A class of organometallic compounds constructed based on terpyridine ligands and preparation methods

Abstract

The present invention relates to the technical field of metal organic supramolecular polymers, and discloses a class of organometallic compounds constructed based on terpyridine ligands and a preparation method thereof. The organometallic compounds are constructed based on terpyridine ligands, and the organometallic compounds contain terpyridine ligands, which are one or more of an organic ligand L1 having a structure of formula (I), a metal organic ligand L2 having a structure of formula (II), an organic ligand L3 having a structure of formula (III), and a metal organic ligand L4 having a structure of formula (IV). The organometallic compounds constructed based on terpyridine ligands provided by the present invention can be used in the fields of luminescent materials, conductive polymers, bioluminescent probes, dye-sensitized solar cells, phototherapy anticancer drugs, etc. The preparation method provided is simple, the reaction conditions are mild, and it is conducive to large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of metal organic supramolecular polymers, and in particular to a class of organometallic compounds constructed based on terpyridine ligands and a preparation method thereof. Background Art

[0002] Nature constructs numerous complex biological systems with unique structures and desirable functions through precise self-assembly. Over the past few decades, inspired by nature's top-down self-assembly, scientists have been dedicated to designing and constructing supramolecules with diverse functions and complex structures by leveraging various non-covalent interactions, such as hydrogen bonds, electrostatic interactions, hydrophobic interactions, π-π interactions, and metal-ligand coordination bonds. Metal-ligand coordination bonds have garnered significant attention due to their strong binding capacity, directional controllability, and rich configurations. Coordination-driven self-assembly has enabled the construction of a wide range of complex supramolecules. Among the numerous ligands used to construct metal-organic supramolecular polymers, pyridine ligands have been widely used due to their high stability, flexible coordination modes, and structural modifiability. Furthermore, the metal complexes they form often exhibit excellent catalytic, photoelectric conversion, and magnetic properties. However, the construction of organometallic compounds based on terpyridine ligands using conventional techniques presents numerous technical difficulties, and no relevant reports have been reported domestically or internationally. Summary of the Invention

[0003] In response to the problems existing in the prior art, the present invention provides a class of organometallic compounds constructed based on terpyridine ligands and a preparation method thereof. Based on the synthesis and self-assembly of terpyridine ligands, a class of organometallic compounds constructed based on terpyridine ligands and a preparation method thereof are proposed, which can obtain organometallic compounds with good performance in batches.

[0004] In the first aspect, the present invention provides a class of organometallic compounds constructed based on terpyridine ligands, which are organometallic compounds constructed based on terpyridine ligands, and the structure is a hexagonal metal-organic supramolecule H1, a hexagonal metal-organic supramolecule H2 or a polymer P1, which is constructed by terpyridine ligands.

[0005] Preferably, the terpyridine ligand is one or more of an organic ligand L1, a metal organic ligand L2, an organic ligand L3, and a metal organic ligand L4.

[0006] More preferably, the organic ligand L1 has the structure of formula (I), as follows:

[0007]

[0008] More preferably, the metal organic ligand L2 has a structure of formula (II), as follows:

[0009]

[0010] More preferably, the organic ligand L3 has a structure of formula (III), as follows:

[0011]

[0012] More preferably, the metal organic ligand L4 has a structure of formula (IV), as follows:

[0013]

[0014] More preferably, the synthesis route of the organic ligand L1 is as follows:

[0015]

[0016] More preferably, the synthesis route of the organic ligand L2 is as follows:

[0017]

[0018] More preferably, the synthesis route of the organic ligand L3 is as follows:

[0019]

[0020] More preferably, the synthesis route of the metal organic ligand L4 is as follows:

[0021]

[0022] Preferably, the hexagonal metal organic supramolecule H1 has a structure of formula (V), the hexagonal metal organic supramolecule H2 has a structure of formula (VI), and the polymer P1 has a structure of formula (VII), as follows:

[0023]

[0024]

[0025] M is a transition metal ion.

[0026] Preferably, the organometallic compound constructed based on the terpyridine ligand includes a transition metal ion M.

[0027] More preferably, the transition metal ion M includes Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd2+ 、Ru 2+ At least one of various transition metal ions.

[0028] More preferably, the transition metal ion M is mainly a divalent metal ion, which can form tpy-M(II)-tpy with a pseudo-octahedral structure with the terpyridine ligand.

[0029] In a second aspect, the present invention further provides a method for preparing an organometallic compound constructed based on a terpyridine ligand, comprising the following steps:

[0030] (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system;

[0031] (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution;

[0032] (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

[0033] Preferably, in step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:0.5-1.5.

[0034] More preferably, in step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:1.

[0035] Preferably, in step (2), the heating temperature is 40-70°C.

[0036] Preferably, in step (2), the reaction time is 8 to 12 hours.

[0037] Preferably, in step (2), in the methanol solution of the metal salt, the metal salt cation is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of the metal salt cations that are easily soluble in alcohol solvents, wherein the anion of the metal salt solution is NO3 - 、SO4 2- or Cl - One of them.

[0038] Preferably, in step (3), the anion displacer is one of ammonium hexafluorophosphate or lithium bis(trifluoromethanesulfonyl)imide.

[0039] Preferably, in step (3), the anion displacer mainly functions to displace the NO3 introduced by the methanol solution of the metal salt. - 、SO4 2- or Cl - The anions enable the organic metal compound constructed based on the terpyridine ligand to be better precipitated in the solvent, which is beneficial to the subsequent separation of the precipitate.

[0040] Preferably, in step (3), the washing solvent is H2O and MeOH.

[0041] More preferably, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal-organic supramolecule H1, the terpyridine ligand in step (1) is an organic ligand L1 or a metal-organic ligand L2.

[0042] More preferably, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H2, the terpyridine ligand in step (1) is an organic ligand L3 or a metal organic ligand L4.

[0043] More preferably, when the organometallic compound constructed based on the terpyridine ligand is polymer P1, the terpyridine ligand in step (1) is the metal organic ligand L2.

[0044] Preferably, the preparation method of the organic ligand L1 comprises the following steps:

[0045] 1,2,3,4-Tetrabromo-5,6-bis(hexyloxy)benzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to a Suzuki coupling reaction to obtain an organic ligand L1.

[0046] Preferably, the reaction solvent of the Suzuki-coupling reaction is tetrahydrofuran and water.

[0047] More preferably, the volume ratio of tetrahydrofuran to water is 10:1.

[0048] Preferably, in step (1), the reaction temperature of the Suzuki-coupling reaction is 90°C.

[0049] Preferably, in step (1), the reaction time of the Suzuki-coupling reaction is 4 days.

[0050] Preferably, the organic ligand L1 is prepared according to the synthesis route of the organic ligand L1.

[0051] Preferably, the method for preparing the metal organic ligand L2 comprises the following steps:

[0052] (1) Substitution reaction of 4-nitrophenol and Br2 to obtain compound 1;

[0053]

[0054] (2) reacting compound 1 with ICH3 to obtain compound 2;

[0055]

[0056] (3) Compound 2 and SnCl4 were refluxed in ethanol for 8 h to obtain compound 3;

[0057]

[0058] (4) Compound 3 and Br2 were refluxed in ethanol for 24 h to obtain compound 4;

[0059]

[0060] (5) reacting compound 4 with KI to obtain compound 5;

[0061]

[0062] (6) Compound 5 and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to Suzuki coupling reaction to obtain compound 6;

[0063]

[0064] (7) 5-bromo-1,2,3-trimethoxybenzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to Suzuki coupling reaction to obtain compound 7;

[0065]

[0066] (8) Compound 7 is reacted with Br2 to obtain compound 8;

[0067]

[0068] (9) Compound 8 is subjected to coordination reaction with RuCl3·3H2O to obtain compound 9;

[0069]

[0070] (10) Compound 6 and compound 9 are reacted to obtain compound 10;

[0071]

[0072] (11) Compound 10 and 4′-(4-boronic acid phenyl)-2,2′:6′,2″-terpyridine were subjected to Suzuki coupling reaction to obtain the metal organic ligand L2.

[0073] Preferably, in step (1), the reaction solvent for the substitution reaction is ethanol.

[0074] Preferably, in step (2), the reaction solvent is acetonitrile.

[0075] Preferably, in step (6), the reaction solvent is tetrahydrofuran and water.

[0076] More preferably, in step (6), the volume ratio of tetrahydrofuran to water is 10:1.

[0077] Preferably, in step (6), the reaction temperature is 90° C. and the reaction time is 1 day.

[0078] Preferably, in step (7), the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0079] More preferably, in step (7), the volume ratio of tetrahydrofuran to water is 10:1.

[0080] Preferably, in step (7), the reaction temperature is 90° C. and the reaction time is 1 day.

[0081] Preferably, in step (8), the reaction solvent is chloroform.

[0082] Preferably, in step (9), the reaction solvent of the coordination reaction is ethanol, and the reaction temperature is 80°C.

[0083] Preferably, in step (10), the reaction solvent is a mixed solution of chloroform and methanol.

[0084] More preferably, in step (10), the volume ratio of the mixed solution of chloroform and methanol is 1:1.

[0085] More preferably, in step (10), the reaction temperature is 80°C.

[0086] Preferably, in step (11), the reaction solvent of the Suzuki-coupling reaction is a mixed solvent of acetonitrile, water and methanol.

[0087] More preferably, in step (11), the volume ratio of acetonitrile, water and methanol is 10:1:1.

[0088] Preferably, in step (11), the preferred temperature is 90° C. and the reaction time is 6 days.

[0089] Preferably, the preparation method of the organic ligand L3 comprises the following steps:

[0090] 1,2,3,4-Tetrabromo-5,6-di(hexyloxy)benzene and compound 12 were subjected to Suzuki coupling reaction to obtain organic ligand L3.

[0091]

[0092] Preferably, the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0093] Preferably, the preparation method of compound 12 is as follows:

[0094] (1) Suzuki coupling reaction of 4-bromoiodobenzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine to obtain compound 11;

[0095]

[0096] (2) Compound 11 is reacted with diboronic acid pinacol ester to obtain compound 12.

