Dinuclear organoboron fused ring compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic light-emitting materials, in particular to a binuclear organoboron fused ring compound as well as a preparation method and application thereof. The binuclear organoboron fused ring compound provided by the invention is structurally characterized by containing a molecular skeleton composed of two boron atoms and heteroatoms (N, O, S) and having 2 or 4 methyl substituents. On one hand, the relaxation degree of an excited state structure can be reduced by utilizing a rigid skeleton structure of the fused ring compound, so that relatively narrow half-peak width is realized; on the other hand, HOMO and LUMO energy level distribution of a fused ring skeleton is regulated and controlled by utilizing the action of a methyl substituent group, side reactions are inhibited in the boron cyclization reaction, the reaction yield is increased, and the material cost is reduced. Experimental results show that the organic boron fused ring compound provided by the invention not only can be used for assembling an OLED device by an evaporation process, but also can be used for a light-emitting layer of the OLED device by a solution processing process, so that the OLED device with high efficiency and long service life can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of organic light-emitting materials, and in particular, to a binuclear organic boron fused-ring compound, a preparation method thereof, and an application thereof. Background Art

[0002] Organic light-emitting devices (OLEDs) have the characteristics of high contrast, rich colors, ultrathin flexibility, fast response, etc., and are applied in multiple fields, including smartphones, high-end TVs, automotive displays, etc. Generally speaking, the classical structure of an OLED device includes an anode, a hole injection layer (TIL), a hole transport layer (HTL), a light-emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode. When a voltage is applied to the electrodes, holes and electrons injected from the positive and negative electrodes on the organic thin film combine to form excitons, and the excitons radiatively decay to generate photons, thereby emitting light. It can be seen that the light-emitting layer plays a crucial role in the OLED device. Thermally activated delayed fluorescence (TADF) materials are a new generation of organic light-emitting materials following traditional fluorescent and phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEST), and use the thermally activated reverse intersystem crossing (RISC) process to transfer triplet excitons to singlet excitons to emit fluorescence, thereby realizing the full utilization of singlet and triplet excitons and achieving an internal quantum efficiency of 100%. With the promulgation of the BT.2020 standard for the new generation of ultra-high-definition video production and display systems, a wider color gamut space will be adopted to meet more abundant color displays. To meet this requirement, researchers have found that improving the color purity of light-emitting materials can achieve a wider color gamut display.

[0003] Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials are composed of a polycyclic aromatic skeleton and embedded electron-donating atoms and electron-withdrawing atoms that are para to each other. Their structural characteristics result in short-range intramolecular charge transfer, inhibiting excited-state structural relaxation, thereby endowing them with narrow-band emission characteristics and TADF effects. MR-TADF materials have the characteristics of high efficiency and high color purity, and can be applied to the new generation of wide color gamut ultra-high definition displays. So far, vapor-deposited MR-TADF organic light-emitting diodes (OLEDs) have achieved excellent external quantum efficiencies (EQEs). For example, the red, green, and blue devices have reached 36.1%, 40.1%, and 43.9% respectively. However, the efficiency of solution-processed MR-TADF devices is significantly lower than that of vapor-deposited devices. For example, the classic vapor-deposited organoboron blue material v-DABNA has a rigid planar structure, resulting in serious molecular aggregation and poor solubility. At the same time, the highest occupied molecular orbital (HOMO) energy level of v-DABNA modified with a diphenylamine group is relatively high, and it is easy to form hole traps when matching with the host material, affecting hole transport, and then bringing problems of unbalanced carrier transport and exciton quenching, resulting in a reduction in the efficiency of solution-processed devices.

[0004] How to develop an organoboron compound that can be used in the light-emitting layer of OLED devices assembled by vapor deposition process and also in the light-emitting layer of OLED devices by solution process through reasonable chemical structure design, and prepare OLED devices with high efficiency and long life has become one of the urgent problems to be solved. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a binuclear organoboron fused-ring compound, its preparation method and application.

[0006] The present invention provides a binuclear organoboron fused-ring compound having the structure shown in Formula I:

[0007]

[0008] Wherein, X1 is selected from -N(R a1 )-, -O-, -S-, -Se- or -Te-;

[0009] X2 is selected from -N(R a2 )-, -O-, -S-, -Se- or -Te-;

[0010] The R a1 , R a2 are independently selected from H, D, substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aromatic groups or substituted or unsubstituted C3-C60 heteroaromatic groups;

[0011] The Ra1 One or two of the benzene rings connected to X1 may be connected through a single bond, -O-, -S-, and any one or more of the following;

[0012] The said R a2 One or two of the benzene rings connected to X2 may be connected through a single bond, -O-, -S-, and any one or more of the following;

[0013] The said R x ′ may be a substituted or unsubstituted C1-C30 alkyl group, C6-C30 aryl group, C3-C30 heteroaryl group, preferably a substituted or unsubstituted C1-C10 alkyl group, C6-C14 aryl group, C3-C14 heteroaryl group, and specifically may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, pyrrolyl, pyridyl, etc.

[0014] L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, a substituted or unsubstituted C1-C30 straight-chain or branched-chain alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 heteroarylene group, or a group formed by connecting any one of the above groups through a single bond;

[0015] Q1 and Q2 are independently selected from H, D, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group or a substituted or unsubstituted C3-C60 heteroaromatic group, -NR 1 R 2 ;

[0016] R1, R2, R3, and R4 are independently selected from H, D, F, Cl, Br, I, -CN, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group or a substituted or unsubstituted C3-C60 heteroaromatic group, or any of the following structures:

[0017]

[0018] R 1 R 2, R 3 independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted straight-chain or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C3-C60 heteroaromatic group;

[0019] and said R 1 , R 2 , R 3 any two or three of them can be connected by a single bond, -O-, -S-, one or more of;

[0020] the heteroatoms of said heteroaromatic group are independently selected from any one or more of Si, Te, Ge, N, P, O, S, Se;

[0021] n1 and n4 are independently selected from any integer from 1 to 4;

[0022] n2 and n3 are independently selected from any integer from 1 to 5;

[0023] m1 and m2 are independently selected from 0, 1 or 2;

[0024] — represents the connection position.

[0025] said m1 and m2 are independently selected from 0, 1 or 2; when m1 or m2 is 0, it means that the corresponding methyl group does not exist.

[0026] In some specific embodiments, said binuclear organoboron fused-ring compound has a structure shown in formula (I-i), formula (I-ii), formula (I-iii) or formula (I-iv):

[0027]

[0028] wherein, the definitions of each substituent group are the same as those in formula I.

[0029] said X1 is selected from -N(R a1 )-, -O-, -S-, -Se- or -Te-; wherein, said R a1 is selected from H, D, a substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, morpholinyl, indolyl, benzofuryl, benzothienyl, carbazolyl or fluorenyl, preferably phenyl.

[0030] The substitution is preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 haloalkyl, and C1-C10 alkoxy, more preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy, and further preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C3 alkyl, C1-C3 haloalkyl, and C1-C3 alkoxy.

[0031] Optionally, the R a1 One or two of the benzene rings connected to X1 can be connected by a single bond, -O-, -S-, with any one or more of them.

[0032] The R a3 , R a4 are independently preferably substituted or unsubstituted C1-C30 alkyl, C6-C30 aryl, C3-C30 heteroaryl; more preferably substituted or unsubstituted C1-C10 alkyl, C6-C14 aryl, C3-C14 heteroaryl; further preferably substituted or unsubstituted C1-C6 alkyl, C6-C10 aryl, C3-C10 heteroaryl; specifically, they can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, pyrrolyl, pyridyl, etc.

[0033] The substitution is preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 haloalkyl, and C1-C10 alkoxy, more preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy, and further preferably substituted by any one or more of deuterium, F, Cl, Br, I, cyano, nitro, amino, C1-C3 alkyl, C1-C3 haloalkyl, and C1-C3 alkoxy.

[0034] The X2 is selected from -N(R a2 )-, -O-, -S-, -Se- or -Te-. Wherein, the R a2Selected from H, D, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, morpholinyl, indolyl, benzofuryl, benzothienyl, carbazolyl or fluorenyl, preferably phenyl.

[0035] The substitution is preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkoxy, more preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, and further preferably substituted by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy.

[0036] Optionally, the R a2 One or two of the benzene rings connected to X2 can be connected by a single bond, -O-, -S-, and any one or more of them.

[0037] The R a3 , R a4 is defined as described above.

[0038] Optionally, L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, substituted or unsubstituted C1-C10 straight-chain or branched-chain alkylene, substituted or unsubstituted C1-C10 alkyleneoxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C3-C6 cycloalkylene, substituted or unsubstituted C6-C14 arylene group, substituted or unsubstituted C3-C14 heteroarylene group, or a group formed by connecting any one of the above groups by a single bond.

[0039] Optionally, L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, substituted or unsubstituted C1-C6 straight-chain or branched-chain alkylene, substituted or unsubstituted C1-C6 alkyleneoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C3-C6 cycloalkylene, substituted or unsubstituted C6-C10 arylene group, substituted or unsubstituted C3-C10 heteroarylene group, or a group formed by connecting any one of the above groups by a single bond.

[0040] Optionally, L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, a substituted or unsubstituted C1-C3 linear or branched alkylene group, a substituted or unsubstituted C1-C3 alkyleneoxy group, a substituted or unsubstituted C1-C3 alkylthio group, a substituted or unsubstituted cyclopropylidene group, a substituted or unsubstituted cyclobutylidene group, a substituted or unsubstituted cyclopentylidene group, a substituted or unsubstituted cyclohexylidene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrrolyl group, or a group formed by connecting any one of the above groups through a single bond.

[0041] The connection through a single bond preferably means selecting any one, two or three of them and connecting them through a single bond to form a group.

[0042] Preferably, L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methoxyethylene group, ethoxyethylene group, propoxyethylene group, methylthioethylene group, ethylthioethylene group, propylthioethylene group, cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group or any of the following structures:

[0043]

[0044] or a group formed by connecting the above groups through a single bond.

[0045] In the above structural formula, * represents the connection position.

[0046] When L1 and L2 are independently selected from u-2 or u-6, it means that L1 and / or L2 is connected to two corresponding Ls. For example, when L1 is selected from u-2, it means that L1 is a phenyl group and is connected to two Q1s; when L2 is selected from u-6, it means that L2 is a triazine group and is connected to two Q2s.

[0047] In the definition of L1 and L2, the substitution is preferably by any one or more of deuterium, halogen, cyano, nitro, amino, a C1-C10 alkyl group, a C1-C10 halogenated alkyl group, a C1-C10 alkoxy group; more preferably by any one or more of deuterium, halogen, cyano, nitro, amino, a C1-C6 alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 alkoxy group; further preferably by any one or more of deuterium, halogen, cyano, nitro, amino, a C1-C3 alkyl group, a C1-C3 halogenated alkyl group, a C1-C3 alkoxy group.

[0048] Preferably, Q1 and Q2 are independently selected from H, D, substituted or unsubstituted C1-C10 linear or branched hydrocarbon groups, substituted or unsubstituted C1-C10 alkoxy groups, substituted or unsubstituted C1-C10 alkylthio groups, substituted or unsubstituted C3-C6 cycloalkyl groups, -NR 1 R 2 or substituted or unsubstituted any one of a) to e); more preferably, Q1 and Q2 are independently selected from H, D, substituted or unsubstituted C1-C6 linear or branched hydrocarbon groups, substituted or unsubstituted C1-C6 alkoxy groups, substituted or unsubstituted C1-C6 alkylthio groups, substituted or unsubstituted C3-C6 cycloalkyl groups, -NR 1 R 2 or substituted or unsubstituted any one of a) to e):

[0049] a) phenyl;

[0050] b) a group formed by linking or fusing 2 to 5 phenyl groups by single bonds;

[0051] c) 5- to 6-membered monocyclic heteroaromatic groups;

[0052] d) a group formed by linking or fusing 2 to 5 5- to 6-membered monocyclic heteroaromatic groups by single bonds;

[0053] e) a group formed by linking or fusing a phenyl group and a 5- to 6-membered monocyclic heteroaromatic group by single bonds; the total number of the phenyl group and the 5- to 6-membered monocyclic heteroaromatic group is 2 to 7.

[0054] The heteroatoms of the monocyclic heteroaromatic group are selected from any one or more of Si, Ge, N, P, O, S, Se.

[0055] The hydrocarbon group includes but is not limited to alkyl, alkenyl, and alkynyl.

[0056] Preferably, b) is naphthyl, anthracenyl, phenanthryl, pyrenyl or perylenyl.

[0057] Preferably, c) is pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, pyranyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl or any of the following structures:

[0058]

[0059] wherein, R 1 、R 2 、R 3 are defined as described above.

[0060] The said d) is preferably a group formed by 2, 3, 4 or 5 5- to 6-membered monocyclic heteroaromatic groups connected or fused by single bonds. More preferably, it is a group formed by 2 to 3 5- to 6-membered monocyclic heteroaromatic groups connected or fused by single bonds. The said 5- to 6-membered monocyclic heteroaromatic group is preferably pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, pyranyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl or oxazolyl.

[0061] The said e) is preferably a group formed by a phenyl group and a 5- to 6-membered monocyclic heteroaromatic group connected or fused by a single bond; the total number of the phenyl group and the 5- to 6-membered monocyclic heteroaromatic group is 2, 3, 4, 5, 6 or 7, preferably 2 to 5, and more preferably 2 to 3. The said 5- to 6-membered monocyclic heteroaromatic group is preferably pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, pyranyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl or oxazolyl.

[0062] The said -NR 1 R 2 is preferably N,N-diphenylamino or N,N-dimethylamino.

[0063] In the definitions of Q1 and Q2, the said substitution is preferably substitution by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 haloalkyl, phenyl, pyridyl, carbazolyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, -NR 1 R 2 ; more preferably, it is substitution by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkyl, phenyl, pyridyl, carbazolyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, -NR 1 R 2 .

[0064] R 1 、R 2 is as defined above.

[0065] The said -NR 1 R 2 is preferably N,N-diphenylamino or N,N-dimethylamino.

[0066] In some specific embodiments, Q1 and Q2 are independently selected from H, D, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, n-propoxy, isopropoxy, methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -NR 1 R 2 or any of the following structures:

[0067]

[0068]

[0069] * indicates the connection position.

[0070] Wherein, the definition of the substituent group is the same as the description of the substituent groups of Q1 and Q2 above.

