyl, C4-C8 polycyclic alkyl, C4-C7 polycyclic alkyl, C4-C6 polycyclic alkyl or C4-C5 polycyclic alkyl.

[0364] 3. Product yield

[0365] In some forms, the products formed by the breaking of the CH bond of an organic compound catalyzed by one or more gold (I) complexes disclosed herein may have yields ranging from about 14% to about 80%, from about 35% to about 80%, or from about 14% to about 55%.

[0366] In some forms, the yield of the product formed by the breaking of the CH bond of an organic compound catalyzed by one or more gold (I) complexes disclosed herein can be at least 5, at least 8, at least 10, at least 15, at least 20, or at least 25 times the yield of the same product formed under the same reaction conditions using the same reaction with [Au2(μ-dppm)2](Cl)2, the same reaction with [Ru(bpy)3](Cl)2, and / or the same reaction with [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]. The amount of each of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and [fac-Ir(ppy)3] in the reaction mixture used to catalyze the breaking of CH bonds in organic compounds can be calculated by the following formula: mol% of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3] = [(number of moles of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3]) / (sum of the moles of one or more organic compounds having at least one CH bond)] × 100%.

[0367] For example, the yield of products of formula XXV, XXVI, XXVII, XXVIII, or XXIX formed by the cleavage of the CH bond of an organic compound of formula XXII, XXIII, or XXIV catalyzed by one or more gold (I) complexes disclosed herein can be at least 5, at least 8, at least 10, at least 15, at least 20, or at least 25 times the yield of the same product formed under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3], wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0368] The following examples describe specific exemplary organic compounds containing CH bonds for cleavage, products and their corresponding yields, and the yields of the same products formed by the same CH bond cleavage reaction using known catalysts such as [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2 and / or [fac-Ir(ppy)3].

[0369] The following paragraphs provide further insight into the disclosed compounds, their uses, and preparation methods.

[0370] 1. Gold (I) complexes having the following structure:

[0371]

[0372] in:

[0373] (a) m is 0, 1, or 2 positive charges;

[0374] (b) n is an integer between 0 and 2;

[0375] (c) When present, each occurrence of A' is an anion;

[0376] (d) X1 to X4 are independently P or N;

[0377] (e) L1 and L2 are independently absent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide group, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid group, phosphoryl group, or phosphonyl group;

[0378] (f) CY1 to CY8 are independently substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl or substituted or unsubstituted cycloynyl.

[0379] (g) R1 to R8 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0380] (h)n1 to n8 are independent integers between 0 and 10;

[0381] (i) Each ------ independently represents non-existent, single bond, double bond, or triple bond;

[0382] (j) Z1 and Z2 are independently absent, halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonates, sulfonates, dicyanoacetates, cyano groups, nitrates, hydroxyl groups, oxalates or carboxylates;

[0383] (k)Z3 is absent, a halide (fluoride, chloride, bromide, or iodide), oxygen, sulfur, oxalate, or carboxylate; and

[0384] (l) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyhexaaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, aryloxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphoryl, phosphonyl or mercapto, or a combination thereof.

[0385] (m) The condition is that when CY1 to CY8 are independently substituted or unsubstituted aryl groups, at least one of R1 to R8 is not hydrogen.

[0386] 2. The gold (I) complex according to paragraph 1 has the following structure:

[0387]

[0388] or

[0389]

[0390] in:

[0391] (a) Each occurrence of A' is an anion;

[0392] (b) X1 to X4 are independently P or N;

[0393] (c) L1 and L2 are independently nonexistent, single bond, double bond, triple bond, oxygen, sulfur, amino, amide, ether, polyether, thioether, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, carbonyl, sulfonyl, sulfonic acid, phosphoryl or phosphonyl.

[0394] (d) CY1 to CY8 are independently substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl or substituted or unsubstituted cycloynyl.

[0395] (e) R1 to R8 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0396] (f) n1 to n8 are independent integers between 0 and 10;

[0397] (g) Each ------ is either non-existent or a single bond;

[0398] (h) Z1 and Z2 are independently halides (fluorides, chlorides, bromides or iodides), trifluoromethanesulfonates, sulfonates, dicyanoacetates, cyano groups, nitrates, hydroxyl groups, oxalates or carboxylates.

[0399] (i) Z3 is a halide (fluoride, chloride, bromide, or iodide), oxygen, sulfur, oxalate, or carboxylate; and

[0400] (j) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, aryloxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0401] 3. The gold(I) complex according to paragraph 1 or 2, wherein L1 and L2 are independently single bonds or R9 and R 10 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n9 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, or 1.

[0402] 4. The gold (I) complex according to any one of paragraphs 1 to 3, wherein X1 to X4 are P.

[0403] 5. The gold (I) complex according to any one of paragraphs 1 to 4, wherein CY1 to CY8 are independently substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted polyheteroaryl.

[0404] 6. The gold (I) complex according to any one of paragraphs 1 to 5, having the following structure:

[0405] or

[0406]

[0407]

[0408] in:

[0409] (a) n10 and n12 are independent integers between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, or 1;

[0410] (b) R1 to R8 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0411] (c) n1 to n8 are independent integers between 0 and 5;

[0412] (d) Each ------ is either non-existent or a single key;

[0413] (e) Z1 and Z2 are independently a halide (fluoride, chloride, bromide or iodide), trifluoromethanesulfonate, sulfonate, dicyanoacetate, cyano, nitrate, hydroxyl, oxalate or carboxylate.

[0414] (f) Z3 is a halide (fluoride, chloride, bromide or iodide), oxygen, sulfur, oxalate or carboxylate;

[0415] (g) Each occurrence of A' is an anion; and

[0416] (h) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, aryloxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0417] 7. The gold (I) complex according to any one of paragraphs 1 to 6, wherein R1 to R8 are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo or alkoxy.

[0418] 8. The gold (I) complex according to any one of paragraphs 1 to 7, wherein R1 to R8 are independently hydrogen, hydroxyl, unsubstituted alkyl, unsubstituted alkenyl, haloalkyl, fatty alcohol, -NR 70 R 71 Substituted or unsubstituted polyaryl groups, substituted or unsubstituted heterocyclic groups, or R 13 and R 14 Independently, it is a halogen, hydrogen, hydroxyl, haloalkyl, alkoxy, unsubstituted alkenyl, or substituted or unsubstituted alkyl, n14 is an integer from 0 to 5, and R 70 and R 71 It is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, amino, alkoxy or carbonyl.

[0419] 9. According to the gold (I) complex in paragraph 8, where R 13 and R 14 Independent of unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0420] 10. The gold (I) complex according to any one of paragraphs 1 to 9, wherein Z1 to Z3 are independently halides.

[0421] 11. The gold (I) complex according to any one of paragraphs 1 to 10, wherein each occurrence of A' is a hydride, oxide, fluoride, sulfide, chloride, bromide, iodide, hydrogen phosphate, dihydrogen phosphate, hexafluorophosphate, trifluoromethanesulfonate, sulfate, nitrate, hydrogen sulfate, nitrite, thiosulfate, sulfite, chlorate, bromate, chlorite, hypochlorite, hypobromate, carbonate, chromate, bicarbonate, dichromate, perchlorate, acetate, formate, cyanide, amine, cyanate, peroxide, thiocyanate, oxalate, hydroxide, or permanganate.

[0422] 12. The gold (I) complex according to any one of paragraphs 1 to 11 has the following structure:

[0423]

[0424]

[0425]

[0426]

[0427]

[0428] 13. The gold (I) complex according to any one of paragraphs 1 to 12, which absorbs light in solution or as a powder at the following wavelengths: up to 520 nm, up to 500 nm, up to 480 nm, up to 450 nm, up to 420 nm, about 250 nm to about 520 nm, about 250 nm to about 500 nm, about 250 nm to about 480 nm, about 250 nm to about 450 nm, about 250 nm to about 420 nm, about 280 nm to about 520 nm, about 280 nm to about 500 nm, about 280 nm to about 480 nm, about 280 nm to about 450 nm, about 280 nm to about 420 nm, about 300 nm to about 520 nm, about 300 nm to about 500 nm, about 300 nm to about 420 nm, about 300 nm to about 520 nm, about 300 nm to about 500 nm, about 300 nm to about 420 nm. 80 nm, about 300 nm to about 450 nm, about 300 nm to about 420 nm, about 320 nm to about 520 nm, about 320 nm to about 500 nm, about 320 nm to about 480 nm, about 320 nm to about 450 nm, about 320 nm to about 420 nm, about 350 nm to about 520 nm, about 350 nm to about 500 nm, about 350 nm to about 480 nm, about 350 nm to about 450 nm, about 350 nm to about 420 nm, about 380 nm to about 520 nm, about 380 nm to about 500 nm, about 380 nm to about 480 nm, about 380 nm to about 450 nm, or about 380 nm to about 420 nm, as determined using the absorption spectrum of the gold (I) complex.

[0429] 14. The gold (I) complex according to any one of paragraphs 1 to 13, having an extinction coefficient (“ε”) in solution or as a powder of at least 0.1 × 10⁻⁶. 4 M -1 cm -1 At least 0.5 × 10 4 M -1 cm -1 At least 1.0 × 10 4 M -1 cm -1 At least 2.0 × 10 4 M -1 cm -1 At least 3.0 × 10 4 M -1 cm -1 At least 5.0 × 10 4 M -1 cm -1 At least 8.0 × 10 4 M -1 cm -1 Or at least 10.0 × 10 4 M -1 cm-1 As determined by the absorption spectrum of gold(I) complexes.

[0430] 15. The gold (I) complex according to any one of paragraphs 1 to 14, having a radiation attenuation rate (“k”) in solution or as a powder, having the following radiative attenuation rate. r "): At least 0.45 × 10 4 s -1 At least 0.80×10 4 s -1 At least 1.00 × 10 4 s -1 At least 2.00 × 10 4 s -1 At least 4.00 × 10 4 s -1 At least 8.00×10 4 s -1 At least 1.00 × 10 5 s -1 At least 1.50 × 10 5 s -1 At least 2.00 × 10 5 s -1 At least 2.50 × 10 5 s -1 Or at least 2.80 × 10 5 s -1 For example, approximately 2.95 × 10 5 s -1 Emission quantum yield and emission lifetime were determined using gold (I) complexes, etc.

[0431] 16. The gold (I) complex according to any one of paragraphs 1 to 15, having the following diffusion-corrected bimolecular quenching rate constant (“k q '”): at least 3.5 × 10 5 s -1 At least 5.0 × 10 5 s -1 At least 1.0 × 10 6 s -1 At least 5.0 × 10 6 s -1 At least 1.0 × 10 7 s -1 At least 5.0 × 10 7 s -1 At least 1.0 × 10 8 s -1 At least 3.5 × 10 8 s -1 At least 5.0 × 10 8 s-1 At least 8.0 × 10 8 s -1 or at least 1.0 × 10 9 s -1 For example, approximately 3.5 × 10 8 s -1 To approximately 1.5 × 10 9 s -1 As determined by the use of a quenching agent.

[0432] 17. The gold (I) complex according to any one of paragraphs 1 to 16, having a reduction potential of less than -1.46 V, less than -1.50 V, less than -1.55 V, or less than -1.60 V relative to a saturated calomel electrode (“SCE”), as determined by cyclic voltammetry.

[0433] 18. A method for catalyzing an organic reaction using one or more gold (I) complexes according to any one of paragraphs 1 to 17, comprising:

[0434] (i) Expose the reaction mixture to light at a certain temperature for a period of time sufficient to form a product.

[0435] The reaction mixture comprises reactants (optionally more than one reactant), a solvent, and one or more gold (I) complexes, and

[0436] The light has wavelengths in the following ranges: about 360 nm to about 450 nm, about 370 nm to about 450 nm, about 380 nm to about 450 nm, about 390 nm to about 450 nm, about 400 nm to about 450 nm, or about 405 nm to about 450 nm, such as about 405 nm or about 445 nm.

[0437] 19. The method according to paragraph 18, wherein the solvent is acetonitrile or an alcohol or a combination thereof.

[0438] 20. The method according to paragraph 18 or 19, wherein the total amount of one or more gold (I) complexes in the reaction mixture is at most 10 mol%, at most 5 mol%, at most 2 mol%, at least 0.05 mol%, at least 0.1 mol%, about 0.05 mol% to about 10 mol%, about 0.05 mol% to about 5 mol%, about 0.05 mol% to about 2 mol%, about 0.05 mol% to about 1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.1 mol% to about 10 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 2 mol%, about 0.1 mol% to about 1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.5 mol% to about 10 mol%, about 0.5 mol% to about 5 mol%, about 0.5 mol% to about 2 mol%, or about 0.5 mol% to about 1 mol%.

[0439] 21. The method according to any one of paragraphs 18 to 20, wherein the organic reaction is carried out at room temperature for a period of about 2 hours to about 20 hours, about 4 hours to about 16 hours, about 4 hours to about 14 hours, or about 6 hours to about 12 hours, such as about 6 hours or about 12 hours.

