CN114591370B - Conjugated molecule based on trimeric indole condensed ring structure and electroluminescent device - Google Patents

Conjugated molecule based on trimeric indole condensed ring structure and electroluminescent device Download PDF

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CN114591370B
CN114591370B CN202210299933.XA CN202210299933A CN114591370B CN 114591370 B CN114591370 B CN 114591370B CN 202210299933 A CN202210299933 A CN 202210299933A CN 114591370 B CN114591370 B CN 114591370B
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王利祥
童辉
刘洋
吴晓甫
韩现超
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a conjugated molecule based on a trimeric indole fused ring structure, which is shown as a formula (I) or a formula (II). Compared with the prior art, the conjugated molecule provided by the invention adopts the trimerization indole condensed ring unit as an electron donor (D) to be connected with an electron acceptor (A) group to form a D-A type molecule with intramolecular charge transfer, and simultaneously, the large torsion angle between D-A is utilized to reduce the overlapping of molecular front line orbitals, so that smaller singlet-triplet state energy level difference and TADF effect are realized; the phenyl of the phenyl trimerization indole is locked through a bridging structure to form a condensed ring donor unit, so that the rigidity of molecules can be obviously enhanced, the non-radiative transition process of the molecules caused by rotation or vibration is inhibited, the quenching effect caused by intermolecular aggregation is reduced, the luminous efficiency and the stability of the material are improved, and finally the aim of improving the efficiency of an electroluminescent device is fulfilled.

Description

Conjugated molecule based on trimeric indole condensed ring structure and electroluminescent device
Technical Field
The invention belongs to the technical field of organic photoelectricity, and particularly relates to a conjugated molecule based on a trimerization indole fused ring structure and an electroluminescent device.
Background
In recent years, with the continuous development of Organic Light-Emitting Diodes (OLED) technology, attention is paid to the novel display technical field and the novel lighting technical field by virtue of the advantages of full solid state, active Light emission, high contrast, bright color, ultra-thin, flexible display, low power consumption, wide viewing angle, fast response speed, wide operating temperature range and the like.
Organic light emitting materials, which are the core of OLED technology, can be classified into fluorescent materials, phosphorescent materials, and thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) materials. Under the condition of electro-excitation, the OLED device based on the traditional fluorescent material can only utilize the energy of singlet excitons, and the theoretical internal quantum efficiency is only 25% at the highest; the phosphorescent material based on Ir or Pt and other heavy metal complexes can simultaneously utilize the energy of singlet excitons and triplet excitons, so that the maximum internal quantum efficiency of the device theory is improved to 100%, but the problems of high price of noble metals, poor material stability, serious roll-off of the device efficiency and the like exist; and the TADF material without noble metal can realize 100% of internal quantum efficiency of the device by utilizing the cross-over between triplet exciton reverse systems, and has the advantages of simple preparation, high luminous efficiency and good stability, thereby bringing great attention to researchers at home and abroad.
Currently, the main design method of TADF materials is to introduce electron donor (D) and electron acceptor (a) units so that the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) are separated, thereby achieving a small Δe ST However, such molecules tend to have significant vibrational relaxation of the excited state, and the non-radiative transitions caused by molecular rotation or vibration are severe, resulting in a decrease in luminous efficiency and a broadening of the luminescence spectrum.
In order to obtain an OLED device with high efficiency and stability, development of a novel heat-activated delayed fluorescent material with high intersystem crossing rate constant and high luminescence quantum yield, good heat stability and film forming property has important significance.
Disclosure of Invention
In view of the above, the present invention aims to provide a conjugated molecule based on a condensed ring structure of trimeric indole and an electroluminescent device thereof, which have the advantages of delayed fluorescence behavior by thermal activation, high luminescence quantum yield, and good thermal stability and film forming property.