[0071] Preferably, R1, R2, R3, and R4 are independently selected from H, D, F, Cl, Br, I, -CN, substituted or unsubstituted C1-C10 straight-chain or branched-chain hydrocarbon groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C14 aromatic groups, or substituted or unsubstituted C3-C14 heteroaromatic groups, or any of the following structures; more preferably, R1, R2, R3, and R4 are independently selected from H, D, F, Cl, Br, I, -CN, substituted or unsubstituted C1-C6 straight-chain or branched-chain hydrocarbon groups, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted tetrahydronaphthyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted C3-C14 heteroaromatic groups, or any of the following structures:

[0072]

[0073] R 1 、R 2 、R 3 are defined as described above.

[0074] Wherein, the substituted or unsubstituted C3-C14 heteroaromatic group is preferably a substituted or unsubstituted five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S, or a bicyclic fused heteroaromatic group, and at least one ring in the bicyclic fused heteroaromatic group is a five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S, and the other ring can be a phenyl group or a five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S.

[0075] The five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S is preferably a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, furyl group, pyranyl group, thienyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, or oxazolyl group.

[0076] In the definitions of R1, R2, R3, and R4, the substitution is preferably by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 haloalkyl, -NR 1 R 2 ; more preferably by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkyl, -NR 1 R 2 ; further preferably by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 haloalkyl, -NR 1 R 2 .

[0077] R 1 , R 2 is as defined above.

[0078] The -NR 1 R 2 is preferably N,N-diphenylamino or N,N-dimethylamino.

[0079] In the present invention, R3 and the phenyl group to which it is attached can be connected by a fused manner. For example, when R3 is a benzofuran group, benzothiophene group, or benzopyrrole group, it is fused with the phenyl group through a heterocyclic group to form a dibenzofuran group, dibenzothiophene group, or dibenzopyrrole group together with the phenyl group. The hydrogen atom connected to the N atom of the dibenzopyrrole group can be further substituted by a group selected from R 1 , and the definition of R 1 is as defined above.

[0080] In the present invention, R2 and the phenyl group to which it is attached can be connected by a fused manner. For example, when R2 is a benzofuran group, benzothiophene group, or benzopyrrole group, it is fused with the phenyl group through a heterocyclic group to form a dibenzofuran group, dibenzothiophene group, or dibenzopyrrole group together with the phenyl group. The hydrogen atom connected to the N atom of the dibenzopyrrole group can be further substituted by a group selected from R 1 , and the definition of R 1 is as defined above.

[0081] In the present invention, the R 1 , R 2 , R 3 are independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted C1-C10 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, or a substituted or unsubstituted C3-C14 heteroaromatic group; preferably H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted C1-C6 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, or a substituted or unsubstituted C3-C14 heteroaromatic group.

[0082] The hydrocarbon group includes, but is not limited to, an alkyl group, an alkenyl group, or an alkynyl group.

[0083] The C1-C6 straight-chain or branched-chain hydrocarbon group is preferably a C1-C3 straight-chain or branched-chain alkyl group, and specifically may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, or a n-hexyl group.

[0084] The C3-C6 cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0085] The C6-C14 aromatic group is preferably a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group.

[0086] The C3-C14 heteroaromatic group is preferably a five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S, or a bicyclic fused heteroaromatic group, where at least one ring in the bicyclic fused heteroaromatic group is a five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S, and the other ring may be a phenyl group or a five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S.

[0087] The five- to six-membered monocyclic heteroaromatic group containing one or more of N, O, and S is preferably a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a furyl group, a pyranyl group, a thiophenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, or an oxazolyl group.

[0088] And the R 1 , R 2 , R 3 can be connected through one or more of a single bond, -O-, -S-, .

[0089] Wherein, when the R 1 , R 2 and R 3Any two or three of them are connected to each other through When connected by one or more of them, the linking group may be connected with a substituent group R a3 . For example, when any two of the said R 1 , R 2 and R 3 are connected by , the linking group may be represented as —N(R a3 ), specifically it may be N-phenylimino. For example, when any two of the said R 1 , R 2 and R 3 are connected by , the linking group may be

[0090] Wherein, R a3 , R a4 are defined as described above.

[0091] The said n1 and n4 are independently selected from any integers of 1 to 4; specifically they may be 1, 2, 3 or 4. When n1 and n4 are not 1, the number of R1 and R4 is not 1, and multiple R1 or multiple R4 may be the same or different.

[0092] n2 and n3 are independently selected from any integers of 1 to 5; specifically they may be 1, 2, 3, 4 or 5. When n2 and n3 are not 1, the number of R2 and R3 is not 1, and multiple R2 or multiple R3 may be the same or different.

[0093] In some specific embodiments, the binuclear organoboron fused-ring compound has any one of the following structures:

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] On the other hand, the present invention provides a preparation method of the above binuclear organoboron fused-ring compound, including the following steps:

[0100] S1. Compound U-1 reacts with compound U-4 to obtain compound U-6; compound U-2 reacts with compound U-3 to obtain compound U-5;

[0101] S2. Compound U-6 reacts with m-dibromobenzene to obtain compound U-7; compound U-5 reacts with m-dibromobenzene to obtain compound U-8;

[0102] S3. Compound U-7 reacts with compound U-8 to obtain compound U-9;

[0103] S4. Compound U-9 reacts with BI3 or BBr3 to form a polycyclic intermediate shown in formula (II);

[0104] S5. The polycyclic intermediate shown in formula (II) reacts with at least one of compound U-10 and U-11 to obtain a binuclear organoboron polycyclic compound shown in formula (I);

[0105]

[0106] Among them, the definitions of X1, X2, R1, R2, R3, R4, n1, n2, n3, n4, m1, and m2 are the same as above.

[0107] In the above step S1), the reaction is preferably carried out under the action of a palladium catalyst. The palladium catalyst is preferably one or more of palladium chloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, and dichlorobis(diphenylphosphino)ferrocene palladium. The molar ratio of the catalyst to compound U-1 or U-2 is preferably (0.005 - 0.5):1.

[0108] The reaction is preferably carried out under the action of a basic compound. The basic compound is preferably one or more of potassium carbonate, cesium carbonate, sodium tert-butoxide, or potassium tert-butoxide. The molar ratio of the basic compound to compound U-1 or U-2 is preferably (0.5 - 5):1.

[0109] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of toluene, xylene, mesitylene, cumene, or p-methylcumene. The dosage ratio of the organic solvent to compound U-1 or U-2 is preferably (50 - 500) mL:(0.1 - 10) mol.

[0110] The reaction is preferably carried out under a protective atmosphere. The present invention has no particular limitation on the type of protective gas providing the protective atmosphere, and it can be a conventional protective gas in the art, such as nitrogen, helium, or argon, etc.

[0111] The temperature of the reaction is preferably 80 - 180 °C; the time of the reaction is preferably 4 - 48 h. After the above reaction, compound U-6 and / or U-5 is generated in the system.

[0112] In the above step S2, the reaction is preferably carried out under the action of a palladium catalyst. The palladium catalyst is preferably one or more of palladium chloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, and dichlorobis(diphenylphosphino)ferrocene palladium. The molar ratio of the catalyst to compound U-5 or U-6 is preferably (0.005 - 0.5)∶1.

[0113] The reaction is preferably carried out under the action of a basic compound. The basic compound is preferably one or more of potassium carbonate, cesium carbonate, sodium tert-butoxide, or potassium tert-butoxide. The molar ratio of the basic compound to compound U-5 or U-6 is preferably (0.5 - 5)∶1.

[0114] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of toluene, xylene, mesitylene, cumene, or p-methylcumene. The dosage ratio of the organic solvent to compound U-5 or U-6 is preferably (50 - 500) mL∶(0.1 - 10) mol.

[0115] The reaction is preferably carried out under a protective atmosphere. The present invention has no particular limitation on the type of protective gas providing the protective atmosphere, and it can be a conventional protective gas in the art, such as nitrogen, helium, or argon, etc.

[0116] The temperature of the reaction is preferably 80 - 180 °C; the time of the reaction is preferably 4 - 48 h. After the above reaction, compound U-7 and / or U-8 is / are generated in the system.

[0117] In the above step S3), the reaction is preferably carried out under the action of a palladium catalyst. The palladium catalyst is preferably one or more of palladium chloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, and dichlorobis(diphenylphosphino)ferrocene palladium. The molar ratio of the catalyst to compound U-7 or U-8 is preferably (0.005 - 0.5)∶1.

[0118] The reaction is preferably carried out under the action of a basic compound. The basic compound is preferably one or more of potassium carbonate, cesium carbonate, sodium tert-butoxide, or potassium tert-butoxide. The molar ratio of the basic compound to compound U-7 or U-8 is preferably (0.5 - 5)∶1.

[0119] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of toluene, xylene, mesitylene, cumene, or p-methylcumene. The dosage ratio of the organic solvent to compound U-7 or U-8 is preferably (50 - 500) mL∶(0.1 - 10) mol.

[0120] Preferably, the reaction is carried out under a protective atmosphere. The present invention has no particular limitation on the type of protective gas providing the protective atmosphere, and any conventional protective gas in the art can be used, such as nitrogen, helium, argon, etc.

[0121] The temperature of the reaction is preferably 80 - 180 °C; the time of the reaction is preferably 4 - 48 h. After the above reaction, compound U-9 is formed in the system.

[0122] In the step S4), the reaction is preferably carried out under the action of boron triiodide or boron tribromide. The molar ratio of boron triiodide or boron tribromide to compound U-9 is preferably (1 - 30) : 1.

[0123] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, and tert-butylbenzene. The dosage ratio of the organic solvent to compound U-9 is preferably (10 - 500) mL : (0.1 - 10) mol. The organic solvent is preferably an anhydrous and oxygen-free organic solvent.

[0124] Preferably, the reaction is carried out under a protective atmosphere. The present invention has no particular limitation on the type of protective gas providing the protective atmosphere, and any conventional protective gas in the art can be used, such as nitrogen, helium, argon, etc.

[0125] The temperature of the reaction is preferably 80 - 200 °C; the time of the reaction is preferably 8 - 48 h. After the above reaction, a polycyclic intermediate shown in formula (II) is formed in the system.

[0126] Specifically, in the above process, the mixing order of each material is preferably: first, compound U-9 is mixed with boron triiodide or boron tribromide, and then the organic solvent is introduced. After all the materials are added, the temperature is raised to the above reaction temperature for reaction. After the reaction, a polycyclic intermediate shown in formula (II) is formed in the system.

[0127] In the step S5), the polycyclic intermediate of formula (II) reacts with at least one of compounds U-10 and U-11 in a solvent to obtain a binuclear organoboron polycyclic compound shown in formula (I).

[0128] Wherein Gu1 and Gu2 are each independently selected from hydrogen, hydroxyl, mercapto, amino,

[0129] In the above structural formula, the wavy line represents the connection position.

[0130] On the other hand, the present invention provides the application of the above binuclear organoboron polycyclic compound as an organic electroluminescent material.

[0131] The present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the binuclear organoboron fused-ring compound shown in the above formula (I).

[0132] The present invention has no particular limitation on the structure of the organic electroluminescent device, and a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to the application situation, quality requirements, and product requirements. Preferably, the structure of the organic electroluminescent device of the present invention comprises: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.

[0133] The thickness of the substrate is preferably 0.3 to 0.7 mm, more preferably 0.4 to 0.6 mm; the present invention has no special limitation on the selection of the substrate, and a substrate of a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to the application situation, quality requirements, and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0134] According to the present invention, the anode is preferably a material easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0135] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; the light-emitting layer comprises the binuclear organoboron fused-ring compound shown in the above formula (I); preferably, the light-emitting layer is directly composed of the binuclear organoboron fused-ring compound shown in formula (I) provided by the present invention.

[0136] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0137] To improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. The present invention has no particular limitation on the materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and they can be selected and adjusted according to the materials and thicknesses well-known to those skilled in the art. The present invention has no particular limitation on the preparation processes of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and preferably vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation. The present invention has no particular limitation on the preparation process of the organic electroluminescent layer, and preferably solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation.

[0138] The present invention has no special limitation on the preparation method of the organic electroluminescent device, and it can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, wherein at least one layer is a light-emitting layer; forming a cathode on the organic thin film layer;

[0139] The light-emitting layer includes one or more binuclear organoboron fused-ring compounds represented by formula (I).

[0140] The present invention has no special limitation on the structure and materials of the organic electroluminescent device in the above preparation method, and the corresponding preferred principles can correspond to the materials and structures, and the corresponding preferred principles in the foregoing organic electroluminescent device, and will not be elaborated herein one by one.

[0141] The present invention first forms an anode on the substrate. The present invention has no special limitation on the formation method of the anode, and it can be carried out according to the method well-known to those skilled in the art. Then, an organic thin film layer below the light-emitting layer, a light-emitting layer, and an organic thin film layer above the light-emitting layer are formed on the anode. The present invention has no special limitation on the formation methods of the organic thin film layers below and above the light-emitting layer, and they can be formed by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. The present invention has no special limitation on the formation method of the light-emitting layer, and it can be formed by solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. After the above-mentioned organic layers are formed, a cathode is prepared on its surface. The present invention has no special limitation on the cathode formation method, and preferably it is a method well-known to those skilled in the art, including but not limited to vacuum deposition.

[0142] Compared with the prior art, the structural feature of the binuclear organoboron fused-ring compound provided by the present invention is that it contains a molecular skeleton composed of two boron atoms and heteroatoms (N, O, S) and has 2 or 4 methyl substituents. On the one hand, the rigid skeleton structure of the fused-ring compound can be used to reduce the degree of excited-state structural relaxation, thereby achieving a narrower full width at half maximum; on the other hand, the role of the methyl substituents is also used to regulate the HOMO and LUMO energy level distributions of the fused-ring skeleton, and side reactions are inhibited in the boron cyclization reaction, the reaction yield is improved, and the material cost is reduced. The experimental results show that the organoboron fused-ring compound provided by the present invention can be used not only for assembling OLED devices by evaporation process, but also for the light-emitting layer of OLED devices by solution processing technology, and high-efficiency and long-life OLED devices can be prepared. Detailed Description of the Invention

[0143] The following examples are used to describe in detail the binuclear organoboron fused-ring compound and the organic electroluminescent device provided by the present invention. However, it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed implementation manners and specific operation processes are given, which are only used to further illustrate the features and advantages of the present invention, rather than a limitation on the claims of the present invention. The protection scope of the present invention is not limited to the following examples.