[0440] 22. The method according to any one of paragraphs 18 to 21, wherein the product has the following yields: at least 12%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at most 99%, at most 98%, at most 95%, about 15%. % to 99%, about 20% to 99%, about 40% to 99%, about 50% to 99%, about 15% to 95%, about 20% to 99%, about 40% to 95%, about 50% to 95%, about 15% to 90%, about 20% to 90%, about 40% to 90%, about 50% to 90%, about 15% to 80%, about 20% to 80%, about 40% to 80%, or about 50% to 80%.

[0441] 23. The method according to any one of paragraphs 18 to 22, which catalyzes the homologous coupling of organohalides, wherein the reaction mixture comprises reactants having the following structure:

[0442]

[0443] in:

[0444] (a)A1' is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl or a substituted or unsubstituted heterocyclic group.

[0445] (b) L3 is a bond or R 15 and R 16 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n16 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.

[0446] (c) Z4 is a halogen; and

[0447] (d) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0448] 24. The method according to paragraph 23, wherein the product has the following structure:

[0449]

[0450] in:

[0451] (a)A1' is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl or a substituted or unsubstituted heterocyclic group.

[0452] (b) L3 is a bond or R 15 and R 16Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n16 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.; and

[0453] (c) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0454] 25. The method according to paragraph 23 or 24, wherein A1' is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted polyheteroaryl.

[0455] 26. The method according to any one of paragraphs 23 to 25, wherein A1' is an unsubstituted alkyl group or has the following structure:

[0456] or

[0457]

[0458] in:

[0459] (a)R 17 To R 20 Independently hydrogen, unsubstituted alkyl, haloalkyl, oxo, alkoxy, halogen, cyano, or carbonyl; and

[0460] (b) n17 to n20 are independent integers between 0 and 5, between 0 and 4, between 0 and 3, and between 0 and 2.

[0461] 27. The method according to any one of paragraphs 23 to 26, wherein R 15 and R 16 Independently hydrogen, unsubstituted C1-C 10Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0462] 28. The method according to any one of paragraphs 23 to 27, wherein the reaction mixture further comprises a base selected from the group consisting of Et3N, iPr2NMe, iPr2NEt, imidazole, 2,4,6-trimethylpyridine, and potassium carbonate and combinations thereof.

[0463] 29. The method according to any one of paragraphs 23 to 28, wherein the total amount of one or more gold (I) complexes in the reaction mixture is in the range of about 1 mol% to about 5 mol%.

[0464] 30. The method according to any one of paragraphs 23 to 29, wherein the product has a yield in the range of about 15% to about 99% or about 15% to about 95%.

[0465] 31. The method according to any one of paragraphs 23 to 30, wherein the yield of said product is at least 2, at least 5, at least 10, at least 12, at least 20, at least 30, at least 40, at least 50, or at least 60 times the yield of said product formed under the same reaction conditions using the same reaction with [Au2(μ-dppm)2](Cl)2, the same reaction with [Ru(bpy)3](Cl)2, and / or the same reaction with [fac-Ir(ppy)3], and wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0466] 32. The method according to any one of paragraphs 18 to 22, which catalyzes the alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, wherein the reaction mixture comprises a first reactant and a second reactant, wherein the first reactant is 2-phenyl-1,2,3,4-tetrahydroisoquinoline, and the structure of the second reactant is:

[0467]

[0468] in:

[0469] (a) A” is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl or a substituted or unsubstituted heterocyclic group.

[0470] (b) L4 is a bond or R 21 and R 22 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto, and n22 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.

[0471] (c) Z5 is a halogen; and

[0472] (d) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0473] 33. The method according to paragraph 32, wherein the product has the following structure:

[0474]

[0475] (a) A” is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloynyl or a substituted or unsubstituted heterocyclic group.

[0476] (b) L4 is a bond or R 21 and R 22 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro, or mercapto; n22 is an integer between 1 and 10, between 1 and 8, between 1 and 6, between 1 and 4, between 1 and 3, between 1 and 2, such as 1 or 2, etc.; and

[0477] (c) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0478] 34. The method according to paragraph 32 or 33, wherein A” is a substituted or unsubstituted straight-chain alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted polyaryl group.

[0479] 35. The method according to any one of paragraphs 32 to 34, wherein A” is an unsubstituted straight-chain alkyl, an unsubstituted branched alkyl, a substituted or unsubstituted polycyclic alkyl, or has the following structure:

[0480] or

[0481]

[0482] in:

[0483] (a)R 23 To R 26 It is independently hydrogen, unsubstituted alkyl, haloalkyl, oxo, amino, alkoxy, halogen, cyano or carbonyl;

[0484] (b) n23 to n26 are independent integers between 0 and 5, between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1;

[0485] (c)Y” is O, S, CR 27 or NR 28 And R 27 and R 28 Independently, it can be absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro, or carbonyl; and

[0486] (d) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0487] 36. The method according to any one of paragraphs 32 to 35, wherein L4 is a key or Where R 21 and R 22 Independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0488] 37. The method according to any one of paragraphs 32 to 36, wherein the reaction mixture further comprises a base selected from the group consisting of 2,4,6-trimethylpyridine, Et3N, iPr2NMe, iPr2NEt, imidazole, potassium carbonate, and sodium carbonate, and combinations thereof.

[0489] 38. The method according to any one of paragraphs 32 to 37, wherein the total amount of one or more gold (I) complexes in the reaction mixture is in the range of about 0.1 mol% to about 2 mol%, such as about 1 mol% or 2 mol%.

[0490] 39. The method according to any one of paragraphs 32 to 38, wherein the reaction is carried out in an inert gas environment such as nitrogen.

[0491] 40. The method according to any one of paragraphs 32 to 39, wherein the product has the following yields: about 40% to about 90%, about 40% to about 85%, about 50% to about 90%, about 50% to about 85%, about 60% to about 90%, about 60% to about 85%.

[0492] 41. The method according to any one of paragraphs 32 to 40, wherein the yield of the product is at least 1.2 times, at least 1.5 times, at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 8 times, or at least 10 times the yield of the product under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3], and wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0493] 42. The method according to any one of paragraphs 18 to 22, which catalyzes the cyclization of indole, wherein the reaction mixture comprises a reactant having the following structure:

[0494]

[0495] in:

[0496] (a)R 29 and R 30 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0497] (b) n30 is an integer between 2 and 10, between 2 and 8, between 2 and 6, or between 2 and 4, such as 3 or 4;

[0498] (c)R 31 and R 32 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono or mercapto, or a combination thereof;

[0499] (d) n31 and n32 are independent integers between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1;

[0500] (e) Z6 is a halogen; and

[0501] (f) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0502] 43. According to the method described in paragraph 42, the reactants have the following structure:

[0503]

[0504] in:

[0505] (a) n33 is an integer between 0 and 8, between 0 and 6, between 0 and 4, between 0 and 2, such as 1 or 2;

[0506] (b) Each occurrence of R 31 and R 32 Independently, it is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof;

[0507] (c) Z6 is a halogen; and

[0508] (d) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0509] 44. The method according to paragraph 42, wherein the product has the following structure:

[0510]

[0511] in:

[0512] (a)R 29 and R 30 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0513] (b) n30 is an integer between 2 and 10, between 2 and 8, between 2 and 6, or between 2 and 4, such as 3 or 4;

[0514] (c)R 31 and R 32 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono or mercapto, or a combination thereof;

[0515] (d) n31 and n32 are independently integers between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1; and

[0516] (e) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0517] 45. The method according to any one of paragraphs 42 to 44, wherein the product has the following structure:

[0518]

[0519] in:

[0520] (a) n33 is an integer between 0 and 8, between 0 and 6, between 0 and 4, between 0 and 2, such as 1 or 2;

[0521] (b) Each occurrence of R 31 and R 32 Independently, it is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof; and

[0522] (c) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0523] 46. ​​The method according to any one of paragraphs 42 to 45, wherein each occurrence of R 31 and R 32 It is independently an unsubstituted alkyl, haloalkyl, oxo, amino, alkoxy, halogen, cyano, or carbonyl group.

[0524] 47. The method according to any one of paragraphs 42 to 46, wherein each occurrence of R 31 and R 32 Independently halogen, or And R 33 and R 34 Independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0525] 48. The method according to any one of paragraphs 42 to 47, wherein the reaction mixture further comprises a base selected from the group consisting of 2,4,6-trimethylpyridine, Et3N, iPr2NMe, iPr2NEt, imidazole, potassium carbonate, and sodium carbonate, and combinations thereof.

[0526] 49. The method according to any one of paragraphs 42 to 48, wherein the total amount of one or more gold (I) complexes in the reaction mixture is in the range of about 0.1 mol% to about 0.5 mol%.

[0527] 50. The method according to any one of paragraphs 42 to 49, wherein the product has a yield in the range of about 90% to about 99% or about 92% to about 98%.

[0528] 51. The method according to any one of paragraphs 42 to 50, wherein the yield of the product is at least 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, or at least 8 times the yield of the product under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3], and wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0529] 52. The method according to any one of paragraphs 18 to 22, which catalyzes the reductive dehalogenation of aryl halides, wherein the reaction mixture comprises reactants having the following structure:

[0530]

[0531] in:

[0532] (a)A”' is a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted polyheteroaryl;

[0533] (b) Z7 is a halogen; and

[0534] (c) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0535] 53. The method according to paragraph 52, wherein the product has the following structure:

[0536]

[0537] in:

[0538] (a) A”' is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted polyheteroaryl group; and

[0539] (b) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0540] 54. According to the method described in paragraph 52 or 53, where A”' has the following structure:

[0541]

[0542] or

[0543] in:

[0544] (a)R 35 To R 39 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono or mercapto, or a combination thereof;

[0545] (b) n35 to n39 are independent integers between 0 and 5, between 0 and 4, between 0 and 3, between 0 and 2, or 0 or 1;

[0546] (c)R 40 and R 41 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0547] (d) n40 is an integer between 0 and 10, between 0 and 8, between 0 and 6, between 0 and 4, between 0 and 3, between 0 and 2, such as 1 or 2;

[0548] (e)------Absent or bonded, and L5 is an absent, substituted or unsubstituted alkylene, ether, polyether or thioether; and

[0549] (f) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0550] 55. According to the method in paragraph 54, where R 35 To R 39 Independent of unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, oxo, alkoxy, halogen, cyano or carbonyl.

[0551] 56. According to the method described in paragraph 54 or 55, where R 40 and R 41 Independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, oxo, alkoxy or carbonyl.

[0552] 57. The method according to any one of paragraphs 54 to 56, wherein ------ is absent or is a bond and L5 is absent or is an unsubstituted alkylene group.

[0553] 58. The method according to any one of paragraphs 52 to 57, wherein the reaction mixture further comprises a base selected from the group consisting of Et3N, iPr2NMe, iPr2NEt, imidazole, potassium carbonate, and sodium carbonate, and combinations thereof.

[0554] 59. The method according to any one of paragraphs 52 to 58, wherein the total amount of one or more gold (I) complexes in the reaction mixture is in the range of about 0.05 mol% to about 5 mol%.

[0555] 60. The method according to any one of paragraphs 52 to 59, wherein the product has a yield in the range of about 25% to about 99%, about 25% to about 70%, or about 55% to about 99%.

[0556] 61. The method according to any one of paragraphs 52 to 60, wherein the yield of the product is at least 1.5 times, at least 2 times, at least 2.5 times, at least 3 times, at least 4 times, 5 times, at least 8 times, at least 10 times, at least 15 times, at least 20 times, or at least 25 times the yield of the same product formed under the same reaction conditions using [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, and / or using [fac-Ir(ppy)3].

[0557] 62. The method according to any one of paragraphs 18 to 22, which catalyzes the breaking of CH bonds, wherein the reaction mixture comprises reactants having the following structure:

[0558] or

[0559]

[0560] in:

[0561] (a)R 42 To R 49 and R 54 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono, or mercapto, or a combination thereof, or two adjacent R groups forming a substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted polyheteroaryl, and R 42 and R 43 At least one of them and R 46 and R 47 One of them is hydrogen;

[0562] (b) n54 is an integer between 0 and 4;

[0563] (c)R 50 To R 53 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0564] (d) n50 and n52 are independent integers between 0 and 6;

[0565] (e)Y”' is O, S, CR 27 or NR 28 And R 27 and R 28 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro or carbonyl;

[0566] (f)R 55 and R 56 Independently being hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl; and

[0567] (g) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0568] 63. The method according to paragraph 62, wherein the product has the following structure:

[0569]

[0570] or

[0571]

[0572] in:

[0573] (a)R 42 R 44 To R 46 R 48 R 49 and R 54 Independently formed by hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono or mercapto or combinations thereof, or by two adjacent R groups forming a substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted polyheteroaryl;

[0574] (b) n54 is an integer between 0 and 4;

[0575] (c)R 50 To R 53 Independently, it can be absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0576] (d) n50 and n52 are independent integers between 0 and 6;

[0577] (e)------Each occurrence is independent and either does not exist or is a key;

[0578] (f)Y”' is O, S, CR 27 or NR 28 And R 27 and R 28 Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro or carbonyl;

[0579] (g)R 55 and R 56Independently being hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl; and

[0580] (h) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0581] 64. The method according to paragraph 63, wherein the product has the following structure:

[0582]

[0583] in:

[0584] (a)R 54 It is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, carbonyl, alkoxy, halogen, hydroxyl, cyano, isocyano, nitro, amino, amide, oxo, sulfonyl, phosphono or mercapto or combinations thereof, or two adjacent R groups forming a substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted polyheteroaryl;

[0585] (b) n54 is an integer between 0 and 4;

[0586] (c)Y”' is O, S, CR 27 or NR 28 And R 27 and R 28 Independently, it is absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, halogen, oxo, amino, alkoxy, cyano, nitro or carbonyl;

[0587] (d)R 57 To R 64Independently, it can be absent, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted polyaryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, halogen, hydroxyl, oxo, amino, azide, alkoxy, cyano, isocyano, carbonyl, nitro or mercapto;

[0588] (e)------Each occurrence is independent and either does not exist or is a key; and

[0589] (f) The substituent is independently a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, substituted or unsubstituted alkoxy, halogen, hydroxyl, phenoxy, alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, carboxyl, amino, amide, oxo, silyl, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphonyl, phosphonyl or mercapto, or a combination thereof.