The invention provides a conjugated molecule based on a trimeric indole fused ring structure, which is shown as a formula (I) or a formula (II):
wherein, -X-is selected from-C (R) 1 R 2 )-、-Si(R 1 R 2 )-、-N(R 1 )-、-PO(R 1 )-、-BR 1 -、-O-、-S-、-Se-、/>-or-SO 2 -；
R 1 And R is R 2 Each independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group;
L 1 ～L 5 Each independently selected from H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group;
m 1 ～m 5 each independently is an integer of 0 to 4;
a and A' are each independently selected from the group consisting of a substituted or unsubstituted C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C6-C60 aromatic group, and a substituted or unsubstituted C5-C60 heteroaromatic group.
The invention also provides an electroluminescent device, which comprises an anode, a cathode and an organic film layer positioned between the anode and the cathode; the organic film layer comprises the conjugated molecule based on the trimeric indole condensed ring structure.
The invention provides a conjugated molecule based on a trimeric indole fused ring structure, which is shown as a formula (I) or a formula (II). Compared with the prior art, the conjugated molecule provided by the invention adopts the trimerization indole condensed ring unit as an electron donor (D) to be connected with an electron acceptor (A) group to form a D-A type molecule with intramolecular charge transfer, and simultaneously, the large torsion angle between D-A is utilized to reduce the overlapping of molecular front line orbitals, so that smaller singlet-triplet state energy level difference and TADF effect are realized; the phenyl of the phenyl trimerization indole is locked through a bridging structure to form a condensed ring donor unit, so that the rigidity of molecules can be obviously enhanced, the non-radiative transition process of the molecules caused by rotation or vibration is inhibited, the quenching effect caused by intermolecular aggregation is reduced, the luminous efficiency and the stability of the material are improved, and finally the aim of improving the efficiency of an electroluminescent device is fulfilled.
Compared with phenyl substituted trimeric indole, the free rotation of the benzene ring around carbon-nitrogen bonds is inhibited by a bridging method, so that the non-radiative transition process in molecules is inhibited, and the luminous efficiency is improved; meanwhile, the donor structure of the full-rigid condensed ring can reduce the configuration change of the excited state, and can realize the narrowing of the spectrum.
Experimental results show that the conjugated molecules provided by the invention are used as the light-emitting layer of the electroluminescent device, so that high external quantum efficiency of the device can be realized, and meanwhile, the electroluminescent spectrum is narrower.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a conjugated molecule based on a trimeric indole fused ring structure, which is shown as a formula (I) or a formula (II):
the conjugated molecule provided by the invention adopts a trimerization indole condensed ring unit as an electron donor (D) to be connected with an electron acceptor (A) group to form a D-A type molecule with intramolecular charge transfer, and simultaneously, the large torsion angle between D-A is utilized to reduce the overlapping of molecular front line orbitals, so that smaller singlet-triplet energy level difference and TADF effect are realized; the phenyl of the phenyl trimerization indole is locked through a bridging structure to form a condensed ring donor unit, so that the rigidity of molecules can be obviously enhanced, the non-radiative transition process of the molecules caused by rotation or vibration is inhibited, the quenching effect caused by intermolecular aggregation is reduced, the luminous efficiency and the stability of the material are improved, and finally the aim of improving the efficiency of an electroluminescent device is fulfilled.
Wherein, -X-is selected from-C (R) 1 R 2 )-、-Si(R 1 R 2 )-、-N(R 1 )-、-PO(R 1 )-、-BR 1 -、-O-、-S-、-Se-、/>-or-SO 2 -。
R 1 And R is R 2 Each independently H, D, a substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, a substituted or unsubstituted C1-C20 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C20 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C40 aromatic group, or a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, a substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aromatic group, or a substituted or unsubstituted C5-C20 heteroaromatic group; more preferably HD, a substituted or unsubstituted C1-C5 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C5 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C10 aromatic group, and a substituted or unsubstituted C5-C10 heteroaromatic group; the heteroatom in the heteroaromatic group is preferably one or more of O, S and N.
L 1 ～L 5 Each independently H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C20 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C20 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C40 aromatic group, a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aromatic group, a substituted or unsubstituted C5-C20 heteroaromatic group; further preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C8 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C8 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C6-C15 aromatic group, a substituted or unsubstituted C5-C15 heteroaromatic group; most preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 Substituted or unsubstituted C1-C5A linear hydrocarbon group, a substituted or unsubstituted C1-C5 branched hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C5 alkoxy group, a substituted or unsubstituted C6-C10 aromatic group, and a substituted or unsubstituted C5-C10 heteroaromatic group.