[0144] There are no special restrictions on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0145] Preparation Example 1

[0146] The chemical structure and synthetic route of I-1 are as follows:

[0147]

[0148] Under an argon atmosphere, diphenylamine (16.9 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (1.24 g, 2 mmol), and t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water many times. The organic phase was separated, and after column separation and solvent removal, compound 1-2 (23.2 g, yield: 71%) was obtained. Elemental analysis: theoretical values C, 69.52; H, 4.61; N, 4.27; measured values C, 69.54; H, 4.58; N, 4.29. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 327.1; experimental value 327.1 (M+ )。

[0149] Under an argon atmosphere, 1-2 (16.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-3 (17.7 g, yield: 86%) was obtained. Elemental analysis: theoretical values C, 78.53; H, 6.10; N, 6.78; measured values C, 78.57; H, 6.15; N, 6.79. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 412.2; experimental value 412.2 (M + )。

[0150] Under an argon atmosphere, 1-3 (9.1 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, product 1-4 (4.9 g, yield: 55%) was obtained. Elemental analysis: theoretical values C, 80.07; H, 5.82; N, 6.23; measured values C, 80.11; H, 5.80; N, 6.26. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 898.3; experimental value 898.3 (M + )。

[0151] Under an argon atmosphere, 1-4 (4.5 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 90 °C for reaction for 10 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was completed, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 1-5 (1.51 g, yield: 33%) was obtained by column separation. Elemental analysis: theoretical values C, 78.71; H, 5.06; N, 6.12; measured values C, 78.75; H, 5.02; N, 6.17. MALDI-TOF (m / z): theoretical value 914.3; experimental value 914.3 (M + ).

[0152] Under an argon atmosphere, 1-5 (0.91 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-1 (0.63 g, yield: 45%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 85.70; H, 6.76; N, 6.00; measured values C, 85.71; H, 6.72; N, 6.03. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1400.7; experimental value 1400.7 (M + ).

[0153] The photophysical properties of the polycyclic compound prepared in Preparation Example 1 of the present invention were detected.

[0154] See Table 1, and Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0155] Preparation Example 2

[0156] The chemical structure and synthetic route of I-4 are as follows:

[0157]

[0158] Under an argon atmosphere, 1-5 (1.0 g, 1 mmol), 3,9'-bicarbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-4 (0.93 g, yield: 62%) was obtained. Elemental analysis: theoretical values C, 86.05; H, 5.08; N, 7.43; measured values C, 86.04; H, 5.06; N, 7.44. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1506.6; experimental value 1506.6 (M + ).

[0159] The photophysical properties of the polycyclic compound prepared in Preparation Example 2 of the present invention were detected.

[0160] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0161] Preparation Example 3

[0162] The chemical structure and synthesis route of I-7 are as follows:

[0163]

[0164] Under an argon atmosphere, 1-5 (0.91 g, 1 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid pinacol ester (0.92 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then it was cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying, and the solvent was removed from the filtered organic phase. The crude product was separated by column chromatography to obtain the polycyclic compound I-7 (0.93 g, yield: 60%). Elemental analysis: theoretical values C, 86.58; H, 6.62; N, 5.41; measured values C, 86.57; H, 6.60; N, 5.43. MALDI-TOF (m / z): theoretical value 1552.8; experimental value 1552.8 (M + )

[0165] The photophysical properties of the polycyclic compound prepared in Preparation Example 3 of the present invention were detected.

[0166] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0167] Preparation Example 4

[0168] The chemical structure and synthetic route of I-8 are as follows:

[0169]

[0170] Under an argon atmosphere, 1-5 (0.86 g, 1 mmol), 9-phenylcarbazole-3-boronic acid pinacol ester (0.92 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol) and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then it was cooled to room temperature. The reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying. The solvent of the filtered organic phase was removed, and the crude product was separated by column chromatography to obtain the polycyclic compound I-8 (0.58 g, yield: 44%). Elemental analysis: theoretical values C, 86.74; H, 5.31; N, 6.32; measured values C, 86.70; H, 5.32; N, 6.31. MALDI-TOF (m / z): theoretical value 1328.5; experimental value 1328.5 (M + )

[0171] The photophysical properties of the polycyclic compound prepared in Preparation Example 4 of the present invention were detected.

[0172] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0173] Preparation Example 5

[0174] The chemical structure and synthetic route of I-8 are as follows:

[0175]

[0176] Weigh 1-5 (0.91 g, 1 mmol), 3-(9H-carbazol-9-yl)phenol (0.65 g, 2.5 mmol), copper(I) iodide (19 mg, 0.1 mmol) and Cs2CO3 (0.65 g, 2 mmol) in a 100 mL three-necked flask. Add 20 mL of DMF to the flask, heat it to 120 °C, and stir the reaction for 12 hours under argon protection. Then cool it to room temperature, pour the reaction solution into water, extract with dichloromethane, and wash with deionized water several times. Separate the organic phase, and obtain the polycyclic compound I-9 (0.88 g, yield: 65%) through column separation and solvent removal. Elemental analysis: theoretical values C, 84.70; H, 5.18; N, 6.17; measured values C, 84.75; H, 5.17; N, 6.16. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1360.5; experimental value 1360.5 (M + ).

[0177] Detect the photophysical properties of the polycyclic compound prepared in Preparation Example 5 of the present invention.

[0178] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0179] Preparation Example 6

[0180] The chemical structure and synthesis route of I-12 are as follows:

[0181]

[0182] Under an argon atmosphere, add 3,3'-dimethyl diphenylamine (19.7 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (1.24 g, 2 mmol), and t-BuONa (19.2 g, 0.2 mol) to a 500 mL Schlenk flask. Then inject 150 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water several times. Separate the organic phase, and obtain the compound 6-1 (25.9 g, yield: 73%) through column separation and solvent removal. Elemental analysis: theoretical values C, 70.79; H, 5.38; N, 3.93; measured values C, 70.76; H, 5.33; N, 3.94. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 355.1; experimental value 355.1 (M + ).

[0183] Under an argon atmosphere, 6-1 (17.7 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 6-2 (18.5 g, yield: 84%) was obtained. Elemental analysis: theoretical values C, 78.98; H, 6.63; N, 6.35; measured values C, 78.93; H, 6.64; N, 6.39. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 440.2; experimental value 440.2 (M + ).

[0184] Under an argon atmosphere, 6-2 (9.7 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, product 6-3 (5.0 g, yield: 52%) was obtained. Elemental analysis: theoretical values C, 80.40; H, 6.33; N, 5.86; measured values C, 80.42; H, 6.31; N, 5.87. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 956.1; experimental value 956.1 (M + ).

[0185] Under an argon atmosphere, 6-3 (4.8 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 6-4 (0.87 g, yield: 18%) was obtained by column chromatography. Elemental analysis: theoretical values C, 79.11; H, 5.60; N, 5.77; measured values C, 79.13; H, 5.61; N, 5.74. MALDI-TOF (m / z): theoretical value 971.6; experimental value 971.6 (M + ).

[0186] Under an argon atmosphere, 6-4 (0.97 g, 1 mmol), 3,6-di-tert-butyl-1,8-diphenylcarbazole (1.34 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-12 (0.6 g, yield: 35%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 87.31; H, 6.50; N, 4.93; measured values C, 87.33; H, 6.52; N, 4.91. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1705.8; experimental value 1705.8 (M + ).

[0187] The photophysical properties of the polycyclic compound prepared in Preparation Example 6 of the present invention were detected.

[0188] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0189] Preparation Example 7

[0190] The chemical structure and synthetic route of I-13 are as follows:

[0191]

[0192] Under an argon atmosphere, 6-4 (0.97 g, 1 mmol), 5,7-dihydro-5-phenylindolo[2,3-b]carbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-13 (0.9 g, yield: 60%) was obtained. Elemental analysis: theoretical values C, 86.05; H, 5.08; N, 7.43; measured values C, 86.03; H, 5.04; N, 7.41. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1506.6; experimental value 1506.6 (M + ).

[0193] The photophysical properties of the polycyclic compound prepared in Preparation Example 7 of the present invention were detected.

[0194] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0195] Preparation Example 8

[0196] The chemical structure and synthesis route of I-24 are as follows:

[0197]

[0198] Under an argon atmosphere, 1-5 (0.91 g, 1 mmol), 4,4'-difluorodiphenylamine (0.6 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-24 (0.85 g, yield: 68%) was obtained. Elemental analysis: theoretical values C, 80.52; H, 4.99; N, 6.71; measured values C, 80.51; H, 4.95; N, 6.72. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1252.5; experimental value 1252.5 (M + ).

[0199] The photophysical properties of the polycyclic compound prepared in Preparation Example 8 of the present invention were detected.

[0200] Refer to Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0201] Preparation Example 9

[0202] The chemical structure and synthetic route of I-25 are as follows:

[0203]

[0204] Under an argon atmosphere, 6-4 (0.97 g, 1 mmol), spiroacridine (9,10H)-2'-adamantane (0.9 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-25 (0.99 g, yield: 66%) was obtained. Elemental analysis: theoretical values C, 86.39; H, 6.58; N, 5.60; measured values C, 86.35; H, 6.56; N, 5.61. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1500.8; experimental value 1500.8 (M + )

[0205] The photophysical properties of the polycyclic compound prepared in Preparation Example 9 of the present invention were detected.

[0206] Refer to Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0207] Preparation Example 10

[0208] The chemical structure and synthetic route of I-26 are as follows:

[0209]

[0210] Under an argon atmosphere, 6-4 (0.97 g, 1 mmol), 4-R-4H-dithieno[3,2-b:2',3'-d]pyrrole (0.54 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-9 (0.69 g, yield: 55%) was obtained. Elemental analysis: theoretical values C, 76.42; H, 4.97; N, 6.68; measured values C, 76.40; H, 4.95; N, 6.66. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1256.4; experimental value 1256.4 (M + ).

[0211] The photophysical properties of the polycyclic compound prepared in Preparation Example 10 of the present invention were detected.

[0212] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0213] Preparation Example 11

[0214] The chemical structure and synthesis route of I-28 are as follows:

[0215]

[0216] In a 1000 mL two-necked flask, 4-chloro-3,5-dimethylaniline (15.5 g, 0.1 mol) and 500 mL of methanol were added and dissolved by stirring at 0 °C. A 40% aqueous HBr solution (44 mL, 0.3 mol) was slowly added dropwise through a constant pressure funnel, and then a 30% aqueous hydrogen peroxide solution (18.4 mL, 0.18 mol) was added dropwise. The mixture was stirred at 0 °C for 5 h. 100 mL of ice water was added for crystallization, and the mixture was filtered by suction. The filter residue was washed with ice water to obtain compound 11-2 (26.3 g, yield: 85%). Elemental analysis: theoretical values C, 30.66; H, 2.57; N, 4.47; measured values C, 30.65; H, 2.54; N, 4.42. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 310.8; experimental value 310.8 (M + ).

[0217] Under an argon atmosphere, 11-2 (15.5 g, 50 mmol) was added to a 250 mL two-necked flask. 80 mL of tetrahydrofuran was taken and added to the flask and stirred to dissolve. After the temperature was raised to 60 °C, tert-butyl nitrite (6.2 g, 60 mmol) was added dropwise, and the mixture was stirred and reacted for 8 hours. The temperature was lowered to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 11-3 (11.8 g, yield: 80%) was obtained. Elemental analysis: theoretical value C, 32.20; H, 2.36; measured value C, 32.21; H, 2.33. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 295.8; experimental value 295.8 (M + ).

[0218] Under an argon atmosphere, diphenylamine (16.9 g, 0.1 mol), 11-3 (29.6 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (1.24 g, 2 mmol), t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. The temperature was lowered to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 11-4 (25.1 g, yield: 65%) was obtained. Elemental analysis: theoretical value C, 62.12; H, 4.43; N, 3.62; measured value C, 62.13; H, 4.40; N, 3.63. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 385.0; experimental value 385.0 (M + ).

[0219] Under an argon atmosphere, 11-4 (19.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 11-5 (16.0 g, yield: 76%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.76; H, 6.37; N, 6.56; measured values C, 78.77; H, 6.34; N, 6.59. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 426.1; experimental value 426.1 (M + ).

[0220] Under an argon atmosphere, 11-5 (9.4 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and product 11-6 (6.2 g, yield: 54%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 70.17; H, 5.20; N, 4.81; measured values C, 70.13; H, 5.21; N, 4.84. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 580.1; experimental value 580.1 (M + ).

[0221] Under an argon atmosphere, 11-9 (17.8 g, 50 mmol), 1-amino-3,5-dimethylbenzene (24.0 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 11-10 (15.3 g, yield: 77%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.28; H, 5.81; N, 7.02; measured values C, 78.26; H, 5.80; N, 7.04. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 398.1; experimental value 398.1 (M + ).

[0222] Under an argon atmosphere, 11-6 (5.8 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and product 11-7 (4.6 g, yield: 51%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 80.07; H, 5.82; N, 6.23; measured values C, 80.01; H, 5.83; N, 6.25. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 898.3; experimental value 898.3 (M + ).

[0223] Under an argon atmosphere, 11-7 (4.5 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 11-8 (1.0 g, yield: 22%) was obtained by column separation. Elemental analysis: theoretical values C, 78.71; H, 5.06; N, 6.12; measured values C, 78.75; H, 5.04; N, 6.13. MALDI-TOF (m / z): theoretical value 914.3; experimental value 914.3 (M + ).

[0224] Under an argon atmosphere, 11-8 (0.91 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, 100 mL of deionized water and dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-28 (0.61 g, yield: 44%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 85.70; H, 6.76; N, 6.00; measured values C, 85.71; H, 6.72; N, 6.03. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1400.7; experimental value 1400.7 (M + ).

[0225] The photophysical properties of the polycyclic compound prepared in Preparation Example 11 of the present invention were detected.

[0226] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0227] Preparation Example 12

[0228] The chemical structure and synthesis route of I-31 are as follows:

[0229]

[0230] Under an argon atmosphere, 11-4 (19.3 g, 50 mmol), 4-butylaniline (8.9 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 12-1 (18.1 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 79.19; H, 6.87; N, 6.16; measured values C, 79.14; H, 6.83; N, 6.17. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 454.2; experimental value 454.2 (M + ).

[0231] Under an argon atmosphere, 12-1 (10.0 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, product 12-2 (7.0 g, yield: 58%) was obtained. Elemental analysis: theoretical values C, 70.88; H, 5.62; N, 4.59; measured values C, 70.83; H, 5.65; N, 4.54. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 608.1; experimental value 608.1 (M + ).

[0232] Under an argon atmosphere, 12-2 (6.1 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the product 12-3 (4.8 g, yield: 52%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 80.24; H, 6.08; N, 6.04; measured values C, 80.20; H, 6.04; N, 6.05. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 926.3; experimental value 926.3 (M + ).

[0233] Under an argon atmosphere, 12-3 (4.6 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for reaction for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 12-4 (0.94 g, yield: 20%) was obtained through column separation. Elemental analysis: theoretical values C, 78.92; H, 5.34; N, 5.94; measured values C, 78.90; H, 5.32; N, 5.93. MALDI-TOF(m / z): theoretical value 942.3; experimental value 942.3 (M + ).