[0590] 65. According to the method described in paragraph 62 or 63, where R 42 To R 49 and R 54 Independently hydrogen, unsubstituted C1-C 10 Alkyl, unsubstituted C1-C8 alkyl, unsubstituted C1-C6 alkyl, unsubstituted C1-C5 alkyl, unsubstituted C1-C4 alkyl, or unsubstituted C1-C3 alkyl.

[0591] 66. The method according to any one of paragraphs 62 to 65, wherein R 55 It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted polyheteroaryl group, and R 56 It is hydrogen.

[0592] 67. The method according to any one of paragraphs 62 to 66, wherein the reaction is carried out in an inert gas environment, such as nitrogen.

[0593] 68. The method according to any one of paragraphs 62 to 67, wherein the total amount of one or more gold (I) complexes in the reaction mixture is in the range of about 0.1 mol% to about 5 mol%.

[0594] 69. The method according to any one of paragraphs 62 to 68, wherein the product has a yield in the range of about 14% to about 80%, about 35% to about 80%, or about 14% to about 55%.

[0595] 70. The method according to any one of paragraphs 62 to 69, wherein the reaction has a conversion number of at least 10, at least 20, at least 30 or at least 40.

[0596] 71. The method according to any one of paragraphs 62 to 70, wherein the yield of the product is at least 5, at least 8, at least 10, at least 15, at least 20, or at least 25 times the yield of the product under the same reaction conditions as the same reaction using [Au2(μ-dppm)2](Cl)2, the same reaction using [Ru(bpy)3](Cl)2, and / or the same reaction using [fac-Ir(ppy)3], and wherein the total amount of one or more gold (I) complexes in the reaction mixture is the same as or less than the amount of [Au2(μ-dppm)2](Cl)2, [Ru(bpy)3](Cl)2, or [fac-Ir(ppy)3].

[0597] The invention will be further understood by referring to the following non-limiting embodiments.

[0598] Example

[0599] Example 1. Exemplary Au(I) complexes and their properties

[0600] Materials and methods

[0601] Material

[0602] All handling of air-sensitive materials was performed under a nitrogen atmosphere using modified Schlenk lines. Unless otherwise specified, all chemicals were purchased from Alfa-Aesar and J&K Scientific Ltd. All solvents were distilled off from appropriate desiccants under argon atmosphere prior to use. [Au2(μ-dppm)2](Cl)2, [Au2(μ-dppm)2](ClO4)2, 1-(4-bromobutyl)-1H-indole, 1-(3-bromopropyl)-1H-indole, 1-(2-bromobenzyl)-1H-indole, 1-(4-bromobutyl)-5-fluoro-1H-indole, dihydroindole-1-carboxylic acid tert-butyl ester, and 2-phenyl-1,2,3,4-tetrahydroisoquinoline were synthesized according to published methods (Massai et al., Dalton Trans. 2015, 44, 11067-11076; Che et al., J. Chem. Soc. Dalton). Trans. 1990, 3215-3219; Greco and Schrock, Inorg. Chem. 2001, 40, 3850-3860; Kaldas et al., Org. Lett. 2015, 17, 2864-2866; Hatzenbuhler et al., J. Med. Chem. 2008, 51, 6980-7004; Jia et al., Org. Lett. 2019, 21, 9339-9342; Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683-15687).

[0603] Structural characterization

[0604] Recorded on a Bruker Mercury Plus 400MHz and 500MHz NMR spectrometer 1 H, 13 C 19 F and 31 P NMR spectral data. Referenced to internal solvent resonances and reported relative to SiMe4. 1 H and 13 Chemical shift (δ) of C relative to external CFC13 standard report. 19 Chemical shift of F. Relative to the external 85% H3PO4 standard report. 31 Chemical shift of P. Elemental analysis was performed on an Elemental Vario EL analyzer. High-resolution mass analysis was performed using an ESI source on a Varian 7.0T Fourier transform mass spectrometer. Gas chromatography-mass spectrometry analysis was performed on a Shimadzu GCMS-QP2020.

[0605] General procedure for the synthesis of Ar2PCH2PAr2

[0606] Synthesis of ligands 2 to 4. In a 100 mL Schlenk apparatus under N2, bis(dichlorophosphine)methane (1.0 g, 4.59 mmol, dissolved in 10 mL THF) was slowly added at 0 °C to a solution of (aryl)magnesium bromide synthesized from aryl bromide (20 mmol) and Mg (0.49 g, 19 mmol) in 40 mL THF. After stirring at room temperature for 12 hours, the mixture was added to a saturated aqueous NH4Cl solution. The organic phase was separated, and the aqueous phase was extracted with CH2Cl2. The combined organic phases were washed with brine, dried over MgSO4, filtered, and concentrated under vacuum. The crude product was purified by rapid column chromatography, eluting with CH2Cl2 / hexane to give the desired Ar2PCH2PAr2.

[0607] Synthesis of ligand 5. In 100 mL of Schlenk apparatus under N2, nBuLi (2.5 M, in n-hexane, 4.4 mL, 11 mmol) was added at -78 °C to a solution of 5'-bromo-4,4”-di-tert-butyl-1,1':3',1”-terphenyl (4.21 g, 10 mmol) in 50 mL of THF over 10 minutes. The solution was maintained at this temperature for 2 hours. Bis(dichlorophosphine)methane (500 mg, 2.3 mmol, in 5 mL of THF) was added dropwise to the solution at -78 °C over 15 minutes. The reaction mixture was further stirred at -78 °C for 1 hour and then at room temperature for 12 hours. The mixture was then added to a saturated aqueous solution of NH4Cl. The organic phase was separated, and the aqueous phase was extracted with CH2Cl2. The combined organic phases were washed with brine, dried over MgSO4, filtered, and concentrated under vacuum. The crude product was purified by rapid column chromatography and eluted with CH2Cl2 / hexane to give ligand 5 as a white solid (1.66 g, 50%).

[0608] Structural characterization of Ar2PCH2PAr2

[0609] Bis(bis(4-(trifluoromethyl)phenyl)phosphino)methane (2). White solid, 1.54 g (51%). 1 H NMR (400MHz, CDCl3): δ7.59 (d, J = 8.0Hz, 8H, Ar), 7.51–7.53 (m, 8H, Ar), 2.92 (s, 2H, PCH2P). 13 CNMR(101MHz,CDCl3):δ142.1(t,J C-P =4.7Hz,Ar),133.1(t,J C-P =10.5Hz,Ar),131.4(q,J C-F=32.7Hz,Ar),125.4(m,Ar),123.8(q,J C-F =272.4Hz,CF3),27.0(t,J C-P =24.4Hz, PCH2P). 31 P NMR (162MHz, CDCl3): δ-21.8 (s). 19 F NMR(376MHz,CDCl3):δ-63.0(s).HRMS(ESI):m / z:[M+H] + C 29 H 19 F 12 Calculated value of P2: 657.0765, measured value: 657.0772.

[0610]

[0611] Bis(bis(4-methoxyphenyl)phosphino)methane (3). White solid, 1.25 g (54%). 1 H NMR (400MHz, CDCl3): δ7.33–7.37(m,8H,Ar),6.83(d,J=8.6Hz,8H,Ar),3.78(s,12H,OMe),2.69(s,2H,PCH2P). 13 C NMR (101MHz, CDCl3): δ160.0 (s, Ar), 134.1 (t, J C-P =11.0Hz,Ar),129.9(s,Ar),114.0(t,J C-P =4.0Hz,Ar),55.1(s,OMe),29.2(t,J C-P =21.5Hz, PCH2P). 31 P NMR(162MHz,CDCl3):δ-25.8(s).HRMS(ESI):m / z:[M+H] + C 29 H 31 Calculated value of O4P2: 505.1692, measured value: 505.1695.

[0612]

[0613] Bis(bis(4-morpholinophenyl)phosphino)methane (4). White solid, 1.4 g (42%). 1H NMR (400MHz, CDCl3): δ7.31–7.35(m,8H,Ar),6.82(d,J=8.0Hz,8H,Ar),3.82–3.85(m,18H,NCH2CH2O),3.14–3.17(m,18H,NCH2CH2O),2.66(s,2H,PCH2P). 13 C NMR (101MHz, CDCl3): δ151.2(s,Ar),133.8(t,J C-P =10.8Hz,Ar),128.8(s,Ar),115.0(t,J C-P =3.8Hz,Ar),66.8(s,ArNCH2CH2O),48.6(s,NCH2CH2O),29.0(t,J C-P =21.5Hz, PCH2P). 31 P NMR(162MHz,CDCl3):δ-26.7(s).HRMS(ESI):m / z:[M+H] + C 41 H 51 Calculated value of N4O4P2: 725.3380, measured value: 725.3384.

[0614]

[0615] Ligand 5. White solid, 1.66 g (50%). 1 H NMR (500MHz, CDCl3): δ7.68–7.69(m,8H,Ar),7.62(s,4H,Ar),7.44(d,J=8.4Hz ,16H,Ar),7.38(d,J=8.4Hz,16H,Ar),3.15(s,2H,PCH2P),1.34(s,72H,CMe3). 13 C NMR (126MHz, CDCl3): δ150.4(s,Ar),141.4(t,J C-P =3.6Hz,Ar),139.6(t,J) C-P =3.7Hz,Ar),138.0(s,Ar),130.3(t,J C-P =10.6Hz,Ar),127.0(s,Ar),126.6(s,Ar),125.7(s,Ar),34.6(s,CMe3),31.4(s,CMe3),27.9(t,J C-P =24.0Hz, PCH2P). 31PNMR(202MHz,CDCl3):δ-19.1(s).HRMS(ESI):m / z:[M+H] + C 105 H 119 Calculated value of P2: 1441.8782, measured value: 1441.8772.

[0616]

[0617] Synthesis of gold complex 2a

[0618] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of bis(bis(4-(trifluoromethyl)phenyl)phosphino)methane (2) (131.3 mg, 0.2 mmol) in CH2Cl2 (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, the product was recrystallized from CH2Cl2 to give a white solid 2a (127 mg, 71%). 1 H NMR (400MHz, CD2Cl2): δ7.96 (d, J=7.1Hz, 16H, Ar), 7.57 (d, J=7.9Hz, 16H, Ar), 4.76 (s, 4H, PCH2P). 13 CNMR(101MHz,CD2Cl2): δ135.7(s,Ar),134.6(q,J C-F =32.9Hz,Ar),134.6(s,Ar),127.0(s,Ar),124.7(q,J C-F =272.8Hz,CF3),32.8(m,PCH2P). 19 F NMR (376MHz, CD2Cl2): δ-63.7(s). 31 PNMR(162MHz,CD2Cl2):δ28.7(s).C 58 H 36 Au2Cl2F 24 P4 analysis calculated values: C, 39.19; H, 2.04. Measured values: C, 39.21; H, 2.05.

[0619]

[0620] Synthesis of gold complex 2b

[0621] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of bis(bis(4-(trifluoromethyl)phenyl)phosphino)methane (2) (131.3 mg, 0.2 mmol) in CH2Cl2 (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, LiClO4 (106.4 mg, 1 mmol) was added to the mixture in MeOH (20 mL), and the mixture was stirred at room temperature for 1 hour. After removing the solvent under vacuum, the product was recrystallized from CH2Cl2 to give 2b as a white solid (162 mg, 85%). 1 HNMR (400MHz, d) 6 -DMSO): δ8.12(br,16H,Ar),7.89(d,J=6.8Hz,16H,Ar),5.24(s,4H,PCH2P). 13 C NMR (101MHz, d) 6 -DMSO): δ135.3(s,Ar),133.2(q,J C-F =32.7Hz,Ar),132.3(m,Ar),123.8(q,J C-F =273.0Hz,CF3),25.8(m,PCH2P). 31 P NMR (162MHz, d) 6 -DMSO):δ35.6(s). 19 FNMR (376MHz, d 6 -DMSO):δ-62.0(s).C 58 H 36 Au2Cl2F 24 O8P4 analytical values: C, 36.58; H, 1.90. Measured values: C, 36.55; H, 1.92.