[0097] More preferably, the volume ratio of tetrahydrofuran to water is 10:1.

[0098] Preferably, the reaction temperature of the Suzuki coupling reaction is 90° C. and the reaction time is 4 days.

[0099] Preferably, the preparation method of the metal organic ligand L4 comprises the following steps:

[0100] (1) Suzuki coupling reaction of 4-bromoiodobenzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine to obtain compound 11;

[0101]

[0102] (2) reacting compound 11 with biboronic acid pinacol ester to obtain compound 12;

[0103]

[0104] (3) reacting compound 12 with compound 5 to obtain compound 13;

[0105]

[0106] (4) Compound 13 and 4-trimethylsilylphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 14;

[0107]

[0108]

[0109] (5) Compound 14 is reacted with Br2 to obtain compound 15;

[0110]

[0111] (6) Compound 11 and 3,4,5-trimethoxyphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 16;

[0112]

[0113] (7) Compound 16 is reacted with Br2 to obtain compound 17;

[0114]

[0115] (8) Compound 17 and 4-trimethylsilylphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 18;

[0116]

[0117] (9) Compound 18 is reacted with Br2 to obtain compound 19;

[0118]

[0119] (10) Compound 19 was reacted with RuCl3·3H2O to obtain compound 20;

[0120]

[0121] (11) Compound 20 and compound 15 are reacted to obtain compound 21;

[0122]

[0123] (12) Compound 21 and 4′-(4-boronic acid phenyl)-2,2′:6′,2″-terpyridine were subjected to Suzuki coupling reaction to obtain metal organic ligand L4.

[0124] Preferably, in step (1), the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0125] More preferably, in step (1), the volume ratio of tetrahydrofuran to water is 10:1.

[0126] Preferably, in step (1), the reaction temperature of the Suzuki-coupling reaction is 90° C., and the reaction time is 12 h.

[0127] Preferably, in step (2), the reaction solvent is 1,4-dioxane, the reaction temperature is 85° C., and the reaction time is 12 h.

[0128] Preferably, in step (3), the reaction solvent is tetrahydrofuran and water.

[0129] More preferably, in step (3), the volume ratio of tetrahydrofuran to water is 10:1.

[0130] Preferably, in step (3), the reaction temperature is 90° C. and the reaction time is 12 h.

[0131] Preferably, in step (4), the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0132] More preferably, in step (4), the volume ratio of tetrahydrofuran to water is 10:1.

[0133] Preferably, in step (4), the reaction temperature of the Suzuki-coupling reaction is 90° C., and the reaction time is 4 days.

[0134] Preferably, in step (6), the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0135] More preferably, in step (6), the volume ratio of tetrahydrofuran to water is 10:1.

[0136] Preferably, in step (6), the reaction temperature of the Suzuki-coupling reaction is 90° C., and the reaction time is 4 days.

[0137] Preferably, in step (8), the reaction solvent for the Suzuki-coupling reaction is tetrahydrofuran and water.

[0138] More preferably, in step (8), the volume ratio of tetrahydrofuran to water is 10:1.

[0139] Preferably, in step (8), the reaction temperature of the Suzuki-coupling reaction is 90° C., and the reaction time is 2 days.

[0140] Preferably, in step (10), the reaction solvent is ethanol and the reaction temperature is 80°C.

[0141] Preferably, in step (11), the reaction solvent is a mixed solution of chloroform and methanol.

[0142] More preferably, in step (11), the volume ratio of the mixed solution of chloroform and methanol is 1:1.

[0143] Preferably, in step (11), the reaction temperature is 80°C.

[0144] Preferably, in step (12), the reaction solvent of the Suzuki-coupling reaction is a mixed solvent of acetonitrile, water and methanol.

[0145] More preferably, in step (12), the volume ratio of the mixed solvent of acetonitrile, water and methanol is 10:1:1.

[0146] Preferably, in step (12), the reaction temperature of the Suzuki-coupling reaction is 90° C., and the reaction time is 6 days.

[0147] More preferably, the Suzuki-coupling reaction in the preparation method of the organic ligand L1, the preparation method of the metal organic ligand L2, the preparation method of the organic ligand L3, and the preparation method of the metal organic ligand L4 of the present invention is obtained by using tetrakis(triphenylphosphine)palladium-catalyzed coupling, and an acid binding agent may be added to the reaction system, and the acid binding agent is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

[0148] In a third aspect, the present invention provides applications of organometallic compounds constructed based on terpyridine ligands.

[0149] The organometallic compound constructed based on the terpyridine ligand is used as a raw material for the manufacture of luminescent materials, conductive polymers, bioluminescent probes, dye-sensitized solar cells, phototherapy anticancer drugs and other products.

[0150] Compared with the prior art, the present invention provides a class of organometallic compounds constructed based on terpyridine ligands and a preparation method thereof, which have the following beneficial effects:

[0151] (1) The organometallic compound constructed based on terpyridine ligands and the preparation method thereof provided by the present invention focus on the terpyridine ligands and coordination reactions. By controlling the metal coordination ions, ratios, solvents, temperature and other conditions, it helps to further improve the morphology selectivity and further prepare uniform hexagonal metal organic supramolecules.

[0152] (2) The organometallic compound constructed based on the terpyridine ligand provided by the present invention has more coordination sites and stronger binding ability than other pyridine ligands, and can coordinate with a variety of transition metals. Therefore, the present invention uses multiple tpy groups to design and construct supramolecular structures, which can not only study their potential application value, but also contribute to the structural diversity and application fields of supramolecular chemistry.

[0153] (3) The preparation method of the organometallic compound constructed based on the terpyridine ligand provided by the present invention is simple in preparation method and mild in reaction conditions, which is conducive to large-scale industrial production.

[0154] (4) The organometallic compounds constructed based on terpyridine ligands provided by the present invention realize metal-to-terpyridine ligand charge transfer (MLCT) by coordinating with transition metal ions, and produce a charge transfer effect under light or electrical stimulation. Therefore, they have broad basic research value and potential application research value in the fields of luminescent materials, conductive polymers, bioluminescent probes, dye-sensitized solar cells, phototherapy and anti-cancer drugs, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0155] Figure 1 1HNMR spectrum of compound 1 prepared in Example 2 of the present invention;

[0156] Figure 2 1HNMR spectrum of compound 2 prepared in Example 2 of the present invention;

[0157] Figure 3 1HNMR spectrum of compound 4 prepared in Example 2 of the present invention;

[0158] Figure 4 1HNMR spectrum of compound 5 prepared in Example 2 of the present invention;

[0159] Figure 5 1HNMR spectrum of compound 6 prepared in Example 2 of the present invention;

[0160] Figure 6 1HNMR spectrum of compound 7 prepared in Example 2 of the present invention;

[0161] Figure 7 1HNMR spectrum of compound 8 prepared in Example 2 of the present invention;

[0162] Figure 8 1HNMR spectrum of compound 10 prepared in Example 2 of the present invention;

[0163] Figure 9 This is the 1H NMR spectrum of compound 11 prepared in Example 4 of the present invention;

[0164] Figure 10 This is the 1HNMR spectrum of compound 12 prepared in Example 4 of the present invention;

[0165] Figure 11 This is the 1HNMR spectrum of compound 13 prepared in Example 4 of the present invention;

[0166] Figure 12 1HNMR spectrum of compound 14 prepared in Example 4 of the present invention;

[0167] Figure 13This is the 1HNMR spectrum of compound 15 prepared in Example 4 of the present invention;

[0168] Figure 14 1HNMR spectrum of compound 16 prepared in Example 4 of the present invention;

[0169] Figure 15 This is the 1H NMR spectrum of compound 17 prepared in Example 4 of the present invention;

[0170] Figure 16 1HNMR spectrum of compound 18 prepared in Example 4 of the present invention;

[0171] Figure 17 This is the 1H NMR spectrum of compound 19 prepared in Example 4 of the present invention;

[0172] Figure 18 This is the 1HNMR spectrum of compound 21 prepared in Example 4 of the present invention;

[0173] Figure 19 1HNMR spectrum of the organic ligand L1 prepared in Example 1 of the present invention;

[0174] Figure 20 1HNMR spectrum of the metal organic ligand L2 prepared in Example 2 of the present invention;

[0175] Figure 21 1HNMR spectrum of the organic ligand L3 prepared in Example 3 of the present invention;

[0176] Figure 22 1HNMR spectrum of the metal organic ligand L4 prepared in Example 4 of the present invention;

[0177] Figure 23 1HNMR spectrum of the hexagonal metal organic supramolecule H1 prepared in Example 8 of the present invention;

[0178] Figure 24 1HNMR spectrum of the hexagonal metal organic supramolecule H2 prepared in Example 9 of the present invention;

[0179] Figure 25 This is the ESI-MS spectrum of the hexagonal metal organic supramolecule H1 prepared in Example 8 of the present invention;

[0180] Figure 26 This is the ESI-MS spectrum of the hexagonal metal organic supramolecule H2 prepared in Example 9 of the present invention;

[0181] Figure 27 This is the ESI-MS spectrum of the metal organic ligand L2 prepared in Example 2 of the present invention;

[0182] Figure 28 This is the ESI-MS spectrum of the metal organic ligand L4 prepared in Example 4 of the present invention;

[0183] Figure 29 TEM image of the hexagonal metal organic supramolecule H1 prepared in Example 8 of the present invention;

[0184] Figure 30 TEM image of the hexagonal metal organic supramolecule H2 prepared in Example 9 of the present invention;

[0185] Figure 31 This is a SEM image of polymer P1 prepared in Example 10 of the present invention;

[0186] Figure 32 This is a TEM image of polymer P1 prepared in Example 10 of the present invention. Figure 32 (a) is the 500 nm TEM image of polymer P1, (b) is the 200 nm TEM image of polymer P1, (c) is the 200 nm TEM image of polymer P1, and (d) is the 50 nm TEM image of polymer P1;