[0234] Under an argon atmosphere, 12-4 (0.87 g, 1 mmol), 3,6-diphenylcarbazole (0.96 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-31 (0.66 g, yield: 44%) was obtained. Elemental analysis: theoretical values C, 87.52; H, 5.48; N, 5.57; measured values C, 87.56; H, 5.45; N, 5.54. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1508.7; experimental value 1508.7 (M + ).

[0235] The photophysical properties of the polycyclic compound prepared in Preparation Example 12 of the present invention were detected.

[0236] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0237] Preparation Example 13

[0238] The chemical structure and synthetic route of I-34 are as follows:

[0239]

[0240] Under an argon atmosphere, 11-5 (9.1 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the product 13-1 (3.7 g, yield: 40%) was obtained. Elemental analysis: theoretical values C, 80.24; H, 6.08; N, 6.04; measured values C, 80.26; H, 6.09; N, 6.05. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 926.3; experimental value 926.3 (M + ).

[0241] Under an argon atmosphere, 13-1 (4.6 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask and heated to 200 °C for reaction for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 13-2 (1.1 g, yield: 23%) was obtained by column separation. Elemental analysis: theoretical values C, 78.92; H, 5.34; N, 5.94; measured values C, 78.93; H, 5.33; N, 5.96. MALDI-TOF (m / z): theoretical value 942.3; experimental value 942.3 (M + ).

[0242] Under an argon atmosphere, 13-2 (0.94 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the polycyclic compound I-34 (0.71 g, yield: 45%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 85.70; H, 6.91; N, 5.88; measured values C, 85.73; H, 6.90; N, 5.89. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1428.8; experimental value 1428.8 (M + ).

[0243] The photophysical properties of the polycyclic compound prepared in Preparation Example 13 of the present invention were detected.

[0244] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0245] Preparation Example 14

[0246] The chemical structure and synthesis route of I-38 are as follows:

[0247]

[0248] Under an argon atmosphere, 11-4 (19.3 g, 50 mmol), 5,6,7,8-tetrahydro-2-naphthylamine (8.8 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 14-1 (17.6 g, yield: 78%) was obtained. Elemental analysis: theoretical values C, 79.54; H, 6.45; N, 6.18; measured values C, 79.54; H, 6.43; N, 6.17. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 452.2; experimental value 452.2 (M + ).

[0249] Under an argon atmosphere, 14-1 (9.1 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, product 14-2 (4.1 g, yield: 42%) was obtained. Elemental analysis: theoretical values C, 80.88; H, 6.17; N, 5.72; measured values C, 80.85; H, 6.14; N, 5.75. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 978.4; experimental value 978.4 (M + ).

[0250] Under an argon atmosphere, 14-2 (4.9 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 14-3 (1.2 g, yield: 24%) was obtained by column separation. Elemental analysis: theoretical values C, 79.61; H, 5.47; N, 5.63; measured values C, 79.62; H, 5.45; N, 5.66. MALDI-TOF (m / z): theoretical value 994.3; experimental value 994.3 (M + ).

[0251] Under an argon atmosphere, 14-3 (1.0 g, 1 mmol), 3-(diphenylamino)carbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-38 (0.73 g, yield: 46%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 86.03; H, 5.57; N, 7.04; measured values C, 86.05; H, 5.54; N, 7.06. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1591.5; experimental value 1591.5 (M + ).

[0252] The photophysical properties of the polycyclic compound prepared in Preparation Example 14 of the present invention were detected.

[0253] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0254] Preparation Example 15

[0255] The chemical structure and synthetic route of I-40 are as follows:

[0256]

[0257] In a 250 mL three-necked flask, weigh phenol (9.4 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol) and Cs2CO3 (65 g, 0.2 mol). Add 100 mL of DMF to the flask, heat up to 120 °C, stir and react for 12 hours under argon protection. Then cool to room temperature, pour the reaction solution into water, add dichloromethane for extraction, and wash with deionized water for several times. After column separation and solvent removal, product 15-1 (18.6 g, yield: 74%) is obtained. Elemental analysis: theoretical value C, 61.68; H, 3.98; measured value C, 61.65; H, 3.96. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 252.0; experimental value 252.0 (M + ).

[0258] Under an argon atmosphere, add 15-1 (12.6 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (9.6 g, 0.1 mol) into a 100 mL Schlenk flask, then inject 40 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water for several times. Separate the organic phase, after column separation and solvent removal, compound 15-2 (14.1 g, yield: 84%) is obtained. Elemental analysis: theoretical value C, 74.66; H, 5.97; N, 4.15; measured value C, 74.63; H, 5.95; N, 4.16. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 337.1; experimental value 337.1 (M + ).

[0259] Under an argon atmosphere, 15-2 (7.4 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 15-3 (6.4 g, yield: 65%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 65.80; H, 4.70; N, 2.84; measured values C, 65.81; H, 4.72; N, 2.83. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 491.0; experimental value 491.0 (M + ).

[0260] Under an argon atmosphere, 15-3 (4.9 g, 10 mmol), 1-3 (4.1 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 15-4 (4.1 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.63; H, 5.74; N, 5.09; measured values C, 78.61; H, 5.74; N, 5.06. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 823.3; experimental value 823.3 (M + ).

[0261] Under an argon atmosphere, 15-4 (4.1 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 90 °C for reaction for 10 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 15-5 (1.17 g, yield: 28%) was obtained by column chromatography. Elemental analysis: theoretical value C, 77.17; H, 4.92; N, 5.00; measured value C, 77.14; H, 4.93; N, 5.02. MALDI-TOF (m / z): theoretical value 839.2; experimental value 839.2 (M + ).

[0262] Under an argon atmosphere, 15-5 (0.84 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-40 (0.53 g, yield: 40%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical value C, 85.12; H, 6.76; N, 5.28; measured value C, 85.17; H, 6.74; N, 5.25. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1325.7; experimental value 1325.7 (M + ).

[0263] The photophysical properties of the polycyclic compound prepared in Preparation Example 15 of the present invention were detected.

[0264] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0265] Preparation Example 16

[0266] The chemical structure and synthetic route of I-41 are as follows:

[0267]

[0268] Under an argon atmosphere, 15-5 (0.84 g, 1 mmol), 3-phenylcarbazole (0.73 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask. Then, 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-40 (0.63 g, yield: 50%) was obtained. Elemental analysis: theoretical values C, 86.19; H, 5.22; N, 5.58; measured values C, 86.17; H, 5.21; N, 5.54. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1254.1; experimental value 1254.1 (M + ).

[0269] The photophysical properties of the polycyclic compound prepared in Preparation Example 16 of the present invention were detected.

[0270] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0271] Preparation Example 17

[0272] The chemical structure and synthetic route of I-44 are as follows:

[0273]

[0274] Under an argon atmosphere, 15-5 (0.91 g, 1 mmol), 3-(9H-carbazol-9-yl)phenylboronic acid pinacol ester (0.92 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then, it was cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying, and the solvent was removed from the filtered organic phase. The crude product was separated by column chromatography to obtain the polycyclic compound I-44 (0.69 g, yield: 55%). Elemental analysis: theoretical values C, 86.19; H, 5.22; N, 5.58; measured values C, 86.15; H, 5.20; N, 5.56. MALDI-TOF(m / z): theoretical value 1253.5; experimental value 1253.5 (M + )

[0275] The photophysical properties of the polycyclic compound prepared in Preparation Example 17 of the present invention were detected.

[0276] Refer to Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0277] Preparation Example 18

[0278] The chemical structure and synthetic route of I-46 are as follows:

[0279]

[0280] Weigh m-cresol (10.8 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol) and Cs2CO3 (65 g, 0.2 mol) in a 250 mL three-necked flask. Add 100 mL of DMF to the flask, heat up to 120 °C, stir and react for 12 hours under argon protection, then cool to room temperature. Pour the reaction solution into water, add dichloromethane for extraction, and wash with deionized water for several times. After column separation and solvent removal, the product 18-1 (20.0 g, yield: 75%) was obtained. Elemental analysis: theoretical value C, 62.94; H, 4.53; measured value C, 62.91; H, 4.54. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 266.0; experimental value 266.0 (M + )

[0281] Under an argon atmosphere, add 18-1 (13.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (9.6 g, 0.1 mol) into a 100 mL Schlenk flask, then inject 40 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water for several times. Separate the organic phase, and after column separation and solvent removal, the compound 18-2 (14.0 g, yield: 80%) was obtained. Elemental analysis: theoretical value C, 75.09; H, 6.30; N, 3.98; measured value C, 75.07; H, 6.31; N, 3.95. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 351.1; experimental value 351.1 (M + )

[0282] Under an argon atmosphere, 18-2 (7.7 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 18-3 (6.2 g, yield: 61%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 66.35; H, 4.97; N, 2.76; measured values C, 66.38; H, 4.96; N, 2.77. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 505.0; experimental value 505.0 (M + ).

[0283] Under an argon atmosphere, 18-3 (5.0 g, 10 mmol), 6-2 (4.4 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 18-4 (4.5 g, yield: 52%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.97; H, 6.16; N, 4.85; measured values C, 78.93; H, 6.10; N, 4.88. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 865.3; experimental value 865.3 (M + ).

[0284] Under an argon atmosphere, 18-4 (4.3 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 90 °C and reacted for 10 hours. The reaction was cooled to 0 °C, and N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 18-5 (1.06 g, yield: 24%) was obtained by column chromatography. Elemental analysis: theoretical values C, 77.57; H, 5.37; N, 4.76; measured values C, 77.53; H, 5.33; N, 4.77. MALDI-TOF (m / z): theoretical value 881.3; experimental value 881.3 (M + ).

[0285] Under an argon atmosphere, 18-5 (0.88 g, 1 mmol), bis(5,6,7,8-tetrahydro-2-naphthyl)amine (0.83 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, 100 mL of deionized water and dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-46 (0.75 g, yield: 55%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 85.39; H, 6.72; N, 5.13; measured values C, 85.33; H, 6.70; N, 5.15. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1363.7; experimental value 1363.7 (M + ).

[0286] The photophysical properties of the polycyclic compound prepared in Preparation Example 18 of the present invention were detected.

[0287] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0288] Preparation Example 19

[0289] The chemical structure and synthetic route of I-47 are as follows:

[0290]

[0291] Under an argon atmosphere, 18-5 (0.88 g, 1 mmol), 3,9'-bicarbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask. Then, 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-47 (0.74 g, yield: 50%) was obtained. Elemental analysis: theoretical values C, 85.53; H, 5.26; N, 6.65; measured values C, 85.54; H, 5.23; N, 6.66. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1473.6; experimental value 1473.6 (M + )).

[0292] The photophysical properties of the polycyclic compound prepared in Preparation Example 19 of the present invention were detected.

[0293] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0294] Preparation Example 20

[0295] The chemical structure and synthesis route of I-49 are as follows:

[0296]

[0297] Under an argon atmosphere, 18-5 (0.88 g, 1 mmol), 3-(diphenylamino)carbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask. Then, 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-49 (0.66 g, yield: 45%) was obtained. Elemental analysis: theoretical values C, 85.30; H, 5.52; N, 6.63;; measured values C, 85.27; H, 5.55; N, 6.64. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1477.6; experimental value 1477.6 (M + )).

[0298] The photophysical properties of the polycyclic compound prepared in Preparation Example 20 of the present invention were detected.

[0299] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0300] Preparation Example 21

[0301] The chemical structure and synthetic route of I-51 are as follows:

[0302]

[0303] Under an argon atmosphere, 18-5 (0.88 g, 1 mmol), spiroacridine (9,10H)-2'-adamantane (0.9 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-51 (0.92 g, yield: 65%) was obtained. Elemental analysis: theoretical values C, 85.88; H, 6.49; N, 4.96; measured values C, 85.86; H, 6.46; N, 4.95. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1411.7; experimental value 1411.7 (M + )

[0304] The photophysical properties of the polycyclic compound prepared in Preparation Example 21 of the present invention were detected.

[0305] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0306] Preparation Example 22

[0307] The chemical structure and synthetic route of I-52 are as follows:

[0308]

[0309] Under an argon atmosphere, 22-1 (12.0 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 22-2 (13.0 g, yield: 81%) was obtained. Elemental analysis: theoretical values C, 74.18; H, 5.60; N, 4.33; measured values C, 74.15; H, 5.61; N, 4.35. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 323.1; experimental value 323.1 (M + ).

[0310] Under an argon atmosphere, 11-6 (5.8 g, 10 mmol), 22-2 (3.2 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, product 22-3 (4.1 g, yield: 50%) was obtained. Elemental analysis: theoretical values C, 78.63; H, 5.74; N, 5.09; measured values C, 78.64; H, 5.76; N, 5.05. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 823.3; experimental value 823.3 (M + ).

[0311] Under an argon atmosphere, 22-3 (4.1 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 22-4 (0.88 g, yield: 21%) was obtained by column separation. Elemental analysis: theoretical values C, 77.17; H, 4.92; N, 5.00; measured values C, 77.15; H, 4.92; N, 5.03. MALDI-TOF (m / z): theoretical value 839.2; experimental value 839.2 (M + ).

[0312] Under an argon atmosphere, 22-4 (0.84 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-52 (0.56 g, yield: 42%) was obtained. Elemental analysis: theoretical values C, 85.12; H, 6.76; N, 5.28; measured values C, 85.17; H, 6.72; N, 5.27. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1325.7; experimental value 1325.7 (M + ).

[0313] The photophysical properties of the polycyclic compound prepared in Preparation Example 22 of the present invention were detected.

[0314] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0315] Preparation Example 23

[0316] The chemical structure and synthesis route of I-55 are as follows:

[0317]

[0318] Under an argon atmosphere, 23-1 (12.6 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 23-2 (13.4 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 74.66; H, 5.97; N, 4.15; measured values C, 74.64; H, 5.93; N, 4.17. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 337.1; experimental value 337.1 (M + ).

[0319] Under an argon atmosphere, 23-2 (7.4 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, product 23-3 (6.1 g, yield: 62%) was obtained. Elemental analysis: theoretical values C, 65.80; H, 4.70; N, 2.84; measured values C, 65.80; H, 4.71; N, 2.82. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 491.0; experimental value 491.0 (M + ).

[0320] Under an argon atmosphere, 23-3 (4.9 g, 10 mmol), 14-1 (4.5 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 23-4 (4.3 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 79.15; H, 5.94; N, 4.86; measured values C, 79.12; H, 5.92; N, 4.88. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 863.3; experimental value 863.3 (M + ).

[0321] Under an argon atmosphere, 23-4 (4.1 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 23-5 (0.82 g, yield: 19%) was obtained through column separation. Elemental analysis: theoretical values C, 77.62; H, 5.00; N, 4.85; measured values C, 77.65; H, 5.02; N, 4.82. MALDI-TOF (m / z): theoretical value 865.3; experimental value 865.3 (M + ).