[0622]

[0623] Synthesis of gold complex 3a

[0624] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of bis(bis(4-methoxyphenyl)phosphino)methane (3) (100.8 mg, 0.2 mmol) in CH2Cl2 (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, the product was recrystallized from CH2Cl2 / MeOH to give 3a as a white solid (118 mg, 80%). 1H NMR (400MHz, CD2Cl2): δ7.76–7.79(m,16H,Ar),6.87(d,J=8.5Hz,16H,Ar),4.42–4.56(m,4H,PCH2P),3.81(s,24H,OMe). 13 C NMR (101MHz, CD2Cl2): δ163.80(s,Ar),136.8(m,Ar),120.5(m,Ar),116.1(m,Ar),56.80(s,OMe),32.4(t,J=15.2Hz,PCH2P). 31 P NMR (162MHz, CD2Cl2): δ30.7(s).C 58 H 60 Analytical values ​​of Au₂Cl₂O₈P₄: C, 47.27; H, 4.10. Measured values: C, 47.25; H, 4.12.

[0625]

[0626] Synthesis of gold complex 3b

[0627] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of bis(bis(4-methoxyphenyl)phosphino)methane (3) (100.8 mg, 0.2 mmol) in CH2Cl2 (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, LiClO4 (106.4 mg, 1 mmol) was added to the mixture in MeOH (20 mL), and the mixture was stirred at room temperature for 1 hour. After removing the solvent under vacuum, the product was recrystallized from CH2Cl2 / MeOH to give 3b as a white solid (141 mg, 88%). 1 H NMR (400MHz, CD2Cl2): δ7.56–7.60(m,16H,Ar),6.93(d,J=8.5Hz,16H,Ar),4.10–4.15(m,4H,PCH2P),3.83(s,24H,OMe). 13 C NMR (101MHz, CD2Cl2): δ162.9(s,Ar),135.3(m,Ar),117.6(m,Ar),115.4(m,Ar),55.6(s,OMe),29.7(t,J=14.1Hz,PCH2P). 31 P NMR (162MHz, CD2Cl2): δ33.1(s).C 58 H 60 Au2Cl2O 16P4 analysis calculated values: C, 43.49; H, 3.78. Measured values: C, 43.52; H, 3.79.

[0628]

[0629] Synthesis of gold complex 4a

[0630] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of bis(bis(4-morpholinophenyl)phosphino)methane (4) (145.0 mg, 0.2 mmol) in CH2Cl2 (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, LiClO4 (106.4 mg, 1 mmol) was added to the mixture in MeOH (20 mL), and the mixture was stirred at room temperature for 1 hour. After removing the solvent under vacuum, the product was recrystallized from CH2Cl2 / MeOH to give a pale yellow solid 4a (169 mg, 83%). 1 H NMR (400MHz, CD2Cl2): δ7.51 (s, 16H, Ar), 6.90 (d, J = 7.4Hz, 16H, Ar), 4.03 (s, 4H, PCH2P), 3.84 (s, 32H, NCH2CH2O), 3.24 (s, 32H, NCH2CH2O). 31 P NMR (162MHz, CD2Cl2): δ31.4(s). 13 C10 NMR was not recorded due to low solubility. 82 H 100 Au2Cl2N8O 16 P4 analysis calculated values: C, 48.22; H, 4.94; N, 5.49. Measured values: C, 48.20; H, 4.96; N, 5.48.

[0631]

[0632] Synthesis of gold complex 5a

[0633] (THT)AuCl (64.1 mg, 0.2 mmol) was added to a solution of ligand 5 (288.4 mg, 0.2 mmol) in CH₂Cl₂ (10 mL), and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. After removing the solvent under vacuum, LiClO₄ (106.4 mg, 1 mmol) was added to the mixture in MeOH (20 mL), and the mixture was stirred at room temperature for 1 hour. After removing the solvent under vacuum, the product was recrystallized from CH₂Cl₂ / MeOH to give 5a as a white solid (229.5 mg, 66%). 1H NMR (400MHz, CD2Cl2): δ7.96(br,16H,Ar),7.77(br,8H,Ar),7.30(d,J=8.3Hz,32 H, Ar), 7.21 (d, J = 8.3Hz, 32H, Ar), 4.63–4.91 (m, 4H, PCH2P), 1.18 (s, 144H, CMe3). 13 C NMR (101MHz, CD2Cl2): δ152.9(s,Ar),144.5(m,Ar),137.1(s,Ar),131.8(s,Ar),131.4(m ,Ar),129.9(m,Ar),128.0(s,Ar),127.3(s,Ar),35.7(s,CMe3),32.2(s,CMe3),29.6(t,J C-P =13.4Hz, PCH2P). 31 P NMR (162MHz, CD2Cl2): δ39.9(s).C 210 H 236 Analytical values ​​of Au₂Cl₂O₈P₄: C, 72.54; H, 6.84. Measured values: C, 72.48; H, 6.81.

[0634]

[0635] Optical physical measurement

[0636] UV-Vis absorption spectra were recorded on a Hewlett-Packard 8453 diode array spectrophotometer. Steady-state emission spectra were obtained on a Horiba Fluorolog-3 spectrophotometer. Nanosecond time-resolution differential absorption spectroscopy (ns-TA) was obtained at room temperature using an LP920-KS laser flash photodispersive spectrophotometer equipped with a Q-switched Nd:YAG laser (Edinburgh Instrument Ltd.). Emission lifetime measurements were performed on a Quanta Ray GCR 150-10 pulsed Nd:YAG laser system. Errors in λ (±1 nm), τ (±10%), and Φ (±10%) were estimated. All solutions used for photophysical measurements at room temperature were degassed using a high-vacuum line in a two-chamber unit with five freeze-pump-thaw cycles. The emission quantum yield of the solution was measured using a solution of [Ru(bpy)3](PF6)2 in CH3CN (Φ=0.062) as a standard. The 10% error is an estimate.

[0637] Instrument setup and associated spectral calibration for femtosecond transient absorption (fs-TA) have been described previously (Kwok et al., J. Am. Chem. Soc. 2006, 128, 11894–11905; Kwok et al., J. Am. Chem. Soc. 2008, 130, 5131–5139; Chan et al., Phys. Chem. Chem. Phys. 2011, 13, 16306–16313; Lu et al., J. Am. Chem. Soc. 2011, 133, 14120–14135). In summary, all these measurements were performed using a commercially available Ti:Sapphire regenerative amplifier laser system (800 nm, 40 fs, 1 kHz, and 3.5 mJ / pulse). In fs-TA, the sample is probed by continuous pulses of white light generated by a rotating CaF2 plate pumped by an 800 nm laser. For fs-TA, the time delay of the probe pump pulse is altered by a computer-controlled optical delay line. The fs-TA signal is collected by a monochromator and detected by a liquid nitrogen-cooled CCD detector. The instrument response function (IRF) of fs-TA is approximately 100 fs to 200 fs, varying slightly with spectral wavelength. To eliminate the effects of rotational diffusion, the polarization direction of the pump laser is set to the magic angle relative to the probe in all measurements. Measurements are performed at room temperature and atmospheric pressure.

[0638] Electrochemical Measurement

[0639] Cyclic voltammetry measurements were performed using a Princeton Applied Research Electrochemical Analyzer (PARSTATMC Multichannel Potentiostat for Gold (I) Complexes and Potentiostat / Currentostat Model 273A for Organic Substrates). The measurements were performed using a DMF... n Bu4NPF6 (0.1M) was used as the supporting electrolyte for the room-temperature electrochemical measurements. The DMF used for the electrochemical measurements was degassed with argon. A saturated calomel electrode (SCE) was used as the reference electrode for the gold (I) complex. A glassy carbon electrode and a platinum wire were used as the working and counter electrodes, respectively.

[0640] X-ray structural determination

[0641] X-ray data were obtained using graphite monochromatic Mo Kα radiation on a Rigaku Saturn CCD diffractometer. and Cu Kα radiation Collected. The structure was analyzed using the direct method (SHELXS-97) (Sheldrick, SHELXS-90 / 96, Program for Structure Solution, ActaCrystallogr.Sect A 1990, 46, 467), and through F... 2Refinement was performed using full matrix least squares. All non-hydrogen atoms were anisotropically refined, while hydrogen atoms were refined using a riding model (SHELXL-97) (Sheldrick, SHELXL97, Program for Crystal Structure Refinement, University of Goettingen:Geottingen, Germany, 1997). Crystal data and details of the structure refinement are listed in Table 1a. Supplementary crystallographic data for this paper are contained in CCDC 1877689(2a), CCDC 1877702(3a), and CCDC 1906508(4a). These data are freely available from the Cambridge Crystallographic Data Centre at ccdc.cam.ac.uk / data_request / cif.

[0642] Calculation details

[0643] DFT / TDDFT calculations were performed using the Gaussian16 package (Frisch et al., Inc.: Wallingford CT 2010). The true vibrational frequencies of these optimized structures were calculated to confirm that all optimized structures were potential minimums. The hybrid function PBE0 with dispersion correction in revision 3 (D3BJ) was employed (Adamo and Barone, J. Chem. Phys. 1999, 110, 6158-6170; Grimme et al., J. Chem. Phys. 2010, 132, 154-104). The LANL2DZ basis set and corresponding effective core potential (ECP) proposed by Hay and Wadt were used for the valence atomic orbitals of Au (Wadt and Hay, J. Chem. Phys. 1985, 82, 284-298; Hay and Wadt, J. Chem. Phys. 1985, 82, 299-310). The 6-31G* basis set was used for other atoms (Frisch et al., J. Chem. Phys. 1984, 80, 3265-3269; Radom et al., J. Am. Chem. Soc. 1973, 95, 6531-6544). Solvent effects were considered using a polarization continuity model (PCM) with CH3CN as the solvent (Cossi et al., J. Chem. Phys. 2002, 117, 43-54). The full width at half maximum (FWHM) of the absorption spectrum convolved with a Gaussian distribution was set to 3000 cm⁻¹. -1 Orbital composition analysis was performed using the natural atomic orbitals (NAO) obtained from the Multiwfn 3.8 software (Lu and Chen, J. Comput. Chem. 2012, 33, 580-592).

[0644] The calculation of SO electronic transitions was performed using the TDDFT method in the ADF2019 package with an optimized T1 structure (TeVelde et al., J. Comput. Chem. 2001, 22, 931-967; Guerra et al., Theor. Chem. Acc. 1998, 99, 391-403), ZORA (Zeroth Order Regular Approximation) (van Lenthe et al., J. Chem. Phys. 1999, 110, 8943-8953; van Lenthe et al., J. Chem. Phys. 1993, 99, 4597-4610; van Lenthe et al., J. Chem. Phys. 1993, 99, 4597-4610; van Lenthe et al., J. Chem. Phys. 1993, 99, 4597-4610; van Lenthe et al., J. Chem. Phys. 1999, 110, 8943-8953 ...99, 4597-4610; van Lenthe et al., J. Chem. Phys. 1999, 99, 4597-4610; van Lenthe et al., J. Chem. Phys. 1999, J Lenthe et al., J. Chem. Phys. 1994, 101, 9783-9792) - PBE0 / TZP level for Pt and DZP level for other atoms (Adamo and Barone, J. Chem. Phys. 1999, 110, 6158-6170; Van Lenthe and Baerends, J. Comput. Chem. 2003, 24, 1142-1156). Molecular orbitals were represented using ADF views. In the medium, k r The refractive index should be corrected according to the Strickler-Berg relation (Nozaki, J. Chin. Chem. Soc. 2006, 53, 101-112; Strickler and Berg, J. Chem. Phys. 1962, 37, 814-822). Therefore, the calculated emissivity k r Multiply by the square of the refractive index of acetonitrile (n = 1.344). Under the assumption of rapid thermalization, the calculated total radiation lifetime is the average of the three substates (Mori et al., PCCP 2014, 16, 14523-14530):

[0645]

[0646] result

[0647] Structural Analysis

[0648] Ligands 2 through 4 were designed to examine the diphosphine ligand pair [Au2(diphosphine)2]. 2+The triplet excited state electronic effect, while ligand 5 is designed to create a hydrophobic environment that can promote the binding of the substrate in the internal ligand sphere. The reaction of ligands 2 and 3 with [Au(tht)Cl] (tht = tetrahydrothiophene) yields complexes 2a and 3a, which are isolated as chloride salts in 71% and 80% yields, respectively. Complexes 2b, 3b, 4a, and 5a are obtained in 66% to 88% yields by metathesis reaction with LiClO4 in MeOH. These complexes have been characterized by NMR spectroscopy and elemental analysis. Diffraction-quality crystals of 2a, 3a, 4a, and 5a were obtained by slow evaporation of Et2O / CH2Cl2 solution at room temperature. Figures 1A to 1D The intramolecular Au-Au distances for 2a, 3a, 4a, and 5a are 3.0112(10), 2.9567(7), 2.9805(5), and 5a, respectively. They fall within the range considered to have weak Au-Au interactions, with 5a having the shortest distance in the entire series. The chloride ions in 2a and 3a exhibit weaker interactions with Au(I), as evidenced by their long Au-Cl distances. 3a:3.047(3) and The Au-P distance is revealed to be between 2.283(3) and... Within this range, the distance is comparable to that in other gold(I)phosphine complexes.