In the present invention, the above-mentioned substituted C1-C30 branched hydrocarbon group, substituted C3-C30 cycloalkyl group, substituted C1-C30 alkoxy group, substituted C6-C60 aromatic group and substituted C5-C60 heteroaromatic group are each independently preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C20 aromatic group, C1-C5 alkoxy, C3-C10 cycloalkyl and C5-C20 heteroaromatic group, more preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C15 aromatic group, C1-C3 alkoxy, C3-C6 cycloalkyl and C5-C15 heteroaromatic group.
m 1 ～m 5 Each independently is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, i.e., preferably m 1 ～m 5 Each independently is 0, 1 or 2.
A and A' are each independently a substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C5-C60 heteroaromatic group.
In the present invention, preferably, each of the A and A' is independently one of the formulas A1 to A16:
wherein R is 1 ～R 12 Each independently H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group,Substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C20 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C20 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C40 aromatic group, a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C5-C30 heteroaromatic group; further preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C8 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C8 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C8 alkoxy group, a substituted or unsubstituted C6-C20 aromatic group, a substituted or unsubstituted C5-C20 heteroaromatic group; most preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C5 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C5 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C6-C10 aromatic group, a substituted or unsubstituted C5-C10 heteroaromatic group; the substituents mentioned above are each independently preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C20 aromatic group, C1-C5 alkoxy, C3-C10 cycloalkyl and C5-C20 heteroaromatic group, more preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C15 aromatic group, C1-C3 alkoxy, C3-C6 cycloalkyl and C5-C15 heteroaromatic group.
-Y 1 -～-Y 3 -each independently selected from the group consisting of single bonds, -C (R 'R "), -Si (R' R"), -B (R '), -N (R'). ` )-、-P(R')-、-PO(R' ` )-、-O-、-S-、-Se-、-SO 2 -or->
Z 1 ～Z 3 Each independently is CR' and a nitrogen atom, and at least one is a nitrogen atom;
wherein R 'and R' are each independently H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C20 linear hydrocarbon group, a substituted or unsubstituted C1-C20 branched hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C40 aromatic group, a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C10 linear hydrocarbon group, a substituted or unsubstituted C1-C10 branched hydrocarbon group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C20 aromatic group, a substituted or unsubstituted C5-C20 heteroaromatic group; further preferably H, D, F, cl, br, I, CN, NO 2 、CF 3 、-OH、SH、NH 2 A substituted or unsubstituted C1-C5 linear hydrocarbon group, a substituted or unsubstituted C1-C5, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C10 aromatic group, a substituted or unsubstituted C5-C10 heteroaromatic group; the substituents mentioned above are each independently preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C20 aromatic group, C1-C5 alkoxy, C3-C10 cycloalkyl and C5-C20 heteroaromatic group, more preferably D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C15 aromatic group, C1-C3 alkoxy, C3-C6 cycloalkyl and C5-C15 heteroaromatic group.
In the present invention, all represent the position of the bond of the substituent group, unless otherwise specified.
Further preferably, each of A and A' is independently selected from one of the structures represented by formulas a1-1 to a 16-4:
。
in the present invention, most preferably, the conjugated molecule is one of the compounds of the formulae (1-1) to (22-6):
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the invention also provides application of the conjugated molecule based on the trimeric indole fused ring structure as a thermal activation delay fluorescent material.
The luminescent material provided by the invention can remarkably enhance the rigidity of a donor unit, inhibit non-radiative transition of molecules caused by rotation or vibration, and be beneficial to improving the luminescent efficiency of the material and reducing the half-peak width of a luminescent spectrum by locking phenyl of phenyl trimerization indole through a bridging structure to form a condensed ring donor unit.
The luminescent material provided by the invention is beneficial to the injection and transmission capacity of the luminescent material to holes by maintaining the trimerization indole planar donor conjugated framework, so that the working voltage of the organic electroluminescent device is reduced.