[0322] Under an argon atmosphere, 23-5 (0.86 g, 1 mmol), 9-phenylcarbazole-2-boronic acid pinacol ester (0.92 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then, it was cooled to room temperature. The reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying. The solvent was removed from the filtered organic phase, and the crude product was separated by column chromatography to obtain polycyclic compound I-55 (0.52 g, yield: 40%). Elemental analysis: theoretical values C, 86.31; H, 5.37; N, 5.41; measured values C, 86.33; H, 5.36; N, 5.42. MALDI-TOF (m / z): theoretical value 1293.5; experimental value 1293.5 (M+)

[0323] The photophysical properties of the polycyclic compound prepared in Preparation Example 23 of the present invention were detected.

[0324] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0325] Preparation Example 24

[0326] The chemical structure and synthesis route of I-58 are as follows:

[0327]

[0328] Phenol (9.4 g, 0.1 mol), 11-3 (29.6 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol), and Cs2CO3 (65 g, 0.2 mol) were weighed in a 250 mL three-necked flask. 100 mL of DMF was added to the flask. The temperature was raised to 120 °C, and the reaction was stirred under argon protection for 12 hours. Then, it was cooled to room temperature. The reaction solution was poured into water and extracted with dichloromethane, and washed several times with deionized water. After column separation and solvent removal, the product 24-1 (23.6 g, yield: 76%) was obtained. Elemental analysis: theoretical values C, 53.96; H, 3.88; measured values C, 53.93; H, 3.84. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 309.9; experimental value 309.9 (M + )

[0329] Under an argon atmosphere, 24-1 (15.5 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 24-2 (13.5 g, yield: 77%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 75.09; H, 6.30; N, 3.98; measured values C, 75.03; H, 6.35; N, 3.97. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 351.1; experimental value 351.1 (M + ).

[0330] Under an argon atmosphere, 24-2 (7.7 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and product 24-3 (6.1 g, yield: 60%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 66.35; H, 4.97; N, 2.76; measured values C, 66.39; H, 4.97; N, 2.71. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 505.0; experimental value 505.0 (M + ).

[0331] Under an argon atmosphere, 24-3 (5.0 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 24-4 (4.1 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.63; H, 5.74; N, 5.09; measured values C, 78.62; H, 5.75; N, 5.03. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 823.3; experimental value 823.3 (M + ).

[0332] Under an argon atmosphere, 24-4 (4.1 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 24-5 (0.84 g, yield: 20%) was obtained through column separation. Elemental analysis: theoretical values C, 77.17; H, 4.92; N, 5.00; measured values C, 77.11; H, 4.94; N, 5.05. MALDI-TOF(m / z): theoretical value 839.2; experimental value 839.2 (M + ).

[0333] Under an argon atmosphere, 24-5 (0.84 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-58 (0.53 g, yield: 40%) was obtained. Elemental analysis: theoretical values C, 85.12; H, 6.76; N, 5.28;; measured values C, 85.11; H, 6.74; N, 5.25. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 1325.7; experimental value 1325.7 (M + )。

[0334] The photophysical properties of the polycyclic compound prepared in Preparation Example 24 of the present invention were detected.

[0335] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0336] Preparation Example 25

[0337] The chemical structure and synthesis route of I-61 are as follows:

[0338]

[0339] Under an argon atmosphere, 24-1 (15.5 g, 50 mmol), 4-n-hexylaniline (10.6 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the compound 25-1 (15.9 g, yield: 78%) was obtained. Elemental analysis: theoretical values C, 76.54; H, 7.41; N, 3.43; measured values C, 76.55; H, 7.42; N, 3.41. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 407.2; experimental value 407.2 (M + )。

[0340] Under an argon atmosphere, 25-1 (9.0 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 25-2 (6.1 g, yield: 60%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 68.27; H, 5.91; N, 2.49; measured values C, 68.28; H, 5.93; N, 2.42. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 561.1; experimental value 561.1 (M + ).

[0341] Under an argon atmosphere, 25-2 (5.6 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 25-3 (4.7 g, yield: 54%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 79.07; H, 6.29; N, 4.77; measured values C, 79.09; H, 6.28; N, 4.75. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 879.3; experimental value 879.3 (M + ).

[0342] Under an argon atmosphere, 25-3 (4.4 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 25-4 (0.84 g, yield: 20%) was obtained by column separation. Elemental analysis: theoretical value C, 77.70; H, 5.51; N, 4.69; measured value C, 77.71; H, 5.52; N, 4.65. MALDI-TOF (m / z): theoretical value 895.3; experimental value 895.3 (M + )

[0343] Under an argon atmosphere, 25-4 (0.86 g, 1 mmol), dibenzothiophene-4-boronic acid pinacol ester (0.78 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol) and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the aqueous potassium carbonate solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then it was cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the crude product was separated by column chromatography to obtain the polycyclic compound I-61 (0.5 g, yield: 42%). Elemental analysis: theoretical value C, 82.61; H, 5.33; N, 3.52; measured value C, 82.62; H, 5.34; N, 3.51. MALDI-TOF (m / z): theoretical value 1191.4; experimental value 1191.4 (M + )

[0344] The photophysical properties of the polycyclic compound prepared in Preparation Example 25 of the present invention were detected.

[0345] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0346] Preparation Example 26

[0347] The chemical structure and synthesis route of I-64 are as follows:

[0348]

[0349] Under an argon atmosphere, 24-3 (5.1 g, 10 mmol), 11-5 (4.3 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 26-1 (4.3 g, yield: 51%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.86; H, 6.03; N, 4.93; measured values C, 78.82; H, 6.01; N, 4.95. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 851.3; experimental value 851.3 (M + ).

[0350] Under an argon atmosphere, 26-1 (4.2 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 26-2 (0.98 g, yield: 22%) was obtained through column separation. Elemental analysis: theoretical values C, 77.44; H, 5.22; N, 4.84; measured values C, 77.42; H, 5.24; N, 4.82. MALDI-TOF (m / z): theoretical value 867.3; experimental value 867.3 (M + ).

[0351] Under an argon atmosphere, 26-2 (0.87 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-64 (0.6 g, yield: 44%) was obtained. Elemental analysis: theoretical values C, 85.13; H, 6.92; N, 5.17; measured values C, 85.11; H, 6.90; N, 5.19. MALDI-TOF (m / z): theoretical value 1353.7; experimental value 1353.7 (M + )

[0352] The photophysical properties of the polycyclic compound prepared in Preparation Example 26 of the present invention were detected.

[0353] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0354] Preparation Example 27

[0355] The chemical structure and synthesis route of I-67 are as follows:

[0356]

[0357] Under an argon atmosphere, 11-4 (19.3 g, 50 mmol), 4-n-hexylaniline (10.6 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 27-1 (17.4 g, yield: 72%) was obtained. Elemental analysis: theoretical values C, 79.56; H, 7.30; N, 5.80; measured values C, 79.50; H, 7.35; N, 5.81. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 482.2; experimental value 482.2 (M + )

[0358] Under an argon atmosphere, 27-1 (4.8 g, 10 mmol), 12-2 (5.6 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 27-2 (4.8 g, yield: 52%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 79.64; H, 7.00; N, 4.35; measured values C, 79.66; H, 7.01; N, 4.39. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 963.4; experimental value 963.4 (M + ).

[0359] Under an argon atmosphere, 27-2 (4.8 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for reaction for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 27-3 (1.12 g, yield: 23%) was obtained through column separation. Elemental analysis: theoretical values C, 78.38; H, 6.27; N, 4.28; measured values C, 78.39; H, 6.25; N, 4.26. MALDI-TOF (m / z): theoretical value 979.4; experimental value 979.4 (M + ).

[0360] Under an argon atmosphere, 27-3 (0.98 g, 1 mmol), 3,9'-bicarbazole (1.0 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-67 (0.63 g, yield: 40%) was obtained. Elemental analysis: theoretical values C, 85.54; H, 5.83; N, 6.23; measured values C, 85.52; H, 5.84; N, 6.27. MALDI-TOF (m / z): theoretical value 1571.7; experimental value 1571.7 (M + )

[0361] The photophysical properties of the polycyclic compound prepared in Preparation Example 27 of the present invention were detected.

[0362] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0363] Preparation Example 28

[0364] The chemical structure and synthetic route of I-70 are as follows:

[0365]

[0366] Under an argon atmosphere, 15-2 (7.4 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the product 28-1 (4.9 g, yield: 65%) was obtained. Elemental analysis: theoretical values C, 76.89; H, 5.65; N, 3.74; measured values C, 76.86; H, 5.62; N, 3.75. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 748.2; experimental value 748.2 (M + )

[0367] Under an argon atmosphere, 28-1 (3.7 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 90 °C for reaction for 10 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 28-2 (1.75 g, yield: 23%) was obtained by column chromatography. Elemental analysis: theoretical values C, 75.33; H, 4.74; N, 3.66; measured values C, 75.32; H, 4.75; N, 3.64. MALDI-TOF (m / z): theoretical value 764.2; experimental value 764.2 (M + ).

[0368] Under an argon atmosphere, 28-2 (0.76 g, 1 mmol), carbazole (0.54 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-70 (0.41 g, yield: 40%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 84.22; H, 5.10; N, 5.46; measured values C, 84.23; H, 5.11; N, 5.44. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1026.4; experimental value 1026.4 (M + ).

[0369] The photophysical properties of the polycyclic compound prepared in Preparation Example 28 of the present invention were detected.

[0370] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0371] Preparation Example 29

[0372] The chemical structure and synthetic route of I-71 are as follows:

[0373]

[0374] Under an argon atmosphere, 28-2 (0.76 g, 1 mmol), 9-phenylcarbazole-3-boronic acid pinacol ester (0.92 g, 2.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol) and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then it was cooled to room temperature. The reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying. The solvent of the filtered organic phase was removed, and the crude product was separated by column chromatography to obtain polycyclic compound I-71 (0.56 g, yield: 50%). Elemental analysis: theoretical values C, 85.57; H, 5.13; N, 4.75; measured values C, 85.55; H, 5.14; N, 4.73. MALDI-TOF (m / z): theoretical value 1178.4; experimental value 1178.4 (M + )

[0375] The photophysical properties of the polycyclic compound prepared in Preparation Example 29 of the present invention were detected.

[0376] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0377] Preparation Example 30

[0378] The chemical structure and synthetic route of I-75 are as follows:

[0379]

[0380] Under an argon atmosphere, 28-2 (0.76 g, 1 mmol), spiroacridine(9,10H)-2'-adamantane (0.9 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask. Then 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, 100 mL of deionized water and dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, polycyclic compound I-75 (0.77 g, yield: 60%) was obtained. Elemental analysis: theoretical values C, 85.17; H, 6.28; N, 4.37; measured values C, 85.16; H, 6.25; N, 4.39. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1282.6; experimental value 1282.6 (M + )

[0381] The photophysical properties of the polycyclic compound prepared in Preparation Example 30 of the present invention were detected.

[0382] Refer to Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0383] Preparation Example 31

[0384] The chemical structure and synthetic route of I-76 are as follows:

[0385]

[0386] Weigh thiophenol (11.0 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol) and Cs2CO3 (65 g, 0.2 mol) in a 250 mL three-necked flask. Add 100 mL of DMF to the flask, heat up to 120 °C, and stir the reaction for 12 hours under argon protection. Then cool to room temperature, pour the reaction solution into water, add dichloromethane for extraction, and wash with deionized water multiple times. After column separation and solvent removal, product 31-1 (18.8 g, yield: 70%) was obtained. Elemental analysis: theoretical value C, 58.00; H, 3.74; measured value C, 58.01; H, 3.72. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 267.9; experimental value 267.9 (M + )

[0387] Under an argon atmosphere, add 31-1 (13.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) to a 100 mL Schlenk flask. Then inject 40 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water multiple times. Separate the organic phase, and after column separation and solvent removal, compound 31-2 (13.8 g, yield: 78%) was obtained. Elemental analysis: theoretical value C, 71.27; H, 5.70; N, 3.96; measured value C, 71.22; H, 5.74; N, 3.97. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 353.1; experimental value 353.1 (M + )

[0388] Under an argon atmosphere, 31-2 (7.7 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 31-3 (6.1 g, yield: 60%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 63.72; H, 4.56; N, 2.75; measured values C, 66.78; H, 4.55; N, 2.77. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 507.0; experimental value 507.0 (M + ).

[0389] Under an argon atmosphere, 31-3 (5.0 g, 10 mmol), 1-3 (4.1 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 31-4 (4.2 g, yield: 50%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 77.13; H, 5.63; N, 5.00; measured values C, 77.14; H, 5.62; N, 5.01. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 839.2; experimental value 839.2 (M + ).

[0390] Under an argon atmosphere, 31-4 (4.2 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask and heated to 90 °C for reaction for 10 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 31-5 (1.06 g, yield: 24%) was obtained by column separation. Elemental analysis: theoretical values C, 75.72; H, 4.82; N, 4.91; measured values C, 75.70; H, 4.83; N, 4.92. MALDI-TOF (m / z): theoretical value 855.2; experimental value 855.2 (M + ).

[0391] Under an argon atmosphere, 31-5 (0.85 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-76 (0.6 g, yield: 45%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 84.10; H, 6.68; N, 5.22; measured values C, 84.09; H, 6.64; N, 5.23. MALDI-TOF (m / z): theoretical value 1341.7; experimental value 1341.7 (M + )

[0392] The photophysical properties of the polycyclic compound prepared in Preparation Example 31 of the present invention were detected.

[0393] See Table 1, and Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0394] Preparation Example 32

[0395] The chemical structure and synthesis route of I-79 are as follows:

[0396]

[0397] In a 250 mL three-necked flask, weigh 3-methylthiophenol (12.4 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol) and Cs2CO3 (65 g, 0.2 mol). Add 100 mL of DMF to the flask, heat up to 120 °C, stir and react for 12 hours under argon protection. Then cool to room temperature, pour the reaction solution into water, add dichloromethane for extraction, and wash with deionized water for several times. After column separation and solvent removal, the product 32-1 (20.3 g, yield: 72%) is obtained. Elemental analysis: theoretical value C, 59.37; H, 4.27; measured value C, 59.35; H, 4.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 282; experimental value 282 (M + ).

[0398] Under an argon atmosphere, add 32-1 (14.1 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (9.6 g, 0.1 mol) into a 100 mL Schlenk flask, then inject 40 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water for several times. Separate the organic phase, and after column separation and solvent removal, the compound 32-2 (13.9 g, yield: 76%) is obtained. Elemental analysis: theoretical value C, 71.82; H, 6.03; N, 3.81; measured value C, 71.83; H, 6.00; N, 3.83. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 367.1; experimental value 367.1 (M + ).