[0649] Photophysical properties

[0650] Perchlorate has been used as a counter anion in the photophysical measurements of these gold(I) complexes to minimize gold(I)-anion binding interactions in both the ground and excited states. In CH3CN, 1b, 2b, and 3b exhibit strong absorption from 270 nm to 320 nm (Table 1b, ...). Figure 2A and 2B ), ε is approximately 10 4 M -1 cm -1 , assigned to singlet states [5dσ*→6pσ] and intraligand transitions. Under photoexcitation, 2b and 3b exhibit unstructured emission bands with a peak-to-maximum value (λ). max The emission quantum yield (Φ) and lifetime (τ) at 611 nm and 569 nm, respectively, are 0.11–0.15 and 23.8–28.1 μs, respectively. Complex 4a has emission quantum yields (Φ) and lifetimes (τ) at 250 nm–360 nm (ε = 2.0 × 10⁻⁶). 4 M -1 cm -1 Up to 15.6×10 4 M -1 cm -1 It exhibits a distinct strong absorption band at ) and trails to approximately 420 nm (ε = 1.5 × 10 at 400 nm).3 M -1 cm -1 This is primarily caused by spin-allowed ligand-metal-metal charge transfer (LMMCT) transitions. It exhibits an unstructured emission band, λ max At 568 nm, Φ is 0.59 and τ is 2.0 μs. Complex 4a exhibits strong absorption, extending to approximately 420 nm (ε = 1.5 × 10⁻⁶ at 400 nm). 3 M -1 cm -1 ), and the prototype [Au2(μ-dppm)2] 2+ Compared to a redshift of 50 nm, the radiative attenuation constant k of complex 4a in degassed CH3CN. r The estimated value is 2.95 × 10⁻⁶. 5 s -1 This is the highest value among binuclear gold(I) complexes. The k-value for the spin-orbit electron T1→S0 transition of 4a in the optimized T1 structure was calculated using the SO-TDDFT method in CH3CN solution. r See Table 1c for ZFS. Complex 5a, with 24 phenyl groups, exhibits very strong absorption, λ. max At 261 nm (ε = 219000 M) -1 cm -1 This is attributed to the combination of spin-allowed ligand centers and the [5dσ*→6pσ] transition. Under photoexcitation, 5a exhibits a broad, unstructured emission band, λ max At 583 nm, Φ is 0.27 and τ is 5.8 μs.

[0651] Table 1a. Summary of crystal and X-ray data collection for gold complexes 2a to 4a.

[0652]

[0653] Table 1b.1b to 3b, 4a and 5a, with their estimated excited-state redox potentials.

[0654]

[0655] Table 1c. k-values ​​of the spin-orbit electron T1→S0 transition at the optimized T1 structure in CH3CN solution calculated using the SO-TDDFT method. r and zfs. T I T II and T III The three sub-levels represent the T1 state.

[0656]

[0657] In the solid state at 77 K, complexes 1b to 3b exhibit unstructured emission bands, λ max The wavelength range is 382nm to 449nm, and the lifetime range is 1.3μs to 3.8μs. Figures 2C to 2G (See Table 1d). An additional broad emission band was observed in 2b, centered at 617 nm, with a lifetime of 31.1 μs. For 4a, the broad, unstructured emission profile remained unchanged in the solid state at 77 K and blue-shifted to 510 nm with a lifetime of 22.7 μs. In the glassy medium at 77 K (DMF:EtOH:MeOH = 1:1:4 (V / V / V)), 1b to 3b and 4a exhibited high-energy emission (~430 nm to 460 nm), with lifetimes of 6.3 μs to 11.9 μs for 1b to 3b and 44.7 μs for 4a. Figures 2C to 2G (and Table 1d). 1b to 3b high-energy emissions at 77K are designated as originating from... 3 Emission of the [5dσ*→6pσ] excited state. The extensive and structureless emission of 1b to 3b in CH3CN at room temperature was designated as a complex-anion excited complex rather than a complex-solvent excited complex because of the emission λ of [Au2(μ-dppm)2(CF3SO3)2]. max It remains almost identical in different solvents (λ in CH3CN, CH3OH, CH2Cl2) max =570nm). Their emission is unlikely to originate from... 3 The [5dσ*→6pσ] excited state is chosen because the energy of this excited state should be very high (<450 nm). The significant difference in the emission behavior of these complexes in solution compared to that at 77 K is due to... 3 The [5dσ*→6pσ] excited state exhibits high reactivity at room temperature, forming excited complexes with surrounding solvent molecules or anions, which is hindered at 77 K. DFT calculations indicate that the emission of 4a originates from... 3 LMMCT excited states (see below).

[0658] Table 1d.1b to 3b, 4a and 5a Emission data at 77K in solid and glassy media [DMF:EtOH:MeOH=1:1:4(V / V / V)].

[0659]

[0660] The excited-state dynamics of 4a have been detected using ultrafast time-resolved absorption differential spectroscopy. The nanosecond time-resolved absorption differential (ns-ta) spectrum of 4a shows λ... max Absorption at 388 nm and 520 nm and a broad absorption band from 650 nm to 800 nm. Figure 3AThe decay lifetime of the absorption difference curve was 1.6 μs, comparable to the emission lifetime of 4a in CH3CN. Femtosecond time-resolution absorption difference (fs-ta) spectra of 4a obtained immediately after 266 nm laser pulse excitation revealed an absorption difference λ at ~390 nm. max and broadband from 450nm to 550nm ( Figure 3B ), which evolves with a time constant of 1.2 ps into another ns-ta profile similar to 4a, showing the effective intersystem crossover of 4a.

[0661] Electrochemical and excited-state redox properties

[0662] Electrochemical studies using cyclic voltammetry showed that 1b exhibited an irreversible reduction potential at -1.46 V relative to the SCE. Modification of dppm resulted in a significant change in the reduction potential; for 2b with the CF3 group (relative to -1.21 V), an Ed was observed. pc Anode displacement was observed for 1b to 3b (-1.52 V relative to SCE) and 4a (-1.63 V relative to SCE), which have electron-donating groups, while cathode displacement was observed for 4a (-1.52 V relative to SCE). No oxidation was observed for 1b to 3b even at up to 1.4 V relative to SCE, but irreversible oxidation waves were observed for 4a. pa The value is 1.42 V relative to SCE, which can be attributed to the oxidation of morpholine. Complex 5a shows an irreversible reduction wave, E pc The voltage is -1.38V relative to SCE, and there is no oxidation signal.

[0663] To estimate the excited-state potentials of these complexes, the diffusion-corrected bimolecular quenching rate constant (kc) of the selected quencher has been obtained. q The following are listed in Table 2. Complex 4a exhibits a large kinematic potential (k) for a range of pyridinium salts with reduction potentials relative to SCE ranging from -1.52 V to -1.14 V. q '(From 3.6×10 8 M -1 s -1 Up to 1.5×10 9 M -1 s -1 The reduction potential of 4a is one to two orders of magnitude larger than that of 1b, and two to three orders of magnitude larger than that of 2b (Table 2). However, 4a exhibits a relatively small k-value relative to neutral organic quenchers with a reduction potential in the range of -2.31V to -1.81V for SCE. q '(10 5 Up to 10 7 M -1 s -1 From ln(k) qIn the relationship diagram between ') and E(Q), by using methoxybenzene / amine as a quencher, the potential [E(4a)] is... + / 4a * The estimate is -1.81V relative to SCE, and [E(4a* / 4a] - The estimated value is 1.57 V relative to SCE, indicating that 4a is a stronger photoreducing agent than 1b. + / 1b*)]=relative to SCE is -1.6V). Typically, if the potential E(M + If M is more negative than -1.5V relative to SCE, then M is considered a strong photoreducing agent.

[0664] Table 2. Rate constants for the emission of complexes 1b, 2b and 4a by various organic substrates in degassed acetonitrile at room temperature.

[0665]

[0666]

[0667]

[0668] [a] E red This refers to the redox reaction Q + e - →Q - The potential of E, where Q represents the quencher; ox This refers to the redox reaction Q. + +e - → The potential of Q. [b] These values ​​are obtained from the Stern-Volmer plot: τ0 / τ=1+k q [τ0][Q]. [c] The diffusion-corrected quenching rate constant is given by k' q =1.0×10 10 ·k q / (1.0×10 10 -k q It was derived from this. [d]Che et al., J. Chem. Soc. Dalton Trans. 1990, 3215–3219. [e] Li et al., Angew. Chem. Int. Ed. 2018, 57, 14129–14133. [f] Hoshi et al., Electrochemistry 2004, 72, 852-854. [g] Broglia et al., J. Photoch. Photobio. A. 2005, 170, 261–265. [h] Yang et al., Chem. Sci. 2016, 7, 3123–3136. [i] Guilbault et al., Anal. Chem. 1963, 35, 582–586. [j] Liddle and Gardinier, J. Org. Chem. 2007, 72, 9794–9797. [k] Ohkubo et al., Chem. Sci. 2011, 2, 715–722. [l] Chow et al., Chem. Asian J. 2014, 9, 534–545.

[0669] DFT and TDDFT calculations

[0670] DFT / TDDFT calculations were performed on 1b and 4a to investigate the properties of their excited states. The optimized structure of 4a is consistent with the X-ray crystal structure, and the calculated Au-Au distance is... The gold-gold distance of 4a in the crystal structure is 2.9805 (5).

[0671] TDDFT calculations have been performed on the optimized 1b and 4a structures to reveal the properties of the lowest energy absorption bands of these binuclear Au complexes. Figure 4A As shown, the calculated lowest energy absorption bands for 1a and 4a are located at 284 nm and 347 nm, respectively, which is consistent with experimental observations (1b and 4a are λ). expt =294nm, 350nm). The S1 (284nm) state of 1b comes from the HOMO→LUMO transition, where the HOMO is composed of 5d-6s hybrid σ*(Au-Au) antibonding orbitals, and the LUMO is mainly composed of 6pσ(Au-Au) bonded orbitals. Figure 4B ).therefore, 1 The MC (metal-centric) transition is assigned to the S1 state of 1b. The S1 transition of 4a is designated as a transition from the π orbital (HOMO) of the morpholine substituent to the 6pσ (Au-Au) bonded orbital. Therefore, the strong lowest energy absorption in 4a is attributed to 1 LMMCT (ligand-metal-metal charge transfer) transitions.

[0672] Unrestricted DFT calculations were performed on the T1 states of 1b and 4a, showing that the Au-Au distance of 1b changes from the S0 state. contracted to T1 state ( Figure 5A The Au-Au distance of 4a from state S0 contracted to T1 state ( Figure 5D This indicates that Au-Au bonding interactions were formed in the T1 state. 3 The MC excited state is responsible for the T1 state of 1b. Therefore, electronic excitation from the 6s-5d hybridized σ(Au-Au) antibonding orbital (HOMO) to the 6pσ(Au-Au) bonding orbital (LUMO) will result in the formation of a net Au-Au bond. For 4a, the electronic transition involving the diphosphine ligand to the 6pσ(Au-Au) bonding orbital (LUMO) is... 3 The LMMCT excited state is responsible for the T1 state of 4a. Since the antibonding orbitals of 4a in the T1 state are still occupied, the increase in Au-Au bond order is only half that of the excited state 1b. This explains the calculation of 4a according to TDDFT. With 1a Compared to the relatively small Au-Au contraction in T1, two excitation complex structures, 1b-ClO4 and 1b-[ClO4]2, in the T1 state have been identified and optimized, with binding energies of -21.8 kcal / mol and -33.7 kcal / mol, respectively. Emission in the T1 state occurs during the HOMO→LUMO transitions of 1b, 1b-ClO4, and 1b-[ClO4]2, with calculated values ​​of 3.18 eV, 2.37 eV, and 2.19 eV, respectively. Therefore, the 1b emission peak observed experimentally at 579 nm in CH3CN (2.14 eV in Table 1b) is designated as originating from the 1b-[ClO4]2 excitation complex in the T1 state. In the optimized 1b-[ClO4]2 excitation complex structure, the calculated Au-ClO4 distance is... and like Figure 5B As shown. ClO4 - Counteracting the antibonding σ* interaction between the counterion and Au atoms in the HOMO, thereby increasing the orbital energy and reducing the HOMO-LUMO gap ( Figure 5B and Figure 5E Therefore, in 1b-ClO4 and 1b-[ClO4]2, the redshifted emission energies were calculated and observed compared to 1b. Similarly, the T1 state exciton structures 4a-ClO4 and 4a-[ClO4]2 were optimized, with binding energies of -10.1 kcal / mol and -20.6 kcal / mol, respectively. Figure 5C As shown, the calculated Au-ClO4 distance in 4a-[ClO4]2 is and This indicates that the Au-ClO4 binding interaction is weaker than that in the 1b-[ClO4]2 excited complex. The calculated emission energies for 4a, 4a-ClO4, and 4a-[ClO4]2 are 2.67 eV, 2.62 eV, and 2.5 eV, respectively. Therefore, the experimentally observed maximum emission peak of 4a at 568 nm (2.18 eV in Table 1b) is designated as originating from the 4a-[ClO4]2 excited complex in the T1 state.