[0187] Figure 33 UV-visible absorption spectra of the organic ligand L1 prepared in Example 1, the metal-organic ligand L2 prepared in Example 2, the organic ligand L3 prepared in Example 3, the metal-organic ligand L4 prepared in Example 4, the hexagonal metal-organic supramolecule H1 prepared in Example 8, and the hexagonal metal-organic supramolecule H2 prepared in Example 9 of the present invention;

[0188] Figure 34 Fluorescence emission spectra of the organic ligand L1 prepared in Example 1, the metal-organic ligand L2 prepared in Example 2, the organic ligand L3 prepared in Example 3, the metal-organic ligand L4 prepared in Example 4, the hexagonal metal-organic supramolecule H1 prepared in Example 8, and the hexagonal metal-organic supramolecule H2 prepared in Example 9 of the present invention;

[0189] Figure 35 Low-temperature fluorescence emission spectra of the organic ligand L1 prepared in Example 1, the metal-organic ligand L2 prepared in Example 2, the organic ligand L3 prepared in Example 3, the metal-organic ligand L4 prepared in Example 4, the hexagonal metal-organic supramolecule H1 prepared in Example 8, and the hexagonal metal-organic supramolecule H2 prepared in Example 9 of the present invention;

[0190] Figure 36 This is a molecular structure diagram of the hexagonal metal organic supramolecule H1 prepared in Example 8 of the present invention;

[0191] Figure 37 This is a molecular structure diagram of the hexagonal metal organic supramolecule H2 prepared in Example 9 of the present invention;

[0192] Figure 38 This is a molecular structure diagram of polymer P1 prepared in Example 10 of the present invention;

[0193] Figure 39 These are molecular structure diagrams of the organometallic compounds constructed based on terpyridine ligands prepared in Example 7 of the present invention, (a) is the molecular structure diagram of the hexagonal metal-organic supramolecule H1, (b) is the molecular structure diagram of the hexagonal metal-organic supramolecule H1, and (c) is the molecular structure diagram of the polymer P1. DETAILED DESCRIPTION

[0194] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings and multiple embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0195] Example 1

[0196] See attached Figure 1-39 This embodiment provides an organometallic compound based on a terpyridine ligand. The organometallic compound is an organometallic compound constructed with a terpyridine ligand. The organometallic compound comprises a terpyridine ligand. The terpyridine ligand is one or more of an organic ligand L1 having a structure of formula (I), a metal organic ligand L2 having a structure of formula (II), an organic ligand L3 having a structure of formula (III), and a metal organic ligand L4 having a structure of formula (IV), as follows:

[0197]

[0198]

[0199] The organometallic compound is a hexagonal metal organic supramolecule H1, a hexagonal metal organic supramolecule H2 or a polymer P1, which is composed of the terpyridine; the hexagonal metal organic supramolecule H1 has a structural formula of formula (V), the hexagonal metal organic supramolecule H2 has a structural formula of formula (VI), and the polymer P1 has a structural formula of formula (VII), as follows:

[0200]

[0201]

[0202] M is a transition metal ion.

[0203] The transition metal ion M includes Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of various transition metal ions.

[0204] The method for preparing an organometallic compound constructed based on a terpyridine ligand provided in an embodiment of the present invention comprises the following steps:

[0205] (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system;

[0206] (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution;

[0207] (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

[0208] This embodiment provides a method for preparing an organic ligand L1, comprising the following steps:

[0209]

[0210] To 1,2,3,4-tetrabromo-5,6-bis(hexyloxy)benzene (594.0 mg, 1.0 mmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (2.1 g, 6.0 mmol) and aqueous sodium hydroxide solution (12 mL, 1 M) was added THF (120 ml). Pd(PPh3)4 (300 mg, 5% m / m) was added to the mixture, which was degassed three times and refluxed under N2 protection for 4 d. After the reaction was completed, the mixture was cooled to room temperature, NH4Cl solution was added, and the aqueous phase was extracted with CHCl3. The combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by chromatography (Al2O3) (dichloromethane / methanol v / v, 100:0.5) to give 950.0 mg of a white solid with a yield of 63%. 1 H NMR (400MHz, CDCl3) δ8.74 (s, 4H, B- Tpy-H 3',5' ),8.69-8.68(d,4H,J=4Hz, B- Tpy-H6,6” ),8.64-8.62(d,4H,J=4Hz, B- Tpy-H 3,3” ),8.58(s,4H, A- Tpy-H 3',5' ),8.58-8.57(d,4H,J=4Hz, A- Tpy-H 6,6” ),8.54-8.52(d,4H,J=8Hz, A- Tpy-H 3,3” ),7.86-7.82(t,4H, B- Tpy-H 4,4” ),7.82-7.80(d,4H,J=8Hz, B- Ph-H g ),7.78-7.74(t,4H, A- Tpy-H 4,4” ),7.57-7.55(d,4H,J=8Hz, A- Ph-H g ),7.39-7.37(d,4H,J=8Hz, B- Ph-H h ),7.33-7.29(t,4H, B- Tpy-H 5,5” ),7.24-7.21(t,4H, A- Tpy-H 5,5” ),7.07-7.05(d,4H,J=8Hz, A- Ph-H h ),3.90-3.87(t,4H,H a ).

[0211] The application of the organometallic compound constructed based on terpyridine ligands provided by the present invention is to use the organometallic compound constructed based on terpyridine ligands as raw materials for the manufacture of products such as luminescent materials, conductive polymers, bioluminescent probes, dye-sensitized solar cells, and phototherapy anti-cancer drugs.

[0212] Example 2

[0213] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, which are based on Example 1 and further include the following contents:

[0214] This embodiment provides a method for preparing the metal organic ligand L2, comprising the following steps:

[0215]

[0216] (1) Synthesis of compound 1: Br2 (5.5 g, 1.75 mL) was added to a solution of 4-nitrophenol (2.0 g, 14.4 mmol) in ethanol (80 mL), and the mixture was stirred at room temperature for 3 h. Saturated sodium bisulfite solution was added, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with brine and dried over sodium sulfate, and concentrated in vacuo to obtain 3.5 g of a white solid with a yield of 83%. 1 HNMR (400 MHz, CDCl3) δ 8.41 (H a ),6.61(H b ).

[0217]

[0218] (2) Synthesis of compound 2: CH3CN (60 mL) was added to compound 1 (1 g, 3.4 mmol), ICH3 (630.0 mg, 4.4 mmol) and an aqueous solution of potassium carbonate (1.4 g, 10.2 mmol), and the mixture was refluxed overnight under N2 protection. After the reaction was completed, the mixture was cooled to room temperature and concentrated in vacuo. The crude product was extracted with dichloromethane and water, and the organic phase was dried and concentrated in vacuo to obtain 960 mg of a white product with a yield of 91%. 1 HNMR (400 MHz, CDCl3) δ 8.42 (H a ),3.98(H b ).

[0219]

[0220] (3) Synthesis of compound 3: Compound 2 (900 mg, 2.9 mmol), tin chloride (2.8 g, 14.5 mmol) and ethanol (160 mL) were added to a round-bottom flask. After reflux for 8 h, the reaction mixture was cooled to room temperature, and then sodium hydroxide was added until the solution pH = 10. The organic layer was separated, and the aqueous phase was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and evaporated under reduced pressure to obtain 745 mg of the product as a light brown solid with a yield of 92%.

[0221]

[0222] (4) Synthesis of compound 4: Br2 (3.1 g, 1.1 mL) was added to an ethanol solution (80 mL) of compound 3 (745 mg, 2.7 mmol). After refluxing for 24 hours, a saturated sodium bisulfite solution was added. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were washed with brine and dried over magnesium sulfate, and concentrated in vacuo to afford 1.1 g of a white solid with a yield of 95%. 1 HNMR (400 MHz, CDCl3) δ 4.79 (Ha ),3.81(H b ).

[0223]

[0224]

[0225] (5) Synthesis of compound 5: Compound 4 (1.1 g, 2.5 mmol) and hydrochloric acid (12 mL, 6 mol / L) were added to a flask, and a sodium nitrite solution (350.0 mg, 5 mmol) was added dropwise in an ice bath. KI aqueous solution (1.7 g, 10.0 mmol) was added first, followed by tetrabutylammonium iodide (1.8 g, 5 mmol). The reaction was allowed to proceed overnight. The crude product was filtered, washed with water, purified by silica gel column chromatography, and recrystallized to obtain 770 mg of a white solid with a yield of 56%. 1 H NMR (400 MHz, CDCl3) δ 3.77 (H a ).

[0226]

[0227] (6) Synthesis of compound 6: To a THF solution (80 mL) of compound 5 (545 mg, 1 mmol) and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (280 mg, 0.8 mmol) was added aqueous sodium hydroxide solution (2.4 mL, 1 M), and Pd(PPh3)4 (100 mg, 5% m / m) was added. The mixture was refluxed under N2 protection for 48 h. The mixture was cooled to room temperature and poured into NH4Cl solution. The aqueous phase was extracted with CHCl3. The combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by column chromatography (Al2O3) to obtain 380 mg of a white solid with a yield of 65%. 1 H NMR(400MHz,CDCl3)δ8.81(s,2H,Tpy-H 3',5' ),8.74-8.73(d,2H,J=8Hz,Tpy-H 6,6” ),8.70-8.68(d,2H,J=8Hz,Tpy-H 3,3” ),8.01-7.99(d,2H,J=8Hz,Ph-H g ),7.91-7.87(t,2H,Tpy-H 4,4” ),7.38-7.35(t,2H,Tpy-H 5,5” ),7.29-7.27(d,2H,J=8Hz,Ph-H h ),3.97(d,3H,H a ).