[0399] Under an argon atmosphere, 32-2 (8.1 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 32-3 (6.1 g, yield: 59%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 64.31; H, 4.82; N, 2.68; measured values C, 64.32; H, 4.83; N, 2.67. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 521.0; experimental value 521.0 (M + ).

[0400] Under an argon atmosphere, 3-methyl-(3’,5’-dimethylphenyl)aniline (21.1 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (1.24 g, 2 mmol), and t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask. Then, 150 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the compound 32-4 (24.0 g, yield: 65%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 71.35; H, 5.72; N, 3.78; measured values C, 71.34; H, 5.73; N, 3.76. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 369.1; experimental value 369.1 (M + ).

[0401] Under an argon atmosphere, 32-4 (14.0 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 32-5 (16.3 g, yield: 72%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 79.19; H, 6.87; N, 6.16; measured values C, 79.16; H, 6.85; N, 6.14. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 454.2; experimental value 454.2 (M + ).

[0402] Under an argon atmosphere, 32-3 (5.2 g, 10 mmol), 32-5 (4.5 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and product 32-6 (5.0 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 77.66; H, 6.18; N, 4.68;; measured values C, 77.67; H, 6.13; N, 4.66. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 895.3; experimental value 895.3 (M + ).

[0403] Under an argon atmosphere, 32-6 (4.9 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C for reaction for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 32-7 (0.96 g, yield: 21%) was obtained by column separation. Elemental analysis: theoretical value C, 76.33; H, 5.41; N, 4.60; measured value C, 76.30; H, 5.42; N, 4.61. MALDI-TOF (m / z): theoretical value 911.3; experimental value 911.3 (M + ).

[0404] Under an argon atmosphere, 32-7 (0.91 g, 1 mmol), 10,11-dihydro-5H-dibenzo[b,f]azepine (0.58 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-79 (0.63 g, yield: 51%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 83.96; H, 5.98; N, 5.69; measured value C, 83.98; H, 5.96; N, 5.65. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1229.5; experimental value 1229.5 (M + ).

[0405] The photophysical properties of the polycyclic compound prepared in Preparation Example 32 of the present invention were detected.

[0406] See Table 1, and Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0407] Preparation Example 33

[0408] The chemical structure and synthetic route of I-82 are as follows:

[0409]

[0410] In a 250 mL three-necked flask, weigh thiophenol (11.0 g, 0.1 mol), 3,5-dichloro-1-bromobenzene (22.6 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol) and Cs2CO3 (65 g, 0.2 mol). Add 100 mL of DMF to the flask, heat up to 120 °C, stir and react for 12 hours under argon protection. Then cool to room temperature, pour the reaction solution into water, add dichloromethane for extraction, and wash with deionized water for several times. After column separation and solvent removal, the product 33-2 (20.3 g, yield: 80%) is obtained. Elemental analysis: theoretical value C, 56.48; H, 3.16; measured value C, 56.46; H, 3.14. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 253.9; experimental value 253.9 (M + ).

[0411] Under an argon atmosphere, add 33-2 (12.7 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (9.6 g, 0.1 mol) into a 100 mL Schlenk flask, then inject 40 mL of toluene and react at 110 °C for 12 hours. Cool to room temperature, add deionized water and 200 mL of dichloromethane for extraction, and wash with deionized water for several times. Separate the organic phase, and after column separation and solvent removal, the compound 33-3 (12.7 g, yield: 75%) is obtained. Elemental analysis: theoretical value C, 70.68; H, 5.34; N, 4.12; measured value C, 70.66; H, 5.32; N, 4.13. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 339.0; experimental value 339.0 (M + ).

[0412] Under an argon atmosphere, 33-3 (3.4 g, 10 mmol), 11-6 (5.8 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 33-4 (4.6 g, yield: 55%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 77.13; H, 5.63; N, 5.00; measured values C, 77.15; H, 5.62; N, 5.01. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 839.2; experimental value 839.2 (M + ).

[0413] Under an argon atmosphere, 33-4 (4.2 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask. The temperature was raised to 200 °C and the reaction was carried out for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 33-5 (0.85 g, yield: 20%) was obtained through column separation. Elemental analysis: theoretical values C, 75.72; H, 4.82; N, 4.91; measured values C, 75.73; H, 4.80; N, 4.93. MALDI-TOF (m / z): theoretical value 855.2; experimental value 855.2 (M + ).

[0414] Under an argon atmosphere, 33-5 (0.85 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-82 (0.66 g, yield: 49%) was obtained. Elemental analysis: theoretical values C, 84.10; H, 6.68; N, 5.22; measured values C, 84.11; H, 6.63; N, 5.25. MALDI-TOF (m / z): theoretical value 1341.7; experimental value 1341.7 (M + )

[0415] The photophysical properties of the polycyclic compound prepared in Preparation Example 33 of the present invention were detected.

[0416] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0417] Preparation Example 34

[0418] The chemical structure and synthetic route of I-85 are as follows:

[0419]

[0420] Under an argon atmosphere, 34-1 (13.4 g, 50 mmol), 4-cyclohexylaniline (10.5 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, the compound 34-2 (16.1 g, yield: 79%) was obtained. Elemental analysis: theoretical values C, 73.60; H, 6.42; N, 3.43; measured values C, 73.61; H, 6.40; N, 3.45. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 407.1; experimental value 407.1 (M + )

[0421] Under an argon atmosphere, 34-2 (8.9 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 34-3 (7.1 g, yield: 63%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 66.13; H, 5.19; N, 2.49; measured values C, 66.14; H, 5.18; N, 2.47. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 561.0; experimental value 561.0 (M + ).

[0422] Under an argon atmosphere, 11-4 (19.2 g, 50 mmol), 4-cyclohexylaniline (10.5 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the compound 34-4 (18.4 g, yield: 77%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 79.89; H, 6.91; N, 5.82; measured values C, 79.86; H, 6.91; N, 5.83. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 480.2; experimental value 480.2 (M + ).

[0423] Under an argon atmosphere, 34-3 (5.6 g, 10 mmol), 34-4 (4.8 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 34-5 (4.3 g, yield: 51%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.56; H, 6.38; N, 4.36; measured values C, 78.56; H, 6.38; N, 4.36. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 961.4; experimental value 961.4 (M + ).

[0424] Under an argon atmosphere, 34-5 (4.8 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 34-6 (0.98 g, yield: 20%) was obtained through column separation. Elemental analysis: theoretical values C, 77.31; H, 5.66; N, 4.29; measured values C, 77.34; H, 5.65; N, 4.27. MALDI-TOF (m / z): theoretical value 977.3; experimental value 977.3 (M + ).

[0425] Under an argon atmosphere, 34-6 (0.98 g, 1 mmol), 5H-benzo[4,5]thieno[3,2-c]carbazole (0.82 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-85 (0.6 g, yield: 41%) was obtained. Elemental analysis: theoretical values C, 81.86; H, 5.20; N, 4.82; measured values C, 81.84; H, 5.21; N, 4.85. MALDI-TOF (m / z): theoretical value 1451.5; experimental value 1451.5 (M + ).

[0426] The photophysical properties of the polycyclic compound prepared in Preparation Example 34 of the present invention were detected.

[0427] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0428] Preparation Example 35

[0429] The chemical structure and synthetic route of I-88 are as follows:

[0430]

[0431] In a 250 mL three-necked flask, benzenethiol (11.0 g, 0.1 mol), 11-3 (29.8 g, 0.1 mol), copper(I) iodide (1.9 g, 10 mmol), and Cs2CO3 (65 g, 0.2 mol) were weighed. 100 mL of DMF was added to the flask, and the temperature was raised to 120 °C. The reaction was stirred under argon protection for 12 hours, and then cooled to room temperature. The reaction solution was poured into water, and dichloromethane was added for extraction, and it was washed with deionized water multiple times. After column separation and solvent removal, the product 35-1 (26.1 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 51.32; H, 3.69; measured values C, 51.33; H, 3.62. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 325.9; experimental value 325.9 (M + ).

[0432] Under an argon atmosphere, 35-1 (16.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 35-2 (12.8 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 71.82; H, 6.03; N, 3.81; measured values C, 71.83; H, 6.00; N, 3.82. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 367.1; experimental value 367.1 (M + ).

[0433] Under an argon atmosphere, 35-2 (8.1 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, product 35-3 (6.3 g, yield: 60%) was obtained. Elemental analysis: theoretical values C, 64.31; H, 4.82; N, 2.68; measured values C, 64.33; H, 4.80; N, 2.66. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 521.0; experimental value 521.0 (M + ).

[0434] Under an argon atmosphere, 35-3 (5.2 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 35-4 (4.4 g, yield: 52%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 77.13; H, 5.63; N, 5.00; measured values C, 77.16; H, 5.61; N, 5.03. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 839.2; experimental value 839.2 (M + ).

[0435] Under an argon atmosphere, 35-4 (4.2 g, 5 mmol), boron tribromide (12.5 g, 50 mmol), and dry o-dichlorobenzene (30 mL) were weighed into a 100 mL two-necked flask, and the temperature was raised to 200 °C for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 35-5 (0.9 g, yield: 21%) was obtained through column separation. Elemental analysis: theoretical values C, 75.72; H, 4.82; N, 4.91; measured values C, 75.70; H, 4.84; N, 4.93. MALDI-TOF (m / z): theoretical value 855.2; experimental value 855.2 (M + ).

[0436] Under an argon atmosphere, 35-5 (0.85 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-88 (0.64 g, yield: 48%) was obtained. Elemental analysis: theoretical values C, 84.10; H, 6.68; N, 5.22; measured values C, 84.13; H, 6.61; N, 5.21. MALDI-TOF (m / z): theoretical value 1341.7; experimental value 1341.7 (M + )

[0437] The photophysical properties of the polycyclic compound prepared in Preparation Example 35 of the present invention were detected.

[0438] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0439] Preparation Example 36

[0440] The chemical structure and synthetic route of I-91 are as follows:

[0441]

[0442] Under an argon atmosphere, 35-1 (16.3 g, 50 mmol), 4-tert-butylaniline (8.9 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 36-1 (14.0 g, yield: 71%) was obtained. Elemental analysis: theoretical values C, 72.79; H, 6.62; N, 3.54; measured values C, 72.74; H, 6.60; N, 3.56. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 395.1; experimental value 395.1 (M + )

[0443] Under an argon atmosphere, 36-1 (8.7 g, 22 mmol), m-dibromobenzene (4.7 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 36-2 (7.2 g, yield: 66%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 65.40; H, 5.31; N, 2.54; measured values C, 65.37; H, 5.32; N, 2.56. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 549.0; experimental value 549.0 (M + ).

[0444] Under an argon atmosphere, 36-2 (5.5 g, 10 mmol), 11-10 (4.0 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 36-3 (4.4 g, yield: 51%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 77.40; H, 5.92; N, 4.84; measured values C, 77.41; H, 5.90; N, 4.86. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 867.3; experimental value 867.3 (M + ).

[0445] Under an argon atmosphere, 36-3 (4.3 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 36-4 (0.97 g, yield: 22%) was obtained by column chromatography. Elemental analysis: theoretical values C, 76.04; H, 5.13; N, 4.75; measured values C, 76.05; H, 5.11; N, 4.77. MALDI-TOF (m / z): theoretical value 883.2; experimental value 883.2 (M + ).

[0446] Under an argon atmosphere, 36-4 (1.76 g, 2 mmol), 3,6-di-tert-butylcarbazole (0.56 g, 2 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.28 g, 3 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and washed with deionized water several times. The organic phase was separated, and the product 36-5 (1.53 g, yield: 68%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 80.96; H, 6.17; N, 4.97; measured values C, 80.93; H, 6.19; N, 4.94. MALDI-TOF (m / z): theoretical value 1126.5; experimental value 1126.5 (M + ).

[0447] Under an argon atmosphere, 36-5 (1.12 g, 1 mmol), dibenzofuran-3-boronic acid pinacol ester (0.44 g, 1.5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then, it was cooled to room temperature. The reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying. The solvent was removed from the filtered organic phase, and the crude product was separated by column chromatography to obtain polycyclic compound I-91 (0.88 g, yield: 70%). Elemental analysis: theoretical values C, 83.93; H, 6.08; N, 4.45; measured values C, 83.92; H, 6.09; N, 4.46. MALDI-TOF (m / z): theoretical value 1258.5; experimental value 1258.5 (M + )

[0448] The photophysical properties of the polycyclic compound prepared in Preparation Example 36 of the present invention were detected.

[0449] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0450] Preparation Example 37

[0451] The chemical structure and synthetic route of I-94 are as follows:

[0452]

[0453] Under an argon atmosphere, 35-3 (5.2 g, 10 mmol), 11-5 (4.3 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask. Then, 40 mL of toluene was injected, and the reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, 100 mL of deionized water and dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 37-1 (4.8 g, yield: 55%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 77.40; H, 5.92; N, 4.84; measured values C, 77.43; H, 5.91; N, 4.85. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 867.3; experimental value 867.3 (M + )

[0454] Under an argon atmosphere, 37-1 (4.3 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 37-2 (1.06 g, yield: 24%) was obtained by column separation. Elemental analysis: theoretical value C, 76.04; H, 5.13; N, 4.75; measured value C, 76.05; H, 5.14; N, 4.77. MALDI-TOF (m / z): theoretical value 883.2; experimental value 883.2 (M + ).

[0455] Under an argon atmosphere, 37-2 (0.88 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-94 (0.62 g, yield: 45%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 84.13; H, 6.84; N, 5.11; measured value C, 84.11; H, 6.87; N, 5.13. MALDI-TOF (m / z): theoretical value 1369.7; experimental value 1369.7 (M + )

[0456] The photophysical properties of the polycyclic compound prepared in Preparation Example 37 of the present invention were detected.

[0457] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0458] Preparation Example 38

[0459] The chemical structure and synthetic route of I-97 are as follows:

[0460]

[0461] Under an argon atmosphere, 11-4 (19.3 g, 50 mmol), 4-tert-butylaniline (8.9 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 38-1 (16.8 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 79.19; H, 6.87; N, 6.16; measured values C, 79.15; H, 6.84; N, 6.18. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 454.2; experimental value 454.2 (M + ).

[0462] Under an argon atmosphere, 36-2 (5.5 g, 10 mmol), 38-1 (4.5 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, product 38-2 (4.6 g, yield: 50%) was obtained. Elemental analysis: theoretical values C, 77.90; H, 6.43; N, 4.54; measured values C, 77.91; H, 6.41; N, 4.56. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF(m / z)): theoretical value 923.3; experimental value 923.3 (M + ).