The condensed ring donor unit of the luminescent material provided by the invention has an intramolecular steric hindrance effect, is easy to realize intramolecular distortion, can reduce quenching effect caused by intermolecular aggregation, can directly connect different electron acceptors through coupling reaction, realizes multiple-color luminescence from deep blue light to near infrared light, and has good comprehensive performance when being used as a luminescent material in electroluminescent devices of solution processing and vacuum evaporation.
The luminescent material provided by the invention can effectively separate HOMO and LUMO by using a twisted D-A structure, and delta E of the material ST Less than or equal to 0.3eV, a sufficiently small ΔE ST The thermal activation delayed fluorescence property can be realized, and particularly, the efficient blue light thermal activation delayed fluorescence material can be obtained.
The luminescent material synthesized by the invention has a relatively large molecular weight and a relatively rigid molecular structure, so that the material has good thermal stability and film forming property, and the application range of the material is wider.
The invention also provides an electroluminescent device, which comprises an anode, a cathode and an organic film layer positioned between the anode and the cathode; the organic film layer comprises the conjugated molecule based on the trimeric indole condensed ring structure.
The structure of all electroluminescent devices is not particularly limited in the present invention, and the electroluminescent devices are well known to those skilled in the art, and those skilled in the art can select and adjust the structure according to the application situation, quality requirements and product requirements.
Preferably, the electroluminescent device 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.
The thickness of the substrate is preferably 0.3 to 0.7mm, more preferably 0.4 to 0.6mm; the choice of the substrate is not particularly limited and may be any substrate known to those skilled in the art for conventional organic electroluminescent devices, and may be chosen and adjusted by those skilled in the art according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.
According to the present invention, the anode is preferably a material that facilitates hole injection, more preferably a conductive metal or conductive metal oxide, and still more preferably indium tin oxide.
The organic film layer can be one layer or a plurality of layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light emitting layer; the light-emitting layer comprises conjugated molecules based on condensed ring units of trimeric indole represented by the above formula (I) and/or formula (II); the conjugated molecules based on condensed ring units of trimeric indole, which are shown in the formula (I) and/or the general formula (II), serve as luminescent materials to directly form an organic electroluminescent layer. In the present invention, the mass of the conjugated molecule based on the condensed ring structure of trimeric indole is preferably 5% to 30% of the mass of the light-emitting layer, more preferably 10% to 30%.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order 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 and an electron injection layer and an electron transport layer. 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 are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the process of preparing the electrode, 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 preferably, the present invention is prepared by using processes of vacuum evaporation, solution spin coating, solution doctor blading, inkjet printing, offset printing and three-dimensional printing.
The preparation method of the electroluminescent device is not particularly limited, and 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, including a light emitting layer; forming a cathode on the organic thin film layer;
the light-emitting layer comprises one or more conjugated molecules of condensed ring units based on trimeric indole represented by formula (I) and/or formula (II).
The structure and the materials of the electroluminescent device and the corresponding preferred principles of the electroluminescent device in the preparation method can be corresponding to the corresponding materials and structures of the electroluminescent device and the corresponding preferred principles, and are not described in detail herein.
The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. The present invention is not particularly limited in the manner of forming the light emitting layer and the organic thin film layers below and above the light emitting layer, and may be formed on the anode by vacuum evaporation, solution spin coating, solution knife coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited as to the manner of forming the cathode after the organic layer is formed, and is preferably a method well known to those skilled in the art, including but not limited to solution processing, to prepare the cathode on the surface thereof.
In order to further illustrate the present invention, the following examples are provided to describe in detail a conjugated molecule and an electroluminescent device based on a condensed ring structure of trimeric indole.
The reagents used in the examples below are all commercially available.
Example 1
The reaction formula is as follows:
1.1 in a 100mL two-necked flask under argon atmosphere, m-1 (3.45 g,10 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB), 8mL methyl o-iodobenzoate (50 mmol) were added, heated to 220℃and stirred under argon for 50 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-2 (800 mg, yield: 13%) was isolated by column separation.