[0228]

[0229] (7) Synthesis of compound 7: 5-Bromo-1,2,3-trimethoxybenzene (2.0 g, 8.1 mmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (3.4 g, 9.6 mmol) and NaOH (970.0 mg, 24.3 mmol) were added to a 250 mL round-bottom flask, followed by the addition of THF (160 mL) and water (16 mL). The catalyst Pd(PPh3)4 (346.0 mg, 0.3 mmol) was added and the mixture was refluxed under N2 protection for 1 d. After the reaction was completed, the mixture was cooled to room temperature and then concentrated in vacuo. The residue was purified by chromatography (Al2O3) to obtain 3.0 g of a white solid with a yield of 78%. 1 H NMR(400MHz, CDCl3)δ8.78(s,2H,tpy-H 3',5' ),8.75-8.74(d,2H,J=4Hz,tpy-H 6,6” ),8.69-8.67(d,2H,J=8Hz,tpy-H 3,3” ),8.00-7.98(d,2H,J=8Hz,Ph-H g ),7.91-7.87(t,2H,tpy-H 4,4” ),7.71-7.69(d,2H,Ph-H h ),7.38-7.35(t,2H,tpy-H 5,5” ),6.85(s,2H,H a ),3.96(s,6H,H b ),3.92(s,3H,H c ).

[0230]

[0231] (8) Synthesis of compound 8: To a solution of compound 7 (3.0 g, 6.3 mmol) in CHCl3 (80 mL) was added Br2 (3.2 mL, 63.0 mmol). After reflux for 36 h, the mixture was washed with saturated sodium bisulfite solution until colorless. The organic layer was dried (anhydrous Na2SO4) and concentrated in vacuo to obtain 3.7 g of a white solid with a yield of 93%. 1 H NMR(400MHz, CDCl3)δ8.81(s,2H,tpy-H 3',5' ),8.73-8.72(d,2H,J=4Hz,tpy-H 6,6” ),8.69-8.67(d,2H,J=8Hz,tpy-H 3,3” ),8.00-7.98(d,2H,J=8Hz,Ph-H g ),7.89-7.85(t,2H,tpy-H 4,4” ),7.36-7.33(m,4H,tpy-H 5,5” ,Ph-H h ),4.01(s,3H,H b ),3.95(s,6H,H a ).

[0232]

[0233] (9) Synthesis of compound 9: Ethanol was added to compound 8 (633.0 mg, 1 mol) and RuCl3·3H2O (313.0 mg, 1.2 mmol), and the mixture was refluxed for 24 h. The mixture was then cooled to room temperature and filtered. The mixture was washed three times with methanol and dried in vacuo to obtain 748.0 mg of a brown powder with a yield of 89%.

[0234]

[0235] (10) Synthesis of compound 10: To a mixed solution of compound 9 (200.0 mg, 0.25 mmol) and compound 6 (160.0 mg, 0.22 mmol) in CHCl3 / MeOH (200 mL) were added a few drops of N-ethylmorpholine. The mixture was refluxed for 1 d, then cooled to room temperature and concentrated in vacuo. The crude product was purified by column chromatography (Al2O3) and then dried in vacuo to obtain 303 mg of a red powder with a yield of 90%. 1 H NMR(400MHz,MeOD)δ9.36(s,4H, A,B- Tpy-H 3',5' ),8.92-8.90(d,4H,J=8Hz, A,B- Tpy-H 3,3” ),8.45-8.43(d,2H,J=8Hz, A- Ph-H g ),8.41-8.39(d,2H,J=8Hz, B- Ph-H g ),8.06-8.02(t,4H, A,B- Tpy-H 4,4” ),7.60-7.59(d,4H,J=8Hz, A,B- Tpy-H 6,6” ),7.57-7.53(t,4H, A,B- Ph-H h ),7.32-7.29(t,4H,A,B- Tpy-H 5,5” ),4.03(s,3H,H a ),3.99(s,3H,H c ),3.97(s,6H,H b ).

[0236]

[0237] (11) Synthesis of metal organic ligand L2: Compound 10 (100 mg, 68.3 μmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (1.1 g, 3.3 mmol) and K2CO3 (455.0 mg, 3.3 mmol) were added to a 100 mL flask, followed by acetonitrile (50 mL), methanol (5 mL) and water (5 mL), and Pd(PPh3)4 (92 mg, 0.08 mmol). The mixture was refluxed under N2 protection for 6 d. After the reaction, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by column chromatography (Al2O3) to obtain 102.3 mg of a red solid with a yield of 53%. 1 H NMR(500MHz,DMSO)δ9.20(s,4H, A,B- Tpy-H 3',5' ),8.83(d,4H, A,B- Tpy-H 3,3” ),8.67-8.65(m,16H, D,E- Tpy-H 3',5' , D,E- Tpy-H 6,6” ),8.62-8.61(d,J=5Hz,8H, D,E- Tpy-H 3,3” ),8.59-8.58(d,4H,J=5Hz, C- Tpy-H 6,6” ),8.53(m,8H, C- Tpy-H 3',5' , C- Tpy-H 3,3” ),8.13-8.12(d,2H,J=5Hz, B- Ph-H g ),8.09-8.07(d,2H,J=10Hz, A- Ph-H g ),8.01-7.97(t,8H, D,E- Tpy-H 4,4” ),7.95-7.91(m,4H, C- Tpy-H 4,4”, C- Ph-H g ),7.87-7.82(m,8H, E- Ph-H g , D- Ph-H g ),7.76(t,2H, B- Tpy-H 4,4” ),7.64(t,2H, A- Tpy-H 4,4” ),7.60-7.58(d,4H, E- Ph-H h ),7.52-7.50(m,2H, B- Ph-H h ),7.48-7.45(m,12H, D,E- Tpy-H 5,5” , D- Ph-H h ),7.43-7.39(m,8H, C- Tpy-H 5,5” , C- Ph-H h ),7.32-7.30(d,2H, A- Ph-H h ),7.27(m,4H, A,B- Tpy-H 6,6” ),6.94(m,2H, A- Tpy-H 5,5” ),6.87(m,2H, B- Tpy-H 5,5” ),4.05(s,3H,H a ),3.73(s,6H,H b ),3.24(s,3H,H c ).ESI-MS(3396.52calcd.For C 188 H 124 F 12 N 26 O 12 RuS4):[M–2NTf2] 2+ (m / z=1418.97)(calcd.m / z=1418.12).

[0238] Example 3

[0239] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, which are based on Examples 1 and 2 and further include the following contents:

[0240] This embodiment provides a method for preparing an organic ligand L3, comprising the following steps:

[0241]

[0242] To 1,2,3,4-tetrabromo-5,6-bis(hexyloxy)benzene (594.0 mg, 1.0 mmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine 3.1 g, 6.0 mmol) and aqueous sodium hydroxide solution (12 mL, 1 M) was added THF (120 ml). Pd(PPh3)4 (300 mg, 5% m / m) was added to the mixture, which was degassed three times and refluxed under N2 protection for 4 d. After the reaction, the mixture was cooled to room temperature, NH4Cl solution was added, and the aqueous phase was extracted with CHCl3. The combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by chromatography (Al2O3) (dichloromethane / methanol v / v, 100:0.5) to give 1.2 g of a white solid with a yield of 66%). 1 HNMR(500MHz,CDCl3)δ8.80(s,4H, B- Tpy-H 3',5' ),8.75-8.74(d,4H,J=4Hz, B- Tpy-H 6,6” ),8.74(s,4H, A- Tpy-H 3',5' ),8.71-8.68(m,8H, B- Tpy-H 3,3” , A- Tpy-H 6,6” ),8.66-8.64(d,4H,J=10Hz, A- Tpy-H 3,3” ),8.02-8.00(d,4H,J=10Hz, B- Ph-H g ),7.94-7.92(d,4H,J=10Hz, A- Ph-H g ),7.92-7.90(t,4H, B- Tpy-H 4,4” ),7.88-7.84(t,4H, A- Tpy-H 4,4” ),7.78-7.77(d,4H,J=5Hz, B- Ph-H h ),7.65-7.63(d,4H,J=10Hz, A- Ph-H h ),7.59-7.57(d,4H,J=10Hz,B- Ph-H j ),7.38-7.36(m,4H, B- Tpy-H 5,5” ),7.36-7.31(m,12H, A- Tpy-H 5,5” , B- Ph-H k , A- Ph-H j ),7.02-7.01(d,4H,J=5Hz, A- Ph-H k ),3.93-3.90(m,4H,H a ).

[0243] Example 4

[0244] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-3, and further includes the following contents:

[0245] This embodiment provides a method for preparing a metal organic ligand L4, comprising the following steps:

[0246]

[0247] (1) Synthesis of compound 11: 4-Bromoiodobenzene (2.8 g, 10.0 mmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (2.5 g, 7.0 mmol) and NaOH (840.0 mg, 21.0 mmol) were added to a 500 mL flask, followed by the addition of THF (160 mL) and water (16 mL), and then Pd(PPh3)4 (346.0 mg, 0.3 mmol). The mixture was refluxed under nitrogen for 12 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by a chromatographic column (Al2O3) to obtain 2.2 g of a white solid with a yield of 69%. 1 H NMR(400MHz,CDCl3)δ8.79(s,2H,Tpy-H 3',5' ),8.75-8.74(d,2H,J=4Hz,Tpy-H 6,6” ),8.70-8.68(d,2H,J=8Hz,Tpy-H 3,3” ),8.02-7.99(d,2H,J=12Hz,Ph-H g ),7.91-7.87(t,2H,Tpy-H 4,4” ),7.72-7.70(d,2H,J=8Hz,Ph-Hh ),7.62-7.60(d,2H,J=8Hz,Ph-H j ),7.55-7.53(d,2H,J=8Hz,Ph-H k ),7.38-7.35(t,2H,Tpy-H 5,5” ).