[0463] Under an argon atmosphere, 38-2 (4.6 g, 5 mmol), boron tribromide (12.5 g, 50 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 38-3 (1.08 g, yield: 23%) was obtained by column separation. Elemental analysis: theoretical value C, 76.61; H, 5.68; N, 4.47; measured value C, 76.62; H, 5.64; N, 4.49. MALDI-TOF (m / z): theoretical value 939.3; experimental value 939.3 (M + ).

[0464] Under an argon atmosphere, 38-3 (0.94 g, 1 mmol), triphenylene-2-boronic acid pinacol ester (1.06 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol) and ligand S-phos (164 mg, 0.4 mmol) were added to a 50 mL Schlenk flask. 20 mL of toluene was added to the flask. Potassium carbonate (0.54 g, 4 mmol) was dissolved in 2 mL of water, and the potassium carbonate aqueous solution was introduced into the flask. The temperature was raised to 100 °C, and the reaction was stirred under argon protection for 8 hours. Then it was cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane to separate the organic phase. Anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the crude product was separated by column chromatography to obtain the polycyclic compound I-97 (0.62 g, yield: 47%). Elemental analysis: theoretical value C, 87.06; H, 5.71; N, 3.17; measured value C, 87.08; H, 5.72; N, 3.13. MALDI-TOF (m / z): theoretical value 1323.5; experimental value 1323.5 (M + )

[0465] The photophysical properties of the polycyclic compound prepared in Preparation Example 38 of the present invention were detected.

[0466] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0467] Preparation Example 39

[0468] The chemical structure and synthetic route of I-109 are as follows:

[0469]

[0470] Under an argon atmosphere, aniline (9.3 g, 0.1 mol), 1,5-dibromo-3-chloro-2-methylbenzene (28.1 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column chromatography and solvent removal, compound 39-2 (9.1 g, yield: 31%) was obtained. Elemental analysis: theoretical values C, 52.64; H, 3.74; N, 4.72; measured values C, 52.63; H, 3.71; N, 4.70. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 294.9; experimental value 294.9 (M + ).

[0471] Under an argon atmosphere, 39-2 (5.9 g, 20 mmol), iodobenzene (8.2 g, 40 mmol), copper(I) iodide (0.96 g, 5 mmol), and anhydrous potassium carbonate (5.5 g, 40 mmol) were added to a 50 mL Schlenk flask. 40 mL of DMI was added to the flask, and the temperature was raised to 170 °C. The reaction was carried out for 16 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column chromatography and solvent removal, compound 39-3 (5.7 g, yield: 88%) was obtained. Elemental analysis: theoretical values C, 69.52; H, 4.61; N, 4.27; measured values C, 69.53; H, 4.56; N, 4.25. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 327.1; experimental value 327.1 (M + ).

[0472] Under an argon atmosphere, 39-3 (16.3 g, 50 mmol), 1-amino-3,5-dimethylbenzene (7.3 g, 60 mmol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (9.6 g, 0.1 mol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 39-4 (17.5 g, yield: 85%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 78.53; H, 6.10; N, 6.78; measured values C, 78.54; H, 6.13; N, 6.76. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 412.1; experimental value 412.1 (M + ).

[0473] Under an argon atmosphere, 39-4 (9.1 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and product 39-5 (4.5 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 80.07; H, 5.82; N, 6.23; measured values C, 80.03; H, 5.80; N, 6.21. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 898.3; experimental value 898.3 (M + ).

[0474] Under an argon atmosphere, 39-5 (4.5 g, 5 mmol), boron triiodide (7.8 g, 20 mmol) and dry o-dichlorobenzene (30 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 90 °C and reacted for 10 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 39-6 (1.37 g, yield: 30%) was obtained by column chromatography. Elemental analysis: theoretical values C, 78.71; H, 5.06; N, 6.12; measured values C, 78.70; H, 5.04; N, 6.10. MALDI-TOF (m / z): theoretical value 914.3; experimental value 914.3 (M + ).

[0475] Under an argon atmosphere, 39-6 (0.91 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.84 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected and reacted at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the polycyclic compound I-109 (0.64 g, yield: 46%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 85.70; H, 6.76; N, 6.00; measured values C, 85.70; H, 6.74; N, 6.01. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1400.7; experimental value 1400.7 (M + ).

[0476] The photophysical properties of the polycyclic compound prepared in Preparation Example 39 of the present invention were detected.

[0477] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0478] Preparation Example 40

[0479] The chemical structure and synthesis route of I-117 are as follows:

[0480]

[0481] Under an argon atmosphere, 39-6 (0.91 g, 1 mmol), 4,4'-difluorodiphenylamine (0.62 g, 3 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.48 g, 5 mmol) were added to a 50 mL Schlenk flask, and then 20 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, the polycyclic compound I-117 (0.57 g, yield: 46%) was obtained. Elemental analysis: theoretical values C, 80.52; H, 4.99; N, 6.71; measured values C, 80.53; H, 4.95; N, 6.70. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1252.5; experimental value 1252.5 (M + ).

[0482] The photophysical properties of the polycyclic compound prepared in Preparation Example 40 of the present invention were detected.

[0483] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0484] Preparation Example 41

[0485] The chemical structure and synthesis route of I-118 are as follows:

[0486]

[0487] Under an argon atmosphere, o-aminobiphenyl (16.9 g, 0.1 mol), 4-bromo-2,6-dichlorotoluene (24.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 40-2 (19.9 g, yield: 61%) was obtained. Elemental analysis: theoretical values C, 69.52; H, 4.61; N, 4.27; measured values C, 69.54; H, 4.60; N, 4.25. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 327.0; experimental value 327.0 (M + ).

[0488] Under an argon atmosphere, 40-2 (7.2 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 40-3 (3.64 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 72.34; H, 4.42; N, 3.83; measured values C, 72.32; H, 4.41; N, 3.84. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 728.1; experimental value 728.1 (M + ).

[0489] Under an argon atmosphere, 40-3 (2.9 g, 4 mmol), diphenylamine (3.38 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and the product 40-4 (2.0 g, yield: 40%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 87.59; H, 5.75; N, 6.66; measured values C, 87.61; H, 5.71; N, 6.68. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1260.5; experimental value 1260.5 (M + ).

[0490] Under an argon atmosphere, 4-(1.2 g, 1 mmol), boron tribromide (2.5 g, 10 mmol) and dry o-dichlorobenzene (15 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The polycyclic compound I-118 (0.34 g, yield: 27%) was obtained by column separation. Elemental analysis: theoretical value C, 86.52; H, 5.21; N, 6.58; measured value C, 86.53; H, 5.20; N, 6.56. MALDI-TOF (m / z): theoretical value 1276.5; experimental value 1276.5 (M + ).

[0491] The photophysical properties of the polycyclic compound prepared in Preparation Example 41 of the present invention were detected.

[0492] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0493] Preparation Example 42

[0494] The chemical structure and synthetic route of I-119 are as follows:

[0495]

[0496] Under an argon atmosphere, 4-bromodibenzofuran (24.7 g, 0.1 mol), 3,5-dichloro-4-methylaniline (17.6 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected and reacted at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 42-2 (20.4 g, yield: 60%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 66.68; H, 3.83; N, 4.09; measured value C, 66.65; H, 3.82; N, 4.05. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 341.0; experimental value 341.0 (M + ).

[0497] Under an argon atmosphere, 42-2 (7.5 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the product 42-3 (3.5 g, yield: 47%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 69.67; H, 3.72; N, 3.69; measured values C, 69.65; H, 3.72; N, 3.66. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 756.0; experimental value 756.0 (M + ).

[0498] Under an argon atmosphere, 42-3 (3.0 g, 4 mmol), diphenylamine (3.38 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the product 42-4 (2.1 g, yield: 41%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 85.69; H, 5.31; N, 6.52; measured values C, 85.67; H, 5.32; N, 6.51. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1288.5; experimental value 1288.5 (M + ).

[0499] Under an argon atmosphere, 42-4 (1.3 g, 1 mmol), boron tribromide (2.5 g, 10 mmol) and dry o-dichlorobenzene (15 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was complete, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The polycyclic compound I-119 (0.33 g, yield: 25%) was obtained by column separation. Elemental analysis: theoretical values C, 84.66; H, 4.79; N, 6.44; measured values C, 84.65; H, 4.74; N, 6.43. MALDI-TOF (m / z): theoretical value 1304.5; experimental value 1304.5 (M + ).

[0500] The photophysical properties of the polycyclic compound prepared in Preparation Example 42 of the present invention were detected.

[0501] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0502] Preparation Example 43

[0503] The chemical structure and synthetic route of I-121 are as follows:

[0504]

[0505] Under an argon atmosphere, 42-1 (17.6 g, 0.1 mol), 3-bromo-2,4-dimethyl-9-phenylcarbazole (35.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), and t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected and reacted at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 43-2 (24.8 g, yield: 56%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 72.81; H, 4.98; N, 6.29; measured values C, 72.82; H, 4.96; N, 6.28. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 444.1; experimental value 444.1 (M + ).

[0506] Under an argon atmosphere, 43-2 (7.2 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 43-3 (4.8 g, yield: 50%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 74.69; H, 4.81; N, 5.81; measured values C, 74.67; H, 4.80; N, 5.82. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 962.2; experimental value 962.2 (M + ).

[0507] Under an argon atmosphere, 43-3 (3.8 g, 4 mmol), diphenylamine (3.38 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 43-4 (2.4 g, yield: 41%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 86.71; H, 5.79; N, 7.49; measured values C, 86.73; H, 5.78; N, 7.48. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1494.7; experimental value 1494.7 (M + ).

[0508] Under an argon atmosphere, 43-4 (1.5 g, 1 mmol), boron tribromide (2.5 g, 10 mmol) and dry o-dichlorobenzene (15 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was completed, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The polycyclic compound I-121 (0.44 g, yield: 29%) was obtained by column separation. Elemental analysis: theoretical values C, 85.82; H, 5.33; N, 7.41; measured values C, 85.81; H, 5.30; N, 7.42. MALDI-TOF (m / z): theoretical value 1510.6; experimental value 1510.6 (M + ).

[0509] The photophysical properties of the polycyclic compound prepared in Preparation Example 43 of the present invention were detected.

[0510] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0511] Preparation Example 44

[0512] The chemical structure and synthesis route of I-124 are as follows:

[0513]

[0514] Under an argon atmosphere, 42-1 (17.6 g, 0.1 mol), 2-bromo-1,3-dimethyl-9-phenylcarbazole (35.0 g, 0.1 mol), Pd2(dba)3 (0.92 g, 1 mmol), BINAP (0.62 g, 1 mmol), t-BuONa (19.2 g, 0.2 mol) were added to a 500 mL Schlenk flask, and then 150 mL of toluene was injected and reacted at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 44-2 (25.3 g, yield: 57%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 72.81; H, 4.98; N, 6.29; measured values C, 72.83; H, 4.95; N, 6.30. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 444.1; experimental value 444.1 (M + ).

[0515] Under an argon atmosphere, 44-2 (7.2 g, 22 mmol), m-dibromobenzene (2.36 g, 10 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 44-3 (4.9 g, yield: 51%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 74.69; H, 4.81; N, 5.81; measured values C, 74.65; H, 4.82; N, 5.83. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 962.2; experimental value 962.2 (M + ).

[0516] Under an argon atmosphere, 44-3 (3.8 g, 4 mmol), diphenylamine (3.38 g, 20 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), t-Bu3PHBF4 (0.58 g, 2 mmol), and t-BuONa (3.84 g, 40 mmol) were added to a 100 mL Schlenk flask, and then 40 mL of toluene was injected. The reaction was carried out at 100 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the product 44-4 (2.5 g, yield: 42%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 86.71; H, 5.79; N, 7.49; measured values C, 86.77; H, 5.76; N, 7.46. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 1494.7; experimental value 1494.7 (M + ).

[0517] Under an argon atmosphere, 44-4 (1.5 g, 1 mmol), boron tribromide (2.5 g, 10 mmol) and dry o-dichlorobenzene (15 mL) were weighed in a 100 mL two-necked flask, and the temperature was raised to 200 °C and reacted for 24 hours. After the reaction was cooled to 0 °C, N,N-diisopropylethylamine was added dropwise to the reaction system. After the addition was completed, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The polycyclic compound I-124 (0.42 g, yield: 28%) was obtained by column separation. Elemental analysis: theoretical value C, 85.82; H, 5.33; N, 7.41; measured value C, 85.83; H, 5.31; N, 7.43. MALDI-TOF (m / z): theoretical value 1510.6; experimental value 1510.6 (M + ).

[0518] The photophysical properties of the polycyclic compound prepared in Preparation Example 44 of the present invention were detected. Refer to Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention.

[0519] Table 1 Photophysical properties of the polycyclic compounds prepared in the preparation examples of the present invention

[0520]

[0521]

[0522] Note: In the table, ΔE ST is the difference between the singlet energy level and the triplet energy level, which is the difference between the onset values of the fluorescence spectrum and the phosphorescence spectrum measured by preparing a sample film by doping the compound in mCP at a concentration of 1.5 wt.%. The test instrument is a HORIBA FluoroMax spectrofluorometer (Japan); the delayed fluorescence lifetime is obtained by preparing a sample by doping the compound in polystyrene at a concentration of 1 wt% and testing it with a time-resolved fluorescence spectrometer. The test instrument is an Edinburgh fluorescence spectrometer (FLS-980, UK).

[0523] As can be seen from Table 1, the polycyclic compounds in the examples provided by the present invention have a small ΔE ST (<0.1 eV), showing a thermally activated delayed fluorescence effect, and its delayed fluorescence lifetime is in the range of 5.5 - 6.8 μs, so it is beneficial to utilize triplet excitons and improve the device efficiency.

[0524] Device Examples

[0525] As a device embodiment, the present invention provides a device structure: ITO / PEDOT:PSS(40nm) / PVK(15nm) / EML(30nm) / mSiTRZ(12nm) / TmPPPyTz(55nm) / LiF(1nm) / Al(150nm). The organic thin film layers are sequentially stacked and include: a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. The light-emitting layer (EML) includes a sensitizing material 5CzTRZ, the polycyclic compound of the present invention, and a host material. The host material is selected from one or more of mCP, mCBP, SiCzCz, SiCzTrz, and mSiCzTrz.

[0526] The steps for preparing the device are as follows: Spin-coat poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) on indium tin oxide loaded on a glass substrate and anneal at 120 °C for 30 minutes; Subsequently, spin-coat a 1,2-dichlorobenzene solution of PVK onto the PEDOT:PSS layer and anneal at 100 °C for 10 minutes; Then spin-coat a toluene solution containing the polycyclic compound of the present invention onto the PVK layer and anneal at 100 °C for 10 minutes; Finally, deposit mSiTRZ, TmPPPPyTz, and a LiF / Al cathode sequentially under a vacuum of 6 x 10 -7 Torr to obtain an organic light-emitting device.