[0673] Spin-orbit (SO) TDDFT calculations have been performed on 4a to obtain the k-axis of the phosphorescence process. r As shown in Table 2, the calculated k for 4a r It is 1.27 × 10 5 s -1 , and the k of 4a in CH3CN r 2.95×10 5 s -1 The experimental values ​​are consistent with the actual values. The spin-orbit coupling matrix element (SOCME) was calculated, and in S 10 And T1 (217.76cm) -1 S8 and T1 (149.44cm) -1) Two large SOCMEs were observed between the couplings. 4a of S 10 The S8 state primarily originates from the HOMO→L+2 and HOMO→L+1 transitions, respectively, while the T1 state primarily originates from the HOMO→LUMO transition. The LUMO, L+1, and L+2 orbitals originate from different Au-6p orbitals (6p... x 6p y Or 6p z The phosphorescence of 4a is attributed to the moderate contribution of the Au-6p orbital to the LMMCT transition.

[0674] Example 2. Materials and methods for catalyzing photo-induced organic reactions using Au(I) complexes under near-ultraviolet and / or visible light.

[0675] Homocoupling of (2-bromoethyl)benzene and alkyl bromide

[0676] Scheme 1. Comparison of 1a and 4a in the homologous coupling of (2-bromoethyl)benzene.

[0677]

[0678] Scheme 2. Photoinduced homocoupling of alkyl bromides [a]

[0679]

[0680] Exemplary reaction schemes that produce 6, 7, and 8:

[0681]

[0682] Other reactants R'-Br:

[0683]

[0684] reactant R'-Cl:

[0685]

[0686] Products R'-R' and their yields:

[0687]

[0688] [a] Alkyl bromide (1 mmol), 4a (0.01 mmol), iPr2NMe (2 mmol), CH3CN (1 mL), and MeOH (1 mL) were irradiated at room temperature with N2 and a 405 nm LED (12 W) for 12 h. [b] Product yields were based on NMR and GC-MS analysis, using 1,3,5-trimethoxybenzene as an internal standard. [c] 4a (0.02 mmol). [d] 4a (0.05 mmol). [e] Separation yields. [f] 4-Methylbenzyl chloride as a substrate. [g] Under 442 nm LED (12 W) irradiation.

[0689] To a round-bottom flask, add alkyl bromide (1 mmol), gold complex 4a (1-5 mol%, 0.01 mmol), iPr₂NMe (3 mmol), CH₃CN (1 mL), and MeOH (1 mL). Stir the mixture at room temperature under N₂ and 405 nm light for 12 hours. After removing volatiles under reduced pressure, the crude product is purified by silica gel chromatography (dichloromethane / n-hexane). Partial product conversion is determined by GC-MS analysis using an internal standard.

[0690] 1,4-Diphenylbutane (5'). Following a standard procedure, 72 mg (68%) of 5' was obtained as a colorless oil (Peng et al., J. Org. Chem. 2013, 78, 10960-10967). 1 H NMR (500MHz, CDCl3): δ7.25–7.28(m,4H,Ar),7.17(t,J=6.5Hz,6H,Ar),2.63(t,J=6.8Hz,4H,ArCH2CH2),1.65–1.68(m,4H,ArCH2CH2). 13C NMR (126MHz, CDCl3): δ142.6(s,Ar), 128.4(s,Ar), 128.2(s,Ar), 125.6(s,Ar), 35.8(s,ArCH2CH2), 31.1(s,ArCH2CH2).

[0691]

[0692] 1,2-Diphenylethane (9). Following the general procedure, 84 mg (92%) of 9 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1 H NMR (500MHz, CDCl3): δ7.28 (t, J = 7.4Hz, 4H, Ar), 7.18–7.21 (m, 6H, Ar), 2.92 (s, 4H, ArCH2). 13 C NMR (126MHz, CDCl3): δ141.8(s,Ar), 128.4(s,Ar), 128.3(s,Ar), 125.9(s,Ar), 37.9(s,ArCH2).

[0693]

[0694] 1,2-Di-p-Tolylethane (10). Following a general procedure, 100 mg (95%) of 10 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1 H NMR (400MHz, CDCl3): δ7.09(s,8H,Ar),2.86(s,4H,ArCH2),2.32(s,6H,Me). 13 C NMR (101MHz, CDCl3): δ138.8(s,Ar), 135.3(s,Ar), 129.0(s,Ar), 128.3(s,Ar), 37.6(s,ArCH2), 21.0(s,Me).

[0695]

[0696] 1,2-Bis(4-methoxyphenyl)ethane (11). Following a general procedure, 61 mg (50%) of 11 was obtained as a white solid (Liu et al., Chem. Asian J. 2017, 12, 673–678). 1H NMR (500MHz, CDCl3): δ7.08 (d, J = 8.4Hz, 4H, Ar), 6.82 (d, J = 8.4Hz, 4H, Ar), 3.79 (s, 6H, OMe), 2.82 (s, 4H, ArCH2). 13 C NMR (126MHz, CDCl3): δ157.8(s,Ar), 134.0(s,Ar), 129.4(s,Ar), 113.7(s,Ar), 55.2(s,OMe), 37.3(s,ArCH2).

[0697]

[0698] 1,2-Bis(4-fluorophenyl)ethane (12). Following a general procedure, 88 mg (81%) of 12 was obtained as a white solid (Park et al., Chem. Eur. J. 2016, 22, 17790–17799). 1 H NMR (500MHz, CDCl3): δ7.05–7.08 (m, 4H, Ar), 6.94 (t, J = 8.4Hz, 4H, Ar), 2.86 (s, 4H, ArCH2). 13 C NMR (126MHz, CDCl3): δ161.4(d,J C-F =243.6Hz,Ar),136.9(d,J) C-F =3.1Hz,Ar),129.8(d,J) C-F =7.8Hz,Ar),115.1(d,J C-F =21.1Hz,Ar),37.1s,ArCH2. 19 F NMR (471MHz, CDCl3): δ-117.5 (s).

[0699]

[0700] 1,2-Bis(4-(trifluoromethyl)phenyl)ethane (14). Following a general procedure, 119 mg (75%) of 14 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1 H NMR (500MHz, CDCl3): δ7.53 (d, J = 8.0 Hz, 4H, Ar), 7.24 (d, J = 8.0 Hz, 4H, Ar), 2.99 (s, 4H, ArCH2). 13C NMR (126MHz, CDCl3): δ145.0(s,Ar),128.8(s,Ar),128.5(s,Ar),125.4(q,J C-F =3.8Hz,Ar),124.4(q,J C-F =315.2Hz,CF3),37.2(s,ArCH2). 19 F NMR (471MHz, CDCl3): δ-62.4 (s).

[0701]

[0702] 4,4'-(ethane-1,2-diyl)dibenzylnitrile (15). Following a general procedure, 89 mg (77%) of 15 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1 H NMR (400MHz, CDCl3): δ7.57 (d, J = 8.1Hz, 4H, Ar), 7.22 (d, J = 8.1Hz, 4H, Ar), 3.00 (s, 4H, ArCH2). 13 C NMR (101MHz, CDCl3): δ146.0(s,Ar), 132.3(s,Ar), 129.2(s,Ar), 118.8(s,CN), 110.3(s,Ar), 37.2(s,ArCH2).

[0703]

[0704] Dimethyl 4,4'-(ethane-1,2-diyl)dibenzoate (16). Following a general procedure, 140 mg (94%) of 16 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1 H NMR (500MHz, CDCl3): δ7.93(d,J=8.1Hz,4H,Ar),7.19(d,J=8.1Hz,4H,Ar),3.90(s,6H,COOMe),2.99(s,4H,ArCH2). 13 C NMR (126MHz, CDCl3): δ167.0(s,COOMe),146.5(s,Ar),129.7(s,Ar),128.5(s,Ar),128.1(s,Ar),52.0(s,COOMe),37.4(s,ArCH2).

[0705]

[0706] 1,2-Di(naphthyl-2-yl)ethane (17). Following a general procedure, 100 mg (71%) of 17 was obtained as a white solid (Cao and Shi, J. Am. Chem. Soc. 2017, 139, 6546-6549). 1 H NMR (400MHz, CDCl3): δ7.76–7.82(m,6H,Ar),7.65(s,2H,Ar),7.40–7.46(m,4H,Ar),7.36(d,J=8.3Hz,2H,Ar),3.18(s,4H,ArCH2). 13 C NMR (101MHz, CDCl3): δ139.3(s,Ar),133.6(s,Ar),132.0(s,Ar),127.9(s,Ar),127.6(s,A r),127.5(s,Ar),127.3(s,Ar),126.5(s,Ar),125.9(s,Ar),125.2(s,Ar),38.0(s,ArCH2).

[0707]

[0708] 1,2-Bis(6-methylpyridin-2-yl)ethane (18). Following a general procedure, 18 mg (17%) of 18 was obtained as a white solid (Ito et al., J. Organomet. Chem. 1986, 303, 301–308). 1 H NMR (500MHz, CDCl3): δ7.45(t,J=7.6Hz,2H,Ar), 6.96(d,J=7.6Hz,2H,Ar), 6.93(d,J=7.7Hz,2H,Ar), 3.17(s,4H,ArCH2), 2.55(s,6H,Me). 13 C NMR (126MHz, CDCl3): δ160.5(s,Ar),157.8(s,Ar),136.6(s,Ar),120.7(s,Ar),119.8(s,Ar),38.5(s,ArCH2),24.4(s,Me).

[0709]

[0710] 1,2-Di-o-Tolylethane (19). Following the general procedure, 91 mg (87%) of 19 was obtained as a white solid (Teo et al., Dalton Trans. 2016, 45, 7312–7319). 1H NMR (500MHz, CDCl3): δ7.11–7.20(m,8H,Ar),2.85(s,4H,ArCH2),2.32(s,6H,Me). 13 C NMR (126MHz, CDCl3): δ140.2(s,Ar),135.9(s,Ar),130.2(s,Ar),128.8(s,Ar),126.1(s,Ar),126.0(s,Ar),34.1(s,ArCH2),19.3(s,Me).

[0711]

[0712] Butane-2,3-dimethyldiphenyl (20). Following a general procedure, 53 mg (50%) of 20 was obtained as a white solid (Fallon et al., New J. Chem. 2016, 40, 9912–9916). 1 H NMR (500MHz, CDCl3): δ7.31(t,J=7.5Hz,4H,Ar),7.20–7.23(m,6H,Ar),2.80(br,2H,ArCHMe),1.02(d,J=5.8Hz,6H,ArCHMe). 13 C NMR (126MHz, CDCl3): δ146.5(s,Ar), 128.3(s,Ar), 127.6(s,Ar), 126.0(s,Ar), 47.2(s,ArCHMe), 21.0(s,ArCHMe).

[0713]

[0714] Alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline

[0715] Scheme 3. Photochemical alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline [a]

[0716]

[0717]

[0718] [a] 2-Phenylacetyl-1,2,3,4-Tetrahydroisoquinoline (0.5 mmol), alkyl bromide (0.6 mmol), 4a (0.005 mmol), 2,4,6-trimethylpyridine (1.2 mmol), and CH3CN (2 mL) were isolated and prepared at room temperature under N2 and 405 nm LED irradiation (12 W) for 12 hours, and the yield was determined. [b] 4a (0.01 mmol), 442 nm LED (12 W). [c] Na2CO3 was used instead of 2,4,6-trimethylpyridine.

[0719] Add 0.5 mmol of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, 0.5 mmol of alkyl bromide, 1-2 mol% of gold complex 4a, 1.2 mmol of 2,4,6-trimethylpyridine, and 2 mL of CH3CN to a round-bottom flask. Stir the mixture at room temperature under N2 light and 405 nm and 442 nm light for 12 hours. After removing volatiles under reduced pressure, the crude product is purified by silica gel chromatography (dichloromethane / n-hexane).

[0720] 1-(4-Methylbenzyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (22). Following a standard procedure, 130 mg (83%) of 22 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1 H NMR (400MHz, CDCl3): δ7.21–7.25(m,2H,Ar),7.11–7.17(m,2H,Ar),7.01–7.06(m,3 H,Ar),6.90(d,J=7.8Hz,2H,Ar),6.85(d,J=8.4Hz,2H,Ar),6.70–6.75(m,2H,Ar),4 .87(t,J=6.5Hz,1H,ArCHN),3.50–3.67(m,2H,ArCH2CH2N),3.19–3.23(m,1H,ArCH2 CH2N),2.93–2.98(m,2H,ArCH2CH),2.72–2.78(m,1H,ArCH2CH2N),2.30(s,3H,Me). 13C NMR (101MHz, CDCl3): δ149.3(s,Ar),137.7(s,Ar),135.7(s,Ar),135.7(s,Ar) ,135.1(s,Ar),129.6(s,Ar),129.2(s,Ar),128.8(s,Ar),128.2(s,Ar),127.7 (s,Ar),126.5(s,Ar),125.4(s,Ar),117.0(s,Ar),113.5(s,Ar),61.5(s,ArCHN),42.1(s,ArCH2CH2N),41.9(s,ArCH2CH2N),27.5(s,ArCH2CH),21.1(s,Me).