[0248]

[0249] (2) Synthesis of compound 12: Compound 11 (2.0 g, 4.3 mmol) and pinacol diboron (1.4 g, 5.6 mmol) were added to a 100 ml flask, followed by the addition of 1,4-dioxane (50 mL) and CH3COOK (1.4 g, 13.8 mmol), and Pd(dppf)2Cl2 (150.0 mg, 0.2 mmol). The mixture was refluxed under nitrogen for 12 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by a chromatographic column (Al2O3) to obtain 1.5 g of a white solid with a yield of 70%. 1 HNMR(400MHz,CDCl3)δ8.72(s,2H,Tpy-H 3',5' ),8.68-8.67(d,2H,J=4Hz,Tpy-H 6,6” ),8.62-8.60(d,2H,J=8Hz,Tpy-H 3,3” ),7.95-7.93(d,2H,J=8Hz,Ph-H g ),7.86-7.80(m,4H,Tpy-H 4 ,4” ,Ph-H j ),7.71-7.69(d,2H,J=8Hz,Ph-H h ),7.63-7.61(d,2H,J=8Hz,Ph-H k ),7.31-7.28(t,2H,Tpy-H 5,5” ),1.31(s,12H,H a ).

[0250]

[0251] (3) Synthesis of compound 13: THF (120 mL) and sodium hydroxide solution (3 mL, 1 M) were added to a mixture of compound 5 (700 mg, 1.3 mmol) and compound 12 (511 mg, 1 mmol). The mixture was degassed three times, and then Pd(PPh3)4 (120 mg, 5% m / m) was added. After refluxing under N2 protection for 12 hours, the mixture was cooled to room temperature and poured into NH4Cl solution. The aqueous phase was extracted with CHCl3, and the combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by column chromatography (Al2O3) to obtain 556 mg of a white solid with a yield of 69%. 1 H NMR(400MHz,CDCl3)δ8.81(s,2H,Tpy-H 3',5' ),8.75-8.74(d,2H,J=4Hz,Tpy-H 6,6” ),8.70-8.68(d,2H,J=8Hz,Tpy-H 3,3” ),8.04-8.02(d,2H,J=8Hz,Ph-H g ),7.92-7.87(t,2H,Tpy-H 4,4” ),7.84-7.82(d,2H,J=8Hz,Ph-H h ),7.80-7.78(d,2H,J=8Hz,Ph-H j ),7.38-7.35(t,2H,Tpy-H 5,5” ),7.25-7.23(d,2H,J=8Hz,Ph-H k ),3.97(s,2H,H a ).

[0252]

[0253] (4) Synthesis of Compound 14: Compound 13 (500 mg, 0.6 mmol), 4-trimethylsilylphenylboronic acid (605 mg, 3.1 mmol), and NaOH (288.0 mg, 7.2 mmol) were added to a 250 mL flask, followed by the addition of THF (120 mL) and water (12 mL). The mixture was degassed three times, and Pd(PPh3)4 (200 mg, 0.2 mmol) was added. The mixture was refluxed under N2 protection for 4 d. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by column chromatography (Al2O3) to obtain 468.0 mg of a white solid with a yield of 72%. 1 H NMR(400MHz,CDCl3)δ8.64-8.62(m,4H,Tpy-H 3',5' ,Tpy-H 6,6”),8.57-8.55(d,2H,J=8Hz,Tpy-H 3,3” ),7.82-7.76(m,4H,Ph-H g ,Tpy-H 4,4” ),7.46-7.44(d,2H,J=8Hz,Ph-H h ),7.26-7.23(t,2H,Tpy-H 5,5” ),7.19-7.16(d,4H,H c ),7.09-7.07(d,2H,J=8Hz,Ph-H j ),7.05-7.04(d,4H,H b ),6.93-6.91(d,4H,J=8Hz,H d ),6.82-6.80(d,2H,J=8Hz,Ph-H k ),6.72-6.71(d,4H,J=4Hz,H e ),3.12(s,3H,H a ),0.10(s,18H,H m ),-0.00(s,18H,H n ).

[0254]

[0255] (5) Synthesis of compound 15: To a solution of compound 14 (400 mg, 0.37 mmol) and NaOH (180.0 mg, 4.4 mmol) in CH2Cl2 / CH3OH (v / v, 2:1) was added bromine at 0°C, followed by stirring under N2 protection for 8 h, vacuum concentration, and subsequent addition of CH3OH and filtration to obtain 468.0 mg of a white powder with a yield of 72%. 1 H NMR(400MHz,CDCl3)δ8.75(s,2H,Tpy-H 3',5' ),8.74-8.73(d,2H,J=4Hz,Tpy-H 6,6” ),8.68-8.66(d,2H,J=8Hz,Tpy-H 3,3” ),7.94-7.92(d,2H,J=8Hz,Ph-H g ),7.90-7.86(t,2H,Tpy-H 4,4” ),7.62-7.60(d,2H,J=8Hz,Ph-H h ),7.36-7.34(m,6H,Tpy-H 5,5” ,H c),7.26-7.24(d,2H,J=8Hz,Ph-H j ),7.09-7.07(d,4H,J=8Hz,H e ),7.05-7.03(d,4H,J=8Hz,H b ),6.84-6.82(d,2H,J=8Hz,H k ),6.73-6.70(d,4H,J=12Hz,H d ),3.13(s,3H,H a ).

[0256]

[0257] (6) Synthesis of Compound 16: 3,4,5-Trimethoxyphenylboronic acid (850 mg, 4 mmol), Compound 11 (928 mg, 2.0 mmol), and NaOH (240.0 mg, 6.0 mmol) were added to a 250 mL flask, followed by the addition of THF (160 mL) and water (16 mL). Catalyst Pd(PPh3)4 (115.4 mg, 0.1 mmol) was added, and the mixture was refluxed under N2 protection for 1 d. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by column chromatography (Al2O3) to obtain 915.0 mg of a white solid with a yield of 83%. 1 H NMR(400MHz,CDCl3)δ8.81(s,2H,Tpy-H 3',5' ),8.75-8.74(d,2H,J=4Hz,Tpy-H 6 ,6” ),8.70-8.68(d,2H,J=8Hz,Tpy-H 3,3” ),8.04-8.02(d,2H,J=8Hz,Ph-H g ),7.91-7.87(t,2H,Tpy-H 4,4” ),7.80-7.78(d,2H,J=8Hz,Ph-H h ),7.76-7.74(d,2H,J=8Hz,Ph-H k ),7.68-7.66(d,2H,J=8Hz,Ph-H j ),7.38-7.35(t,2H,Tpy-H 5,5” ),6.85(s,2H,H a ),3.96(s,6H,H b ),3.92(s,3H,H c ).

[0258]

[0259] (7) Synthesis of compound 17: To a solution of compound 16 (900.0 mg, 1.6 mmol) in CHCl3 (80 mL) was added Br2 (1.6 mL, 32.0 mmol) dropwise. After reflux for 36 h, the mixture was washed with saturated NaHSO3 until colorless. The organic layer was dried over anhydrous Na2SO4 and then concentrated in vacuo to obtain 1.0 g of a white solid with a yield of 92%. 1 H NMR(500MHz,CDCl3)δ8.73(s,2H,Tpy-H 3',5' ),8.67-8.66(d,2H,J=4Hz,Tpy-H 6,6” ),8.62-8.60(d,2H,J=8Hz,Tpy-H 3,3” ),7.96-7.94(d,2H,J=8Hz,Ph-H g ),7.83-7.79(t,2H,Tpy-H 4,4” ),7.76-7.75(d,2H,J=4Hz,Ph-H h ),7.71-7.69(d,2H,J=8Hz,Ph-H j ),7.29-7.27(t,2H,Tpy-H 5,5” ),7.23-7.21(d,2H,J=8Hz,Ph-H k ),3.93(s,3H,H b ),3.88(s,6H,H a ).

[0260]

[0261] (8) Synthesis of compound 18: Compound 17 (707 mg, 1.0 mmol), 4-trimethylsilylphenylboronic acid (582.0 mg, 3.0 mmol) and NaOH (240.0 mg, 6.0 mmol) were added to a 250 mL flask, followed by the addition of THF (160 mL) and water (16 mL). The mixture was degassed three times, and Pd(PPh3)4 (200 mg, 0.2 mmol) was added. The mixture was refluxed under nitrogen for 2 d. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by column chromatography (Al2O3) to obtain 625.0 mg of a white solid with a yield of 74%. 1 H NMR(400MHz,CDCl3)δ8.75(s,2H,Tpy-H 3',5' ),8.74-8.73(d,2H,J=4Hz,Tpy-H 6,6”),8.68-8.66(d,2H,J=8Hz,Tpy-H 3,3” ),7.93-7.91(d,2H,J=8Hz,Ph-H g ),7.90-7.86(t,2H,Tpy-H 4,4” ),7.56-7.54(d,2H,J=4Hz,Ph-H h ),7.37-7.34(t,2H,Tpy-H 5 ,5” ),7.32-7.30(d,4H,J=8Hz,H d ),7.18-7.16(d,2H,J=8Hz,Ph-H j ),7.08-7.06(d,4H,J=8Hz,H c ),6.80-6.78(d,2H,J=8Hz,Ph-H k ),4.06(s,3H,H b ),3.68(s,6H,H a ),0.21(s,18H,H e ).

[0262]

[0263] (9) Synthesis of compound 19: Bromine was added to a solution of compound 18 (600 mg, 0.7 mmol) and NaOH (168.0 mg, 4.2 mmol) in CH2Cl2 / CH3OH (v / v, 2:1) at 0°C, followed by stirring under nitrogen for 8 h, vacuum concentration, and subsequent addition of CH3OH and filtration to obtain 433.0 mg of a white powder with a yield of 72%. 1 H NMR(400MHz,CDCl3)δ8.79(s,2H,Tpy-H 3',5' ),8.77-8.76(d,2H,J=4Hz,Tpy-H 6,6” ),8.71-8.69(d,2H,J=8Hz,Tpy-H 3,3” ),7.99-7.97(d,2H,J=8Hz,Ph-H g ),7.94-7.90(t,2H,Tpy-H 4,4” ),7.67-7.65(d,2H,J=8Hz,Ph-H h ),7.41-7.37(t,2H,Tpy-H 5,5” ),7.33-7.31(d,4H,J=8Hz,H d ),7.31-7.29(d,2H,J=8Hz,Ph-Hj ),7.00-6.98(d,4H,J=8Hz,H c ),6.82-6.80(d,2H,J=8Hz,Ph-H k ),4.07(s,3H,H b ),3.68(s,6H,H a ).