[0527] The structures of some materials in this device embodiment are as follows:

[0528]

[0529] Example 1

[0530] Taking I-1 in Preparation Example 1 as the implementation object, doping I-1 into the organic light-emitting layer, and preparing an organic light-emitting device using the device structure, and testing the obtained device.

[0531] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with I-1 provided by the present invention.

[0532] Example 2

[0533] Taking I-4 in Preparation Example 2 as the implementation object, doping I-4 into the organic light-emitting layer, and preparing an organic light-emitting device using the device structure, and testing the obtained device.

[0534] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with I-4 provided by the present invention.

[0535] Example 3

[0536] Taking I-7 in Preparation Example 3 as the object of implementation, I-7 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0537] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-7 provided by the present invention.

[0538] Example 4

[0539] Taking I-8 in Preparation Example 4 as the object of implementation, I-8 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0540] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-8 provided by the present invention.

[0541] Example 5

[0542] Taking I-9 in Preparation Example 5 as the object of implementation, I-9 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0543] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-9 provided by the present invention.

[0544] Example 6

[0545] Taking I-12 in Preparation Example 6 as the object of implementation, I-12 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0546] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-12 provided by the present invention.

[0547] Example 7

[0548] Taking I-13 in Preparation Example 7 as the object of implementation, I-13 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0549] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-13 provided by the present invention.

[0550] Example 8

[0551] Taking I-24 in Preparation Example 8 as the object of implementation, I-24 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0552] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-24 provided by the present invention.

[0553] Example 9

[0554] Taking I-25 in Preparation Example 9 as the implementation object, I-25 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0555] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-25 provided by the present invention.

[0556] Example 10

[0557] Taking I-26 in Preparation Example 10 as the implementation object, I-26 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0558] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-26 provided by the present invention.

[0559] Example 11

[0560] Taking I-28 in Preparation Example 11 as the implementation object, I-28 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0561] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-28 provided by the present invention.

[0562] Example 12

[0563] Taking I-31 in Preparation Example 12 as the implementation object, I-31 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0564] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-31 provided by the present invention.

[0565] Example 13

[0566] Taking I-34 in Preparation Example 13 as the implementation object, I-34 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0567] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-34 provided by the present invention.

[0568] Example 14

[0569] Taking I-38 in Preparation Example 14 as the object, I-38 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0570] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-38 provided by the present invention.

[0571] Example 15

[0572] Taking I-40 in Preparation Example 15 as the object, I-40 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0573] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-40 provided by the present invention.

[0574] Example 16

[0575] Taking I-41 in Preparation Example 16 as the object, I-41 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0576] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-41 provided by the present invention.

[0577] Example 17

[0578] Taking I-44 in Preparation Example 17 as the object, I-44 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0579] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-44 provided by the present invention.

[0580] Example 18

[0581] Taking I-46 in Preparation Example 18 as the object, I-46 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0582] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-46 provided by the present invention.

[0583] Example 19

[0584] Taking I-47 in Preparation Example 19 as the object, I-47 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0585] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-47 provided by the present invention.

[0586] Example 20

[0587] Taking I-49 in Preparation Example 20 as the implementation object, I-49 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0588] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-49 provided by the present invention.

[0589] Example 21

[0590] Taking I-51 in Preparation Example 21 as the implementation object, I-51 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0591] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-51 provided by the present invention.

[0592] Example 22

[0593] Taking I-52 in Preparation Example 22 as the implementation object, I-52 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0594] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-52 provided by the present invention.

[0595] Example 23

[0596] Taking I-55 in Preparation Example 23 as the implementation object, I-55 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0597] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-55 provided by the present invention.

[0598] Example 24

[0599] Taking I-58 in Preparation Example 24 as the implementation object, I-58 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0600] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-58 provided by the present invention.

[0601] Example 25

[0602] Taking I-61 in Preparation Example 25 as the object, I-61 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0603] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-61 provided by the present invention.

[0604] Example 26

[0605] Taking I-64 in Preparation Example 26 as the object, I-64 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0606] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-64 provided by the present invention.

[0607] Example 27

[0608] Taking I-67 in Preparation Example 27 as the object, I-67 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0609] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-67 provided by the present invention.

[0610] Example 28

[0611] Taking I-70 in Preparation Example 28 as the object, I-70 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0612] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-70 provided by the present invention.

[0613] Example 29

[0614] Taking I-71 in Preparation Example 29 as the object, I-71 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0615] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-71 provided by the present invention.

[0616] Example 30

[0617] Taking I-75 in Preparation Example 30 as the object, I-75 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0618] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-75 provided by the present invention.

[0619] Example 31

[0620] Taking I-76 in Preparation Example 31 as the implementation object, I-76 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0621] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-76 provided by the present invention.

[0622] Example 32

[0623] Taking I-79 in Preparation Example 32 as the implementation object, I-79 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0624] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-79 provided by the present invention.

[0625] Example 33

[0626] Taking I-80 in Preparation Example 33 as the implementation object, I-80 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0627] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-80 provided by the present invention.

[0628] Example 34

[0629] Taking I-85 in Preparation Example 34 as the implementation object, I-85 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0630] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-85 provided by the present invention.

[0631] Example 35

[0632] Taking I-88 in Preparation Example 35 as the implementation object, I-88 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0633] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-88 provided by the present invention.

[0634] Example 36

[0635] Taking I-91 in Preparation Example 36 as the object, I-91 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0636] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-91 provided by the present invention.

[0637] Example 37

[0638] Taking I-94 in Preparation Example 37 as the object, I-94 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0639] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-94 provided by the present invention.

[0640] Example 38

[0641] Taking I-97 in Preparation Example 38 as the object, I-97 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0642] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-97 provided by the present invention.

[0643] Example 39

[0644] Taking I-109 in Preparation Example 39 as the object, I-109 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0645] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-109 provided by the present invention.

[0646] Example 40

[0647] Taking I-117 in Preparation Example 40 as the object, I-117 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0648] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with I-117 provided by the present invention.

[0649] Example 41

[0650] Taking I-118 in Preparation Example 41 as the object, I-118 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0651] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-118 provided by the present invention.

[0652] Example 42

[0653] Taking I-119 in Preparation Example 42 as the object of implementation, I-119 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0654] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-119 provided by the present invention.

[0655] Example 43

[0656] Taking I-121 in Preparation Example 43 as the object of implementation, I-121 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0657] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-121 provided by the present invention.

[0658] Example 44

[0659] Taking I-124 in Preparation Example 44 as the object of implementation, I-124 was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0660] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with I-124 provided by the present invention.

[0661] Comparative Example 1

[0662] Taking υ-DABNA as the object of implementation, it was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0663] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared in Comparative Example 1.

[0664] Comparative Example 2

[0665] Taking Cz-DABNA as the object of implementation, it was doped into the organic light-emitting layer, and an organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0666] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared in Comparative Example 2.

[0667] Comparative Example 3

[0668] Taking t-BuCz-DABNA as the object of implementation, doping it into the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0669] See Table 2, which provides the performance parameters of the electroluminescent device prepared in Comparative Example 3. Chemical structures of υ-DABNA, Cz-DABNA, and t-BuCz-DABNA:

[0670] Table 2 Performance parameters of the electroluminescent device prepared from the polycyclic compound provided by the present invention

[0671]

[0672]

[0673] Note: The turn-on voltage in the table is the driving voltage of the device when the luminance is 1 cd / m 2 ; The maximum external quantum efficiency is obtained according to the calculation method described in the literature (Jpn. J. Appl. Phys. 2001, 40, L783) based on the current-voltage curve and electroluminescent spectrum of the device; The full width at half maximum is the peak width at half of the peak height of the electroluminescent spectrum, that is, a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the distance between the two intersection points of this straight line and both sides of the peak.

[0674] As can be seen from Table 2, the solution-processed organic electroluminescent device prepared from the dendritic polycyclic compound provided by the present invention not only has a very high luminous efficiency, with the maximum external quantum efficiency being 29.3% - 30.5%, significantly higher than the device efficiencies of the comparative compounds υ-DABNA, Cz-DABNA, and t-BuCz-DABNA, but also all have a relatively narrow electroluminescent spectrum, with the full width at half maximum being less than 20 nm.

[0675] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A binuclear organoboron fused-ring compound having the structure shown in Formula I: Among them, X1 is selected from -N(R a1 )-, -O-, -S-, -Se- or -Te-; X2 is selected from -N(R a2 )-, -O-, -S-, -Se- or -Te-; Said R a1 , R a2 independently selected from H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C3-C60 heteroaromatic group; The R a1 One or two of the benzene rings connected to X1 can be connected by a single bond, -O-, -S-, with any one or more of; The R a2 One or two of the benzene rings connected to X2 may be connected by a single bond, -O-, -S-, with any one or more of the following; The R a3 , R a4 are independently selected from substituted or unsubstituted C1-C30 alkyl, C6-C30 aryl, and C3-C30 heteroaryl; L1 and L2 are independently selected from any one of a carbon-carbon single bond, -O-, -S-, -Se-, a substituted or unsubstituted C1-C30 straight-chain or branched-chain alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C3-C30 cycloalkylene group, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 heteroarylene group, or a group formed by connecting the above groups through a single bond; Q1 and Q2 are independently selected from H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group or a substituted or unsubstituted C3-C60 heteroaromatic group, -NR 1 R 2 ; R1, R2, R3, and R4 are independently selected from H, D, F, Cl, Br, I, -CN, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C3-C60 heteroaromatic group, or any of the following structures: -O-R 1 -S-R 1 , R 1 、R 2 、R 3 independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted C1-C30 straight-chain or branched alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C3-C60 heteroaromatic group; and the R 1 , R 2 , R 3 Any two or three of them can be connected by one or more of single bond, -O-, -S-, ; The heteroatoms of the heteroarylene group are selected from any one or more of Si, Te, Ge, N, P, O, S, Se; n1 and n4 are independently selected from any integer from 1 to 4; n2 and n3 are independently selected from any integer from 1 to 5; m1 and m2 are independently selected from 0, 1 or 2; — represents the connection position.

2. The binuclear organoboron fused-ring compound according to claim 1, wherein Said R a1 and R a2 are independently selected from H, D, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, morpholinyl, indolyl, benzofuranyl, benzothienyl, carbazolyl or fluorenyl; The substitution is by any one or more of deuterium, halogen, cyano, nitro, amino, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkoxy group.

3. The binuclear organoboron fused-ring compound according to claim 1, characterized in that, L1 and L2 are independently selected from a carbon-carbon single bond, -O-, -S-, -Se-, a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methyleneoxy group, ethyleneoxy group, propyleneoxy group, methylthio group, ethylthio group, propylthio group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group or any of the following structures: or a group formed by connecting the above groups through a single bond; The substitution is by any one or more of deuterium, halogen, cyano, nitro, amino, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkoxy group; * represents the connection position.

4. The binuclear organoboron fused-ring compound according to claim 1, wherein Q1 and Q2 are independently selected from H, D, substituted or unsubstituted C1-C10 linear or branched hydrocarbon groups, substituted or unsubstituted C1-C10 alkoxy groups, substituted or unsubstituted C1-C10 alkylthio groups, substituted or unsubstituted C3-C6 cycloalkyl groups, -NR 1 R 2 or any one of the following substituted or unsubstituted a) to e): a) Phenyl; b) A group formed by connecting or fusing 2 to 5 phenyl groups through a single bond; c) A 5- to 6-membered monocyclic heteroarylene group; d) A group formed by connecting or fusing 2 to 5 5- to 6-membered monocyclic heteroarylene groups through a single bond; e) A group formed by connecting or fusing a phenyl group and a 5- to 6-membered monocyclic heteroarylene group through a single bond; the total number of the phenyl group and the 5- to 6-membered monocyclic heteroarylene group is 2 to 7; The heteroatoms of the monocyclic heteroarylene group are selected from any one or more of Si, Ge, N, P, O, S, Se; The substitution is replaced by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 haloalkyl, phenyl, pyridyl, carbazolyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, -NR 1 R 2 substituted; R 1 and R 2 are defined as in claim 1.

5. The binuclear organoboron fused-ring compound according to claim 4, wherein The 5- to 6-membered monocyclic heteroarylene group is selected from: Pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, pyranyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl or any of the following structures: R 1 、R 2 、R 3 are defined in the same way as in claim 1.

6. The binuclear organoboron fused-ring compound according to claim 4, wherein Q1 and Q2 are independently selected from H, D, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, n-propoxy, isopropoxy, methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -NR 1 R 2 or any one of the following structures: The substitution is carried out by any one or more of deuterium, halogen, cyano, nitro, amino, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 haloalkyl, phenyl, pyridyl, carbazolyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, -NR 1 R 2 substitution; R 1 and R 2 are defined the same as in claim 1; * represents the connection position.

7. The binuclear organoboron fused-ring compound according to claim 1, wherein R1, R2, R3, and R4 are independently selected from H, D, F, Cl, Br, I, -CN, a substituted or unsubstituted C1-C10 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, or a substituted or unsubstituted C3-C14 heteroaromatic group, or any of the following structures: -O-R 1 -S-R 1 , The R 1 , R 2 , R 3 is independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted C1-C10 straight-chain or branched hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, or a substituted or unsubstituted C3-C14 heteroaromatic group; and the R 1 , R 2 , R 3 can be connected by one or more of a single bond, -O-, -S-, .

8. The binuclear organoboron fused-ring compound according to claim 1, wherein Having any of the following structures:

9. A method for preparing the binuclear organoboron fused-ring compound according to any one of claims 1 to 8, comprising the following steps: S1. Compound U-1 reacts with compound U-4 to obtain compound U-6; compound U-2 reacts with compound U-3 to obtain compound U-5; S2. Compound U-6 reacts with m-dibromobenzene to obtain compound U-7; compound U-5 reacts with m-dibromobenzene to obtain compound U-8; S3. Compound U-7 reacts with compound U-8 to obtain compound U-9; S4. Compound U-9 reacts with BI3 or BBr3 to form a fused-ring intermediate shown in formula (II); S5. The fused-ring intermediate shown in formula (II) reacts with at least one of compounds U-10 and U-11 to obtain a binuclear organoboron fused-ring compound shown in formula (I); wherein, the definitions of X1, X2, R1, R2, R3, R4, L1, L2, Q1, Q2, n1, n2, n3, n4, m1, and m2 are the same as those described in any one of claims 1 to 8; The Gu1 and Gu2 are independently selected from hydrogen, hydroxyl group, mercapto group, amino group, Indicates the connection position.

10. Use of the binuclear organoboron fused-ring compound according to any one of claims 1 to 8 as an organic electroluminescent material.

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