[0721]

[0722] 4-((2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)methyl)benzyl nitrile (23). Following a standard procedure, 104 mg (64%) of 23 was obtained as a pale yellow oil (Wang et al., Org. Lett. 2015, 17, 3982-3985). 1 H NMR (400MHz, CDCl3): δ7.50(d,J=8.1Hz,2H,Ar),7.07–7.24(m,7H,Ar),6.75–6.82(m,4H,Ar),4.92(t,J=6.5Hz,1H,ArCHN),3.51–3.65(m ,2H,ArCH2CH2N),3.26–3.30(m,1H,ArCH2CH),3.07–3.12(m,1H,ArCH2CH),2.95–3.02(m,1H,ArCH2CH2N),2.64–2.71(m,1H,ArCH2CH2N). 13 CNMR (101MHz, CDCl3): δ149.1(s,Ar),144.5(s,Ar),136.8(s,Ar),135.1(s,Ar ),131.9(s,Ar),130.5(s,Ar),129.3(s,Ar),128.5(s,Ar),127.3(s,Ar),126.9 (s,Ar),125.8(s,Ar),119.1(s,CN),117.9(s,Ar),114.0(s,Ar),110.1(s,Ar),61.0(s,ArCHN),42.5(s,ArCH2CH2N),42.1(s,ArCH2CH2N),27.3(s,ArCH2CH).

[0723]

[0724] 1-(naphthyl-2-methyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (24). Following a standard procedure, 143 mg (82%) of 24 was obtained as a pale yellow oil. 1 H NMR (400MHz, CDCl3): δ7.69–7.80(m,3H,Ar),7.41–7.44(m,3H,Ar),7.23–7.26(m,2H,Ar) ,7.14–7.16(m,3H,Ar),6.98–7.02(m,1H,Ar),6.90(d,J=8.3Hz,2H,Ar),6.70–6.76(m,2H, Ar),4.99–5.02(m,1H,ArCHN),3.52–3.70(m,2H,ArCH2CH2N),3.39–3.44(m,1H,ArCH2CH), 3.13–3.19(m,1H,ArCH2CH),2.95–3.03(m,1H,ArCH2CH2N),2.73–2.80(m,1H,ArCH2CH2N). 13 C NMR (101MHz, CDCl3): δ149.3(s,Ar),137.5(s,Ar),136.4(s,Ar),135.0(s,Ar),133.4(s,Ar),1 32.1(s,Ar),129.3(s,Ar),128.3(s,Ar),128.2(s,Ar),127.7(s,Ar),127.6(s,Ar),127.5(s,A r),126.6(s,Ar),125.8(s,Ar),125.5(s,Ar),125.3(s,Ar),117.3(s,Ar),113.8(s,Ar),61.4( s,ArCHN),42.5(s,ArCH2CH2N),42.2(s,ArCH2CH2N),27.5(s,ArCH2CH).HRMS(ESI):m / z:[M+H] + C 26 H 24 Calculated value of N: 350.1903, measured value: 350.1901.

[0725]

[0726] 1-Phenylacetyl-2-phenyl-1,2,3,4-tetrahydroisoquinoline (25). Following a standard procedure, 64 mg (41%) of 25 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1HNMR(400MHz, CDCl3): δ7.26–7.28(m,1H,Ar),7.11–7.23(m,10H,Ar),6.83(d, J=8.2Hz,2H,Ar),6.72(t,J=7.2Hz,1H,Ar),4.68(t,J=7.1Hz,1H,ArCHN),3.63 –3.66(m,2H,ArCH2CH2N),2.99–3.07(m,1H,ArCH2CH2N),2.70–2.86(m,3H,ArCH2CH2N+PhCH2CH2),2.23–2.33(m,1H,PhCH2CH2),2.01–2.10(m,1H,PhCH2CH2). 13 C NMR (101MHz, CDCl3): δ149.7(s,Ar),141.9(s,Ar),138.8(s,Ar),135.0(s,Ar),129.2(s,Ar),128.6(s,Ar),128.5(s,Ar),128.3(s,Ar),127.3(s,Ar),12 6.5(s,Ar),125.8(s,Ar),117.3(s,Ar),114.2(s,Ar),58.4(s,ArCHN),41.8(s,PhCH2CH2),38.3(s,ArCH2CH2N),32.9(s,ArCH2CH2N),26.8(s,PhCH2CH2).

[0727]

[0728] 1-Butyl-2-phenyl-1,2,3,4-tetrahydroisoquinoline (26). Following the general procedure, 62 mg (47%) of 26 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1H NMR (400MHz, CDCl3): δ7.21–7.23(m,1H,Ar),7.09–7.17(m,4H,Ar),6.86(d,J=8.3Hz,2H ,Ar),6.71(t,J=7.2Hz,1H,Ar),4.63(t,J=7.1Hz,1H,ArCHN),3.56–3.66(m,2H,ArCH2CH 2N),2.82–3.06(m,2H,ArCH2CH2N),1.91–1.99(m,1H,CH2CH2CH2CH3),1.66–1.73(m,1H, CH2CH2CH2CH3),1.31–1.50(m,4H,CH2CH2CH2CH3),0.89(t,J=7.1Hz,3H,CH2CH2CH2CH3). 13 CNMR (101MHz, CDCl3): δ149.6(s,Ar),139.2(s,Ar),135.0(s,Ar),129.2(s,Ar), 128.5(s,Ar),127.3(s,Ar),126.3(s,Ar),125.7(s,Ar),116.8(s,Ar),113.6(s,A r),59.2(s,ArCHN),41.8(s,ArCH2CH2N),36.5(s,ArCH2CH2N),29.1(s,CH2CH2CH2CH3),27.0(s,CH2CH2CH2CH3),22.8(s,CH2CH2CH2CH3),14.1(s,CH2CH2CH2CH3).

[0729]

[0730] 1-Cyclohexyl-2-phenyl-1,2,3,4-tetrahydroisoquinoline (27). Following a standard procedure, 128 mg (88%) of 27 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1 HNMR (400MHz, CDCl3): δ7.06–7.23(m,6H,Ar),6.85(d,J=8.3Hz,2H,Ar),6.67(t,J=7.2Hz,1H,Ar),4.42(d,J=8.1Hz,1H,ArCHN),3.69 –3.75(m,1H,ArCH2CH2N),3.43–3.49(m,1H,ArCH2CH2N),2.96–3.03(m,2H,ArCH2CH2N),1.61–1.98(m,6H,Cy),1.03–1.16(m,5H,Cy).13 CNMR (101MHz, CDCl3): δ149.9(s,Ar),137.8(s,Ar),135.3(s,Ar),129.1(s,Ar),128.3(s,Ar),128.1(s,Ar),126.5(s,Ar),125.1(s,Ar),116.2(s,Ar), 112.9(s,Ar),63.7(s,ArCHN),44.1(s,ArCH2CH2N),42.9(s,ArCH2CH2N),30 .9(s,Cy),30.6(s,Cy),27.4(s,Cy),26.6(s,Cy),26.4(s,Cy),26.4(s,Cy).

[0731]

[0732] 1-(tert-butyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (28). Following the general procedure, 76 mg (57%) of 28 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1 HNMR (400MHz, CDCl3): δ7.11–7.22(m,6H,Ar),6.92(d,J=8.4Hz,2H,Ar),6.67(t,J=7.2Hz,1H,Ar),4.67(s,1H,ArCH N),3.84–3.90(m,1H,ArCH2CH2N),3.50–3.57(m,1H,ArCH2CH2N),2.94–3.10(m,2H,ArCH2CH2N),1.02(s,9H,CMe3). 13 C NMR (101MHz, CDCl3): δ151.1(s,Ar),137.0(s,Ar),135.4(s,Ar),128.9(s,Ar),128.7(s,Ar),128.3(s,Ar),126.5(s,Ar),125. 0(s,Ar),116.6(s,Ar),114.1(s,Ar),66.0(s,ArCHN),44.0(s,ArCH2CH2N),39.2(s,ArCH2CH2N),29.2(s,CMe3),27.3(s,CMe3).

[0733]

[0734] 1-(adamantane-1-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (29). Following a standard procedure, 151 mg (88%) of 29 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1 ¹H NMR (400MHz, CDCl₃): δ 7.12–7.23 (m, 6H, Ar), 6.94 (d, J = 8.4Hz, 2H, Ar), 6.66 (t, J = 7.2Hz, 1H, Ar), 4.55 (s, 1H, ArCHN), 3.88–3.94 (m, 1H, ArCH₂CH₂N), 3.43–3.50 (m, 1H, ArCH₂CH₂N), 3.13–3.21 (m, 1H, ArCH₂CH₂N), 2.92–2.99 (m, 1H, ArCH₂CH₂N), 1.55–1.93 (m, 15H, 1-adamantyl). 13 C NMR (101 MHz, CDCl3): δ 151.2 (s, Ar), 136.2 (s, Ar), 135.5 (s, Ar), 129.1 (s, Ar), 128.9 (s, Ar), 128.0 (s, Ar), 126.6 (s, Ar), 125.0 (s, Ar), 116.2 (s, Ar), 113.7 (s, Ar), 66.9 (s, ArCHN), 45.1 (s, ArCH2CH2N), 41.3 (s, ArCH2CH2N), 41.0 (s, 1-adamantyl), 36.8 (s, 1-adamantyl), 28.8 (s, 1-adamantyl), 27.8 (s, 1-adamantyl).

[0735]

[0736] 2-Phenyl-1-(tetrahydro-2H-pyran-4-yl)-1,2,3,4-tetrahydroisoquinoline (30). Following a general procedure, 128 mg (87%) of 30 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1H NMR (500MHz, CDCl3): δ7.12–7.23(m,5H,Ar),7.06(d,J=7.3Hz,1H,Ar),6.87(d,J=8.2Hz,2H, Ar),6.70(t,J=7.2Hz,1H,Ar),4.43(d,J=8.7Hz,1H,ArCHN),3.95–4.01(m,2H,OCH2CH2CH),3 .50–3.75(m,2H,,OCH2CH2CH),3.21–3.34(m,2H,ArCH2CH2N),2.94–3.06(m,2H,ArCH2CH2N), 1.93–2.01(m,1H,OCH2CH2CH),1.82–1.87(m,1H,OCH2CH2CH),1.44–1.55(m,3H,OCH2CH2CH). 13 C NMR (126MHz, CDCl3): δ149.9(s,Ar),136.8(s,Ar),135.1(s,Ar),129.2(s,Ar),12 8.5(s,Ar),128.2(s,Ar),126.9(s,Ar),125.3(s,Ar),116.9(s,Ar),113.4(s,Ar), 68.3(s,ArCHN),67.9(s,OCH2CH2CH),63.2(s,OCH2CH2CH),42.8(s,ArCH2CH2N),41 .4(s,ArCH2CH2N),30.9(s,OCH2CH2CH),30.8(s,OCH2CH2CH),27.0(s,OCH2CH2CH).

[0737]

[0738] 4-(2-Phenyl-1,2,3,4-Tetrahydroisoquinolin-1-yl)piperidine-1-carboxylic acid tert-butyl ester (31). Following a general procedure, 147 mg (75%) of 31 was obtained as a pale yellow oil (Zhou et al., Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1H NMR (500MHz, CDCl3): δ7.12–7.24(m,5H,Ar),7.05(d,J=7.3Hz,1H,Ar),6.85(d,J=8.2Hz,2H,Ar),6.70(t,J=7.2Hz,1H,A r),4.43(d,J=8.4Hz,1H,ArCHN),3.75–4.31(m,2H,Me3COOCNCH2CH2CH),3.70–3.75(m,1H,Me3COOCNCH2CH2CH),3.48–3.5 3(m,1H,Me3COOCNCH2CH2CH),2.95–3.02(m,2H,ArCH2CH2N),2.33–2.77(m,2H,ArCH2CH2N),1.84–1.93(m,2H,Me3COOCNCH 2CH2CH),1.59–1.64(m,1H,Me3COOCNCH2CH2CH),1.44(s,9H,Me3COOCNCH2CH2CH),1.24–1.36(m,2H,Me3COOCNCH2CH2CH). 13 C NMR (126MHz, CDCl3): δ154.7(s,Me3COOCNCH2CH2CH),149.8(s,Ar),136.9(s,Ar),135.2(s,Ar),129. 2(s,Ar),128.4(s,Ar),128.3(s,Ar),126.9(s,Ar),125.4(s,Ar),116.9(s,Ar),113.3(s,Ar),79.3( s,Me3COOCNCH2CH2CH),63.0(s,ArCHN),42.9(s,ArCH2CH2N),42.6(s,ArCH2CH2N),30.0(s,Me3COOCN CH2CH2CH), 29.8 (s, Me3COOCNCH2CH2CH), 28.4 (s, Me3COOCNCH2CH2CH), 27.1 (s, Me3COOCNCH2CH2CH).