[0264]

[0265] (10) Synthesis of compound 20: Ethanol was added to compound 19 (430.0 mg, 0.5 mmol) and RuCl3·3H2O (157.0 mg, 0.6 mmol), and the mixture was refluxed for 24 h. The mixture was then cooled to room temperature and filtered. The mixture was washed three times with methanol and dried in vacuo to obtain 748.0 mg of a brown powder with a yield of 89%.

[0266]

[0267] (11) Synthesis of compound 21: To a mixed solution of compound 20 (240.0 mg, 0.23 mmol) and compound 15 (221.0 mg, 0.2 mmol) in CHCl3 / MeOH (300 mL) were added a few drops of N-ethylmorpholine. The mixture was refluxed for 1 d, then cooled to room temperature and concentrated in vacuo. The crude product was purified by column chromatography (Al2O3) and then dried in vacuo to obtain 375 mg of a red powder with a yield of 87%. 1 H NMR(400MHz,MeOD)δ9.30(s,2H, A- Tpy-H 3',5' ),9.29(s,2H, B- Tpy-H 3',5' ),8.90-8.80(d,4H,J=8Hz, A,B- Tpy-H 3,3” ),8.33-8.30(t,4H, A,B- Ph-H g ),8.05-8.02(t,4H, A,B- Tpy-H 4,4” ),7.90-7.89(d,2H,J=4Hz, A- Ph-H g ),7.87-7.86(d,2H,J=4Hz, B- Ph-H g ),7.57-7.56(d,4H,J=4Hz, A,B- Tpy-H 6,6” ),7.45-7.41(t,8H,Hn,p ),7.38-7.36(d,4H,J=8Hz, A,B- Ph-H j ),7.30-7.28(t,4H, A,B- Tpy-H 5,5” ),7.17-7.15(d,8H,J=8Hz,H m,i ),7.07-7.06(m,6H, B- Ph-H k ,H e ),6.97-6.96(d,2H,J=4Hz, A- Ph-H k ),6.91-6.89(d,4H,J=8Hz,H d ),4.06(s,3H,H a ),3.70(s,6H,H b ),3.17(s,3H,H c ).

[0268]

[0269] (12) Synthesis of metal organic ligand L4: Compound 21 (100 mg, 48.4 μmol), 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine (812.0 mg, 2.3 mmol) and K2CO3 (317.0 mg, 2.3 mmol) were added to a 100 mL flask, followed by acetonitrile (50 mL), methanol (5 mL) and water (5 mL), and Pd(PPh3)4 (70 mg, 0.06 mmol). The mixture was refluxed under N2 protection for 6 d. After the reaction, the reaction solution was cooled to room temperature, concentrated in vacuo, and then purified by column chromatography (Al2O3) to obtain 92.3 mg of a red solid with a yield of 56%. 1 H NMR(500MHz,DMSO)δ9.42(s,4H, A,B- Tpy-H 3 ',5' ),9.04(d,4H, A,B- Tpy-H 3,3” ),8.75(m,16H, D,E- Tpy-H 3',5' , D,E- Tpy-H 6,6” ),8.69-8.66(m,16H, D,E- Tpy-H 3,3” , C- Tp 3' ,5' , C- Tpy-H 6,6” ),8.63-8.62(d,4H, C- Tpy-H 3,3” ),8.43-8.41(m,4H, A,B- Ph-H g ),8.05-7.99(m,16H, D,E- Tpy-H 4,4” , D,E- Ph-H g ),7.95-7.88(m,20H, A,B,C- Tpy-H 4 ,4” , C- Ph-H g,A,B,D- Ph-H h ),7.77(m,4h, C- Ph-H h ),7.68-7.67(m,10H, B,C- Ph-H j , E- Ph-H h ),7.59(m,4H, D- Ph-H j ),7.52-7.44(m,26H, C,D,E- Tpy-H 5,5” , A,E- Ph-H j , A,B- Tpy-H 6,6” , E- Ph-H k ),7.33-7.32(d,4H, C- Ph-H k ),7.26-7.24(m,4H, A,B- Ph-H k ),7.14(m,8H, A,B- Tpy-H 5,5” , D- Ph-H k ),4.03(s,3H,H a ),3.70(s,6H,H b ),3.19(s,3H,H c ).ESI-MS(4005.30calcd.ForC 236 H 156 F 12 N 26 O 12 RuS4):[M–2NTf2] 2+(m / z=1723.60)(calcd.m / z=1722.51).

[0270] Example 5

[0271] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, which are based on Examples 1-4 and further include the following:

[0272] This embodiment provides a method for preparing an organometallic compound constructed based on a terpyridine ligand, comprising the following steps:

[0273] (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system;

[0274] (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution;

[0275] (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

[0276] Wherein, in step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:1.

[0277] Wherein, in step (2), the heating temperature is 70° C. and the reaction time is 8 h.

[0278] Wherein, in step (2), in the methanol solution of the metal salt, the metal salt cation is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of the metal salt cations that are easily soluble in alcohol solvents, wherein the anion of the metal salt solution is NO3 - 、SO4 2- or Cl - One of them.

[0279] Wherein, in step (3), the anion displacer is one of ammonium hexafluorophosphate or lithium bis(trifluoromethanesulfonyl)imide; the anion displacer mainly functions to displace NO3 introduced by the methanol solution of the metal salt. - 、SO4 2- or Cl -The anions enable the organic metal compound constructed based on the terpyridine ligand to be better precipitated in the solvent, which is beneficial to the subsequent separation of the precipitate; the washing solvents are H2O and MeOH.

[0280] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H1, the terpyridine ligand in step (1) is an organic ligand L1 or a metal organic ligand L2.

[0281] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H2, the terpyridine ligand in step (1) is an organic ligand L3 or a metal organic ligand L4.

[0282] Wherein, when the organometallic compound constructed based on the terpyridine ligand is polymer P1, the terpyridine ligand in step (1) is the metal organic ligand L2.

[0283] Example 6

[0284] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-5, and further includes the following contents:

[0285] This embodiment provides a method for preparing an organometallic compound constructed based on a terpyridine ligand, comprising the following steps:

[0286] (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system;

[0287] (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution;

[0288] (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

[0289] Wherein, in step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:1.5.

[0290] Wherein, in step (2), the heating temperature is 70° C. and the reaction time is 12 h.

[0291] Wherein, in step (2), in the methanol solution of the metal salt, the metal salt cation is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu2+ 、Cd 2+ 、Ru 2+ At least one of the metal salt cations that are easily soluble in alcohol solvents, wherein the anion of the metal salt solution is NO3 - 、SO4 2- or Cl - One of them.

[0292] Wherein, in step (3), the anion displacer is one of ammonium hexafluorophosphate or lithium bis(trifluoromethanesulfonyl)imide; the anion displacer mainly functions to displace NO3 introduced by the methanol solution of the metal salt. - 、SO4 2- or Cl - The anions enable the organic metal compound constructed based on the terpyridine ligand to be better precipitated in the solvent, which is beneficial to the subsequent separation of the precipitate; the washing solvents are H2O and MeOH.

[0293] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H1, the terpyridine ligand in step (1) is an organic ligand L1 or a metal organic ligand L2.

[0294] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H2, the terpyridine ligand in step (1) is an organic ligand L3 or a metal organic ligand L4.

[0295] Wherein, when the organometallic compound constructed based on the terpyridine ligand is polymer P1, the terpyridine ligand in step (1) is the metal organic ligand L2.

[0296] Example 7

[0297] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-6, and further includes the following contents:

[0298] This embodiment provides a method for preparing an organometallic compound constructed based on a terpyridine ligand, comprising the following steps:

[0299] (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system;

[0300] (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution;

[0301] (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

[0302] Wherein, in step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:1.

[0303] Wherein, in step (2), the heating temperature is 70° C. and the reaction time is 12 h.

[0304] Wherein, in step (2), in the methanol solution of the metal salt, the metal salt cation is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of the metal salt cations that are easily soluble in alcohol solvents, wherein the anion of the metal salt solution is NO3 - 、SO4 2- or Cl - One of them.

[0305] Wherein, in step (3), the anion displacer is one of ammonium hexafluorophosphate or lithium bis(trifluoromethanesulfonyl)imide; the anion displacer mainly functions to displace NO3 introduced by the methanol solution of the metal salt. - 、SO4 2- or Cl - The anions enable the organic metal compound constructed based on the terpyridine ligand to be better precipitated in the solvent, which is beneficial to the subsequent separation of the precipitate; the washing solvents are H2O and MeOH.

[0306] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H1, the terpyridine ligand in step (1) is an organic ligand L1 or a metal organic ligand L2.

[0307] Wherein, when the organometallic compound constructed based on the terpyridine ligand is a hexagonal metal organic supramolecule H2, the terpyridine ligand in step (1) is an organic ligand L3 or a metal organic ligand L4.

[0308] Wherein, when the organometallic compound constructed based on the terpyridine ligand is polymer P1, the terpyridine ligand in step (1) is the metal organic ligand L2.

[0309] Example 8

[0310] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-7, and further includes the following contents:

[0311] This embodiment provides a method for preparing a hexagonal metal organic supramolecule H1, comprising the following steps:

[0312]

[0313] The organic ligand L1 (20.0 mg, 13.3 μmol) prepared in Example 1, the metal organic ligand L2 (37.6 mg, 13.3 μmol) prepared in Example 2, and Cd(NO3)2·4H2O (20.5 mg, 66.5 μmol) were added to a 100 mL flask, and then a CH3CN / CHCl3 (30 ml, V:V, 2:1) solution was added. After stirring and reflux for 8 h, the mixture was cooled to room temperature, and a methanol solution of lithium bis(trifluoromethanesulfonimide) (LiNTf2) was added. After a red precipitate was precipitated, it was filtered and washed with H2O and MeOH to obtain a red solid hexagonal metal organic supramolecular H1 with a mass of 74 mg and a yield of 96%. 1 H NMR(500MHz,CD3CN)δ8.83(m,4H, A,B- Tpy-H 3',5' ),8.80(m,4H, D,G- Tpy-H 3',5' ),8.70-8.68(m,4H, A,B- Tpy-H 3,3” ),8.65-8.64(m,12H, C,E,F- Tpy-H 3',5' ),8.60(m,8H, D,G- Tpy-H 3,3” ),8.54(m,4H, E- Tpy-H 3,3” ),8.50(m,4H, C- Tpy-H 3,3” ),8.40(m,4H, F- Tpy-H 3,3” ),8.01-7.97(m,24H, D,E,G- Tpy-H 4,4” , A,B,D,G- Ph-H g ),7.82(m,28H, A,B,C,F- Tpy-H 4,4” , C , E,F- Ph-H g ,A ,B- Ph-H h ),7.71(m,8H, D,G- Ph-H h),7.58(m,8H, C,E- Ph-H h ),7.51(m,4H, F- Ph-H h ),7.33-7.31(m,20H, C,D,E,F,G- Tpy-H 6,6” ),7.17-7.16(m,24H, A,B- Tpy-H 6 ,6” , C,D,E,F,G- Tpy-H 5,5” ),6.89-6.85(m,4H, A,B- Tpy-H 5,5” ),4.06(s,3H,H a ),4.01(m,3H,H c ),3.75(s,3H,H b ),3.33(m,3H,H d ).ESI-MS(49620.72calcd.For C 1860 H 1236 Cd 30 F 432 N 288 O 324 Ru6S 144 ):[M-32NTf2 - ] 32+ (m / z=1270.06)(Calcd.m / z=1270.51),[M-31NTf2 - ] 31+ (m / z=1320.23)(Calcd.m / z=1320.53),[M-30NTf2 - ] 30+ (m / z=1373.70)(Calcd.m / z=1373.88),[M-29NTf2 - ] 29+ (m / z=1430.65)(Calcd.m / z=1430.92),[M-28NTf2 - ] 28+ (m / z=1492.13)(Calcd.m / z=1492.03),[M-27NTf2 - ] 27+ (m / z=1557.39)(Calcd.m / z=1557.66),[M-26NTf2 - ] 26+(m / z=1628.20)(Calcd.m / z=1628.34),[M-25NTf2 - ] 25+ (m / z=1704.59)(Calcd.m / z=1704.59),[M-24NTf2 - ] 24+ (m / z=1787.19)(Calcd.m / z=1787.39),[M-23NTf2 - ] 23+ (m / z=1877.08)(Calcd.m / z=1877.28),[M-22NTf2 - ] 22+ (m / z=1974.91)(Calcd.m / z=1975.34),[M-21NTf2 - ] 21+ (m / z=2082.49)(Calcd.m / z=2082.75),[M-20NTf2 - ] 20+ (m / z=2200.39)(Calcd.m / z=2200.89),[M-19NTf2 - ] 19+ (m / z=2331.04)(Calcd.m / z=2331.47),[M-18NTf2 - ] 18+ (m / z=2476.29)(Calcd.m / z=2476.56),[M-17NTf2 - ] 17+ (m / z=2638.74)(Calcd.m / z=2638.72),[M-16NTf2 - ] 16+ (m / z=2820.06)(Calcd.m / z=2821.15),[M-15NTf2 - ] 15+ (m / z=3027.28)(Calcd.m / z=3027.90).

[0314] Example 9

[0315] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-8, and further includes the following contents:

[0316] This embodiment provides a method for preparing a hexagonal metal organic supramolecule H2, comprising the following steps:

[0317]

[0318] The organic ligand L3 (18.1 mg, 10 μmol) prepared in Example 3, the metal organic ligand L4 (34.5 mg, 10 μmol) prepared in Example 4, and Cd(NO3)2·4H2O (15.4 mg, 50 μmol) were added to a 100 mL flask, and then a CH3CN / CHCl3 (30 ml, V:V, 2:1) solution was added. After the mixture was refluxed for 8 h, it was cooled to room temperature and a methanol solution of lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) was added. A red precipitate was precipitated, which was filtered and washed with H2O and MeOH to obtain a red solid hexagonal metal organic supramolecular H2 with a mass of 65.3 mg and a yield of 96%. 1 H NMR(500MHz,CD3CN)δ8.88(s,16H, A,B,D,E,G- Tpy-H 3',5' ),8.82-8.80(m,8H, C,F- Tpy-H 3',5' ),8.69(m,14H, B,D,E,G- Tpy-H 3,3” ),8.63(m,10H, A,C,F- Tpy-H 3,3” ),8.52(m,4H, A,B- Ph-H g ),8.18(m,8H, D,G- Ph-H g ),8.11(m,12H, A,B- Tpy-H 4,4” , C,E- Ph-H g ),8.02(m,16H, D,E,G- Tpy-H 4,4” , F- Ph-H g ),7.96-7.90(m,28H, C,F- Tpy-H 4,4” , C,D,E,F,G- Ph-H h ),7.79(m,16H, A,B- Ph-H h , D,E,G- Ph-H j ),7.71(m,8H, C,F- Ph-H j ),7.66(m,8H, D,E- Ph-H k ),7.48(m,4H, A,B- Ph-H j),7.39-7.37(m,28H, C,D,E,F,G- Tpy-H 6,6” , C,G- Ph-H k ),7.29(m,24H, A,B- Tpy-H 6,6” , C,E,F,G- Tpy-H 5,5” , A,B- Ph-H k ),7.11(m, D- Tpy-H 5,5” ),7.03-7.01(m,4H, A,B- Tpy-H 5,5” ),4.01(s,6H,H a,c ),3.71(s,6H,H b ),3.25(t,4H,H d ).ESI-MS(55094.98calcd.ForC 2292 H 1524 Cd 30 F 432 N 288 O 324 Ru6S 144 ):[M-36NTf2 - ] 36+ (m / z=1248.84)(Calcd.m / z=1250.27),[M-35NTf2 - ] 35+ (m / z=1290.22)(Calcd.m / z=1294.00),[M-34NTf2 - ] 34+ (m / z=1335.02)(Calcd.m / z=1340.30),[M-33NTf2 - ] 33+ (m / z=1396.36)(Calcd.m / z=1389.40),[M-32NTf2 - ] 32+ (m / z=1446.08)(Calcd.m / z=1441.57),[M-31NTf2 - ] 31+ (m / z=1504.92)(Calcd.m / z=1497.12),[M-30NTf2 - ] 30+ (m / z=1563.75)(Calcd.m / z=1556.36),[M-29NTf2 - ] 29+(m / z=1624.68)(Calcd.m / z=1619.68),[M-28NTf2 - ] 28+ (m / z=1695.60)(Calcd.m / z=1687.54),[M-27NTf2 - ] 27+ (m / z=1767.88)(Calcd.m / z=1760.41),[M-26NTf2 - ] 26+ (m / z=1846.84)(Calcd.m / z=1838.90),[M-25NTf2 - ] 25+ (m / z=1930.77)(Calcd.m / z=1923.66),[M-24NTf2 - ] 24+ (m / z=2023.47)(Calcd.m / z=2015.48),[M-23NTf2 - ] 23+ (m / z=2118.24)(Calcd.m / z=2115.29),[M-22NTf2 - ] 22+ (m / z=2229.42)(Calcd.m / z=2224.19),[M-21NTf2 - ] 21+ (m / z=2342.63)(Calcd.m / z=2343.43).

[0319] Example 10

[0320] This embodiment provides a class of organometallic compounds based on terpyridine ligands, preparation methods, and applications thereof, based on Examples 1-9, and further includes the following contents:

[0321] This embodiment provides a method for preparing a polymer P1, comprising the following steps:

[0322]

[0323] The metal organic ligand L2 (34.1 mg, 10 μmol) and Cd(NO3)2·4H2O (9.3 mg, 30 μmol) were added to a 100 mL flask, followed by the addition of CH3CN / CHCl3 (30 ml, V:V, 2:1) solution. The mixture was refluxed for 8 h, cooled to room temperature, and a methanol solution of lithium bis(trifluoromethanesulfonimide) (LiNTf2) was added. A red precipitate was filtrated and washed with H2O and MeOH to obtain a red solid polymer P1.

[0324] Experimental Example 1

[0325] The hexagonal metal organic supramolecule H1 prepared in Example 8 was subjected to transmission electron microscopy (TEM) experiment. The results are as follows: Figure 29 As shown by Figure 29 It can be seen that the hexagonal metal-organic supramolecule H1 prepared in Example 8 is a cyclic hexagonal metal-organic supramolecule with an average diameter of 9.6 nm.

[0326] Experimental Example 2

[0327] The hexagonal metal organic supramolecule H2 prepared in Example 9 was subjected to transmission electron microscopy (TEM) experiment. The results are as follows: Figure 30 As shown by Figure 30 It can be seen that the hexagonal metal-organic supramolecule H2 prepared in Example 9 is a cyclic hexagonal metal-organic supramolecule with an average diameter of 13 nm.

[0328] Experimental Example 3

[0329] The polymer P1 prepared in Example 10 was subjected to scanning electron microscopy (SEM) and the results were as follows: Figure 31 As shown by Figure 30 It can be seen that the polymer P1 based on the terpyridine ligand prepared in Example 10 is in a chain shape.

[0330] Experimental Example 4

[0331] The polymer P1 prepared in Example 10 was subjected to transmission electron microscopy (TEM) and the results were as follows: Figure 32 As shown, Figure 32 (a) is the 500nm TEM image of polymer P1, (b) is the 200nm TEM image of polymer P1, (c) is the 200nm TEM image of polymer P1, and (d) is the 50nm TEM image of polymer P1; Figure 32 It can be seen that the polymer P1 prepared in Example 10 is in the shape of strips.