[0739]

[0740] (3S,5S,8R,9S,10S,13S,14S)-10,13-dimethyl-3-((S)-2-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)hexadecylhydro-17H-cyclopenta[a]phenanthrene-17-one (32). Following a general procedure, 140 mg (58%) of 32 was obtained as a white solid. A mixture of cis and trans isomers (1:1). 1H NMR (500MHz, CDCl3): δ7.07–7.23(m,7H,Ar),6.84–6.87(m,2H,Ar),6.66–6.69(m,1H,Ar),4.41(t, J=7.4Hz,1H,CHNPh),3.46–3.74(m,2H,CH2CH2NPh),2.96–3.01(m,2H,CH2CH2NPh),2.39–2.44(m,1H ,alkyl-H), 2.00–2.08(m,1H,alkyl-H), 1.87–1.93(m,1H,alkyl-H), 1.70–1.83(m,4H,alkyl-H), 1.43–1.55(m,3H,alkyl-H), 1.16–1.33(m,8H,alkyl-H), 0.84–1.03(m,7H,alkyl-H), 0.77(s,3H,Me), 0.63–0.68(m,1H,alkyl-H). 13C NMR (126MHz, CDCl3): δ221.41(s,CO),150.08(s,Ar),149.96(s,Ar),137.79(s,Ar),137.68(s,Ar),13 5.20(s,Ar),135.17(s,Ar),129.12(s,Ar),128.32(s,Ar),128.27(s,Ar),126.56(s,Ar),125.18(s,Ar ), 125.16(s,Ar), 116.51(s,Ar), 116.42(s,Ar), 113.31(s,Ar), 113.10(s,Ar), 63.77(s,CHNPh), 63.55(s,CHNPh), 54.72(s,CCO), 54.66(s,CCO), 51.48(s,alkyl-C), 47.80(s,alkyl-C), 46.92(s,alkyl-C), 46.71(s, Alkyl-C), 44.24 (s, alkyl-C), 44.19 (s, alkyl-C), 42.79 (s, alkyl-C), 38.59 (s, alkyl-C), 38.50 (s, alkyl-C), 36.06 (s, alkyl-C), 36.04 (s, alkyl-C), 35.84 (s, alkyl-C), 35.08 (s, alkyl-C), 32.89 (s, alkyl-C), 32.76 (s, alkyl-C), 31.58 (s, alkyl-C) ,30.95(s,alkyl-C),28.74(s,alkyl-C),28.71(s,alkyl-C),27.22(s,alkyl-C),27.11(s,alkyl-C),26.21(s,alkyl-C),26.16(s,alkyl-C),21.73(s,alkyl-C),20.28(s,alkyl-C),13.81(s,alkyl-C),12.39(s,alkyl-C).HRMS(ESI):m / z:[M+H] + C 34 H 44 NO calculated value: 482.3417, measured value: 482.3420.

[0741]

[0742] Cycloning of indole

[0743] Scheme 4a. Preparation of 1-(4-bromobutyl)-4-methoxy-1H-indole.

[0744]

[0745] At room temperature under N2, a solution of 4-methoxy-1H-indole (1.47 g, 10 mmol) in anhydrous THF (20 mL) was added dropwise to a stirred suspension of sodium hydride (0.29 g, 12 mmol) in anhydrous THF (20 mL). The mixture was stirred at room temperature for 0.5 h, followed by the addition of 1,4-dibromobutane (4.32 g, 10 mmol) in anhydrous THF (20 mL) over 1 h. The resulting mixture was then stirred at room temperature for 4 h. A saturated aqueous solution of NH4Cl was then added, the layers separated, and the aqueous phase was extracted with Et2O. The organic layers were combined, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was then purified by rapid silica gel chromatography, eluting with CH2Cl2 / hexane, to give a pale yellow oil (1.16 g, 41%) of 1-(4-bromobutyl)-4-methoxy-1H-indole.

[0746] 1 H NMR (400MHz, CDCl3): δ7.11–7.16(m,1H,Ar),6.95–6.99(m,2H,Ar),6.51–6.61(m,2H,Ar),4.14(t,J=6.8Hz,2H,NCH2CH2CH2CH2Br),3 .96(s,3H,OMe),3.36(t,J=6.5Hz,2H,NCH2CH2CH2CH2Br),1.96–2.04(m,2H,NCH2CH2CH2CH2Br),1.80–1.87(m,2H,NCH2CH2CH2CH2Br). 13 C NMR (101MHz, CDCl3): δ153.5(s,Ar),137.4(s,Ar),126.1(s,Ar),122.4(s,Ar),119.1(s,Ar),102.7(s,Ar),99.2(s,Ar),98.6(s,Ar),55.3(s, OMe),45.7(s,NCH2CH2CH2CH2Br),33.0(s,NCH2CH2CH2CH2Br),29.9(s,NCH2CH2CH2CH2Br),28.8(s,NCH2CH2CH2CH2Br).HRMS(ESI):m / z:[M+H] + C 13 H 17 Calculated BrNO value: 282.0488, measured value: 282.0484.

[0747] Scheme 4b. Preparation of 1-(1-(4-bromobutyl)-1H-indol-3-yl)ethane-1-one.

[0748]

[0749] At room temperature under N2, a solution of 1-(1H-indol-3-yl)ethane-1-one (1.59 g, 10 mmol) in anhydrous THF (20 mL) was added dropwise to a stirred suspension of sodium hydride (0.29 g, 12 mmol) in anhydrous THF (20 mL). The mixture was stirred at room temperature for 0.5 h, and then a solution of 1,4-dibromobutane (4.32 g, 10 mmol) in anhydrous THF (20 mL) was added over a period of 1 h. The resulting mixture was then stirred at room temperature for 4 h. A saturated aqueous solution of NH4Cl was then added, the layers separated, and the aqueous phase was extracted with Et2O. The organic layers were combined, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was then purified by silica gel rapid chromatography, eluted with CH2Cl2 / hexane, to give a pale yellow oil (1.06 g, 36%) of 1-(1-(4-bromobutyl)-1H-indol-3-yl)ethane-1-one.

[0750] 1 H NMR (400MHz, CDCl3): δ8.36–8.39(m,1H,Ar),7.73(s,1H,Ar),7.29–7.36(m,3H,Ar),4.19(t,J=7.0Hz,2H,NCH2CH2CH2CH2Br),3.40 (t,J=6.4Hz,2H,NCH2CH2CH2CH2Br),2.53(s,3H,COMe),2.03–2.10(m,2H,NCH2CH2CH2CH2Br),1.85–1.92(m,2H,NCH2CH2CH2CH2Br). 13 CNMR (101MHz, CDCl3): δ192.9(s,COMe),136.6(s,Ar),134.4(s,Ar),126.3(s,Ar),123.3(s,Ar),122.7(s,Ar),122.5(s,Ar),117.2(s,Ar),109.6(s,Ar) ,46.2(s,COMe),32.6(s,NCH2CH2CH2CH2Br),29.7(s,NCH2CH2CH2CH2Br),28.4(s,NCH2CH2CH2CH2Br),27.6(s,NCH2CH2CH2CH2Br).HRMS(ESI):m / z:[M+H] + C 14 H 17 Calculated BrNO value: 294.0488, measured value: 294.0485.

[0751] Option 4c. Photoinduced cyclization of indole.

[0752]

[0753] Reaction conditions: bromoalkane (0.5 mmol), Na₂CO₃ (1.5 mmol), and 4a (0.0025 mmol, 0.5 mol%) in CH₃CN (2 mL) at room temperature under N₂ and 405 nm LED (12 W) irradiation for 6 hours. [a] 1 mol% of 4a.

[0754] Add bromoalkanes (0.5 mmol), gold complex 4a (0.5–1 mol%), Na₂CO₃ (1.5 mmol), and CH₃CN (2 mL) to a round-bottom flask. Stir the mixture at room temperature under N₂ and 405 nm light for 6 hours. After removing volatiles under reduced pressure, purify the crude product by silica gel chromatography (dichloromethane / n-hexane).

[0755] 6,7,8,9-Tetrahydropyrido[1,2-a]indole (33). Following the general procedure, 81 mg (94%) of 33 was obtained as a white solid (Che et al., J. Chem. Soc. Dalton Trans. 1990, 3215–3219). 1 H NMR (400MHz, CDCl3): δ7.52(d,J=7.5Hz,1H,Ar),7.25(d,J=8.0Hz,1H,Ar),7.05–7.14(m,2H,Ar),6.18(s,1H,Ar),4.03(t,J=6.2Hz,2H,N CH2CH2CH2CH2Ar),2.97(t,J=6.3Hz,2H,NCH2CH2CH2CH2Ar),2.04–2.10(m,2H,NCH2CH2CH2CH2Ar),1.85–1.91(m,2H,NCH2CH2CH2CH2Ar). 13 C NMR(101MHz,CDCl3)δ137.1(s,Ar),136.2(s,Ar),128.2(s,Ar),120.1(s,Ar),119.5(s,Ar),119.5(s,Ar),108.5(s,Ar),97 .5(s,Ar),42.3(s,NCH2CH2CH2CH2Ar),24.2(s,NCH2CH2CH2CH2Ar),23.4(s,NCH2CH2CH2CH2Ar),21.2(s,NCH2CH2CH2CH2Ar).

[0756]

[0757] 2,3-Dihydro-1H-pyrrolo[1,2-a]indole (34). Following the general procedure, 75 mg (95%) of 34 was obtained as a white solid (Che et al., J. Chem. Soc. Dalton Trans. 1990, 3215–3219). 1 H NMR (400MHz, CDCl3): δ7.53(d,J=7.7Hz,1H,Ar),7.24(s,1H,Ar),7.02–7.12(m,2H,Ar),6.15(s,1H,Ar),4. 05(t,J=6.9Hz,2H,NCH2CH2CH2Ar),3.01(t,J=7.3Hz,2H,NCH2CH2CH2Ar),2.56–2.63(m,2H,NCH2CH2CH2Ar). 13 C NMR (101MHz, CDCl3): δ144.5(s,Ar),133.2(s,Ar),132.7(s,Ar),120.3(s,Ar),120.1(s,Ar),119.1(s,A r),109.3(s,Ar),92.3(s,Ar),43.6(s,NCH2CH2CH2Ar),27.8(s,NCH2CH2CH2Ar),24.3(s,NCH2CH2CH2Ar).

[0758]

[0759] 1-Methoxy-6,7,8,9-Tetrahydropyrido[1,2-a]indole (35). Proceeded according to the general procedure, 96 mg (95%) of 35 was obtained as a white solid (Zhou et al., Angew. Chem. 2017, 129, 15889–15893; Angew. Chem. Int. Ed. 2017, 56, 15683–15687). 1 H NMR (400MHz, CDCl3): δ7.05(t,J=7.9Hz,1H,Ar),6.90(d,J=8.2Hz,1H,Ar),6.52(d,J=7.7Hz,1H,Ar),6.27(d,J=0.9Hz,1H,Ar),4.01(t,J=6.2Hz,2H,N CH2CH2CH2CH2...

Claims

1. Gold (I) complexes having the following structure: ， in: (a) n10 and n12 are both 1; (b) R1 to R8 are unsubstituted morpholino groups, and n1 to n8 are 1; and (c) Each occurrence of A' is an anion.

2. The gold (I) complex according to claim 1, wherein each occurrence of A' is a fluoride ion, chloride ion, bromide ion, iodide ion, dihydrogen phosphate, hexafluorophosphate, trifluoromethanesulfonate, nitrate, bisulfate, chlorate, bromate, chlorite, bicarbonate, perchlorate, acetate, formate, cyanide, cyanate, thiocyanate, or hydroxide ion.

3. The gold (I) complex according to claim 1, wherein the gold (I) complex has the following structure: 。 4. The gold(I) complex according to claim 1, wherein the gold(I) complex has the following extinction coefficient in solution or as a powder: at least 0.1 × 10⁻⁶. 4 M -1 cm -1 The extinction coefficient was determined using the absorption spectrum of the gold (I) complex.

5. The gold(I) complex according to claim 1, wherein the gold(I) complex has the following radiation attenuation rate in solution or as a powder: at least 0.45 × 10⁻⁶. 4 s -1 The radiation attenuation rate is determined using the emission quantum yield and emission lifetime of the gold (I) complex.

6. The gold(I) complex according to claim 1, wherein the gold(I) complex has the following diffusion-corrected bimolecular quenching rate constant: at least 3.5 × 10⁻⁶. 5 s -1 The diffusion-corrected bimolecular quenching rate constant is determined using a quencher.

7. The gold (I) complex according to claim 1, wherein the gold (I) complex has a reduction potential of less than -1.46 V relative to a saturated calomel electrode, the reduction potential being determined by cyclic voltammetry.

8. A method for catalyzing a photo-redox reaction using one or more gold (I) complexes according to claim 1, wherein the method comprises: (i) Expose the reaction mixture to light at a certain temperature for a period of time sufficient to form a product. The reaction mixture comprises reactants, solvents, and one or more gold (I) complexes, and The light described has a wavelength in the range of 360 nm to 450 nm.

9. The method according to claim 8, wherein, The photo-oxidation-reduction reaction is the homologous coupling of organohalides, alkylation of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, cyclization of indole, reductive dehalogenation of aryl halides, or cleavage of CH bonds, or a combination thereof.

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