[0332] Experimental Example 5

[0333] The organic ligand L1 prepared in Example 1 and the organic ligand L3 prepared in Example 3 were dissolved in dichloromethane to prepare 2×10 -6 mol / L solution, the metal organic ligand L2 prepared in Example 2, the metal organic ligand L4 prepared in Example 4, the hexagonal metal organic supramolecule H1 prepared in Example 8, and the hexagonal metal organic supramolecule H2 prepared in Example 9 were dissolved in acetonitrile to prepare 2×10 -6 mol / L solution, and UV-visible spectroscopy experiments were performed. The results were as follows Figure 33 As shown by Figure 33 It can be seen that both the hexagonal metal-organic supramolecule H1 and the hexagonal metal-organic supramolecule H2 have absorption peaks at short wavelengths.

[0334] Experimental Example 6

[0335] The organic ligand L1 prepared in Example 1 and the organic ligand L3 prepared in Example 3 were dissolved in dichloromethane to prepare 2×10 -6 mol / L solution, the metal organic ligand L2 prepared in Example 2, the metal organic ligand L4 prepared in Example 4, the hexagonal metal organic supramolecule H1 prepared in Example 8, and the hexagonal metal organic supramolecule H2 prepared in Example 9 were dissolved in acetonitrile to prepare 2×10 -6 mol / L solution, and conduct fluorescence emission spectrum experiment. The results are as follows Figure 34 As shown by Figure 34 It can be seen that the fluorescence intensities of the hexagonal metal-organic supramolecule H1 and the hexagonal metal-organic supramolecule H2 are close to those of the metal-organic ligand L2 and the metal-organic ligand L4.

[0336] Experimental Example 7

[0337] The organic ligand L1 prepared in Example 1 and the organic ligand L3 prepared in Example 3 were dissolved in dichloromethane to prepare 2×10 -6 mol / L solution, the metal organic ligand L2 prepared in Example 2, the metal organic ligand L4 prepared in Example 4, the hexagonal metal organic supramolecule H1 prepared in Example 8, and the hexagonal metal organic supramolecule H2 prepared in Example 9 were dissolved in acetonitrile to prepare 2×10 -6 mol / L solution, and conduct low temperature fluorescence emission spectrum experiment. The results are as follows Figure 35 As shown by Figure 35 It can be seen that the fluorescence intensity of the hexagonal metal-organic supramolecule H1 in the low-temperature fluorescence emission spectrum experiment is higher than that of the organic ligand L1 and the metal-organic ligand L2, and the fluorescence intensity of the hexagonal metal-organic supramolecule H2 in the low-temperature fluorescence emission spectrum experiment is higher than that of the organic ligand L3 and the metal-organic ligand L4.

[0338] The above embodiments of the present invention provide an organometallic compound based on a terpyridine ligand and a method for preparing the same. The key point is that based on the terpyridine ligand and the coordination reaction, by controlling the metal coordination ion, ratio, solvent, temperature and other conditions, it helps to further improve the morphology selectivity and further prepare uniform hexagonal metal organic supramolecules.

[0339] The organometallic compounds constructed based on terpyridine ligands provided in the above embodiments of the present invention can be used in the fields of luminescent materials, conductive polymers, bioluminescent probes, dye-sensitized solar cells, phototherapy and anti-cancer drugs; the preparation method provided is simple and the reaction conditions are mild, which is conducive to large-scale industrial production.

[0340] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It is apparent to those skilled in the art that various changes, modifications, substitutions, and variations to these embodiments may be made without departing from the principles and spirit of the present invention, and these changes and modifications still fall within the scope of protection of the present invention.

Claims

1. A class of organometallic compounds constructed based on terpyridine ligands, characterized in that: It is an organometallic compound constructed with a terpyridine ligand, which contains a terpyridine ligand. The terpyridine ligand is one or more of an organic ligand L1 having a structure of formula (I), a metal organic ligand L2 having a structure of formula (II), an organic ligand L3 having a structure of formula (III), and a metal organic ligand L4 having a structure of formula (IV), as follows: The organometallic compound is a hexagonal metal organic supramolecule H1, a hexagonal metal organic supramolecule H2 or a polymer P1, which is composed of the terpyridine; the structural formula of the hexagonal metal organic supramolecule H1 is the formula (V), the structural formula of the hexagonal metal organic supramolecule H2 is the formula (VI), and the polymer P1 is the formula (VII), which are specifically as follows: M is a transition metal ion.

2. The organometallic compound constructed based on a terpyridine ligand according to claim 1, characterized in that: The transition metal ion M is selected from the transition metal ion Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of .

3. A method for preparing an organometallic compound constructed based on a terpyridine ligand according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) dissolving the terpyridine ligand in a mixed solution of chloroform and methanol to obtain a mixed system; (2) adding a methanol solution of a metal salt dropwise to the mixed system, heating under reflux and stirring to react, and cooling to room temperature after the reaction to obtain a reaction solution; (3) Adding an excess amount of anion displacer to the reaction solution, stirring until a large amount of precipitate is precipitated in the reaction solution, filtering and washing to obtain an organometallic compound constructed based on the terpyridine ligand.

4. The method for preparing an organometallic compound constructed based on a terpyridine ligand according to claim 3, wherein: When the organometallic compound constructed based on the terpyridine ligand is the hexagonal metal-organic supramolecule H1, the terpyridine ligand is the organic ligand L1 and the metal-organic ligand L2; when the organometallic compound constructed based on the terpyridine ligand is the hexagonal metal-organic supramolecule H2, the terpyridine ligand is the organic ligand L3 and the metal-organic ligand L4; when the organometallic compound constructed based on the terpyridine ligand is the polymer P1, the terpyridine ligand is the metal-organic ligand L2.

5. The method for preparing an organometallic compound constructed based on a terpyridine ligand according to claim 3, wherein: In step (1), the volume ratio of chloroform to methanol in the mixed solution of chloroform and methanol is 1:0.5-1.5; in step (2), the heating temperature is 40-70°C, and the reaction time is 8-12h; in step (3), the metal salt cation in the methanol solution of the metal salt is selected from the metal salt cation Cr that is easily soluble in alcohol solvents 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2 + 、Ru 2+ At least one of the metal salt solution anions is NO3 - 、SO4 2- or Cl - The anion displacer is one of ammonium hexafluorophosphate or lithium bis(trifluoromethanesulfonyl)imide, and the washing solvent is H2O and MeOH.

6. The method for preparing an organometallic compound constructed based on a terpyridine ligand according to claim 3, characterized in that: When the terpyridine ligand is a metal organic ligand L2, the preparation method comprises the following steps: (1) Substitution reaction of 4-nitrophenol and Br2 to obtain compound 1; (2) reacting compound 1 with ICH3 to obtain compound 2; (3) Compound 2 and SnCl4 were refluxed in ethanol for 8 h to obtain compound 3; (4) Compound 3 and Br2 were refluxed in ethanol for 24 h to obtain compound 4; (5) reacting compound 4 with KI to obtain compound 5; (6) Compound 5 and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to Suzuki coupling reaction to obtain compound 6; (7) 5-bromo-1,2,3-trimethoxybenzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to Suzuki coupling reaction to obtain compound 7; (8) Compound 7 is reacted with Br2 to obtain compound 8; (9) Compound 8 is subjected to coordination reaction with RuCl3·3H2O to obtain compound 9; (10) Compound 6 and compound 9 are reacted to obtain compound 10; (11) Compound 10 and 4′-(4-boronic acid phenyl)-2,2′:6′,2″-terpyridine were subjected to Suzuki coupling reaction to obtain the metal organic ligand L2.

7. The method for preparing an organometallic compound constructed based on a terpyridine ligand according to claim 3, characterized in that: When the terpyridine ligand is a metal organic ligand L4, the preparation method comprises the following steps: (1) Suzuki coupling reaction of 4-bromoiodobenzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine to obtain compound 11; (2) reacting compound 11 with biboronic acid pinacol ester to obtain compound 12; (3) reacting compound 12 with compound 5 to obtain compound 13; (4) Compound 13 and 4-trimethylsilylphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 14; (5) Compound 14 is reacted with Br2 to obtain compound 15; (6) Compound 11 and 3,4,5-trimethoxyphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 16; (7) Compound 16 is reacted with Br2 to obtain compound 17; (8) Compound 17 and 4-trimethylsilylphenylboronic acid were subjected to Suzuki coupling reaction to obtain compound 18; (9) Compound 18 is reacted with Br2 to obtain compound 19; (10) Compound 19 was reacted with RuCl3·3H2O to obtain compound 20; (11) Compound 20 and compound 15 are reacted to obtain compound 21; (12) Compound 21 and 4′-(4-boronic acid phenyl)-2,2′:6′,2″-terpyridine were subjected to Suzuki coupling reaction to obtain metal organic ligand L4.

8. The method for preparing an organometallic compound constructed based on a terpyridine ligand according to claim 3, characterized in that: When the terpyridine ligand is an organic ligand L1, the preparation method comprises the following steps: 1,2,3,4-tetrabromo-5,6-bis(hexyloxy)benzene and 4'-(4-boronic acid phenyl)-2,2':6',2"-terpyridine were subjected to Suzuki coupling reaction to obtain organic ligand L1; When the terpyridine ligand is an organic ligand L3, the preparation method comprises the following steps: 1,2,3,4-Tetrabromo-5,6-di(hexyloxy)benzene and compound 12 were subjected to Suzuki coupling reaction to obtain organic ligand L3.

9. The use of the organometallic compound constructed based on the terpyridine ligand according to any one of claims 1 to 2, characterized in that: The organometallic compound constructed based on the terpyridine ligand is applied to the manufacture of luminescent materials, conductive high molecular polymers, biological fluorescent probes, dye-sensitized solar cells, and phototherapy anticancer drugs.

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