Analysis by nuclear magnetic resonance to obtain 1 H-NMR(500MHz,DMSO)：δ11.91(s,1H),8.82(d,J＝5.0Hz,1H),8.2(m,2H),7.95(m,4H),7.73(m,3H),7.45(m,2H),7.73(m,1H)7.21(t,J＝5.0Hz,2H),6.92(m,1H),6.67(m,2H),5.89(m,1H),5.64(t,J＝5.0Hz,1H),3.20(m,6H)。
Elemental analysis structure (C) 40 H 27 N 3 O 4 ): theoretical value C,78.29; h,4.43; n,6.85; test value C,78.30; h,4.40; n,6.80.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 613.20; experimental value 613.2 (M + )。
1.2 m-2 (1.2 g,2 mmol) was added to a 100mL two-necked flask under argon atmosphere, 18mL of tetrahydrofuran was introduced, stirred at room temperature, then 20mL (20 mmol) of methylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-3 was obtained by column separation (200 mg, yield: 33%).
Elemental analysis structure (C) 42 H 35 N3O 2 ): theoretical value C,82.19; h,5.75; n,6.85; test value C,82.41; h,5.70; n,6.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 613.27; experimental values 613.3 (M + )。
1.3 in a 100mL single neck flask under argon atmosphere, weighing m-3 (313 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-4 (300 mg, 51%) by column.
Elemental analysis structure (C) 42 H 31 N 3 ): theoretical value C,87.32; h,5.41; n,7.27 test value C,87.30; h,5.40; n,7.30.Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 577.25; experimental value 577.3 (M + )。
1.4 in a 50mL one-neck flask under argon atmosphere, m-4 (577 mg,1 mmol), m-5 (3838 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 1-2 (530 mg, 60%) was isolated by column separation.
Elemental analysis structure (C) 63 H 44 N 6 ): theoretical value C,85.49; h,5.01; n,9.50; test value C,85.30; h,4.90; n,9.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 884.36; experimental values 884.4 (M + )。
Example 2
The reaction formula is as follows:
2.1 in a 100mL two-necked flask under argon atmosphere, m-2 (1.2 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of n-butylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-6 was obtained by column separation (500 mg, yield: 64%).
Elemental analysis structure (C) 54 H 59 N 3 O 2 ): theoretical value C,82.93; h,7.60; n,5.37; test value C,82.91; h,7.70; n,5.40. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 781.46; experimentValue 781.5 (M + )。
2.1 in a 100mL single neck flask under argon atmosphere, weighing m-6 (782 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, removing the solvent from the organic phase obtained by filtration, and separating the product m-7 (480 mg, 63%) by column separation.
Elemental analysis structure (C) 54 H 55 N 3 ): theoretical value C,86.94; h,7.43; n,5.63; test value C,86.90; h,7.40; n,5.70. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 745.44; experimental values 745.4 (M + )。
2.3 in a 50mL one-neck flask under argon atmosphere, m-7 (745 mg,1 mmol), m-5 (3838 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 1-24 (610 mg, 58%) was isolated by column separation.
Elemental analysis structure (C) 75 H 68 N 6 ): theoretical value C,85.52; h,6.51; n,7.98; test value C,85.30; h,6.60; n,7.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1052.55; experimental values 1052.6 (M + )。
Example 3
The reaction formula is as follows:
3.1 in a 100mL two-necked flask under argon atmosphere, m-1 (3.45 g,10 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB), 8mL methyl 4-tert-butylo-iodobenzoate (50 mmol) were added, the temperature was raised to 220℃and stirred for 50 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the obtained organic phase by filtration, and the product m-8 (900 mg, yield: 12%) was obtained by column separation.
Elemental analysis structure (C) 48 H 43 N 3 O 4 ): theoretical value C,79.42; h,5.97; n,5.79; test value C,79.30; h,5.80; n,5.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 725.33; experimental values 725.3 (M + )。
3.2 in a 100mL two-necked flask under argon atmosphere, m-8 (1.5 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of methylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-9 was obtained by column separation (820 mg, yield: 56%).
Elemental analysis structure (C) 50 H 51 N 3 O 2 ): theoretical value C,82.72; h,7.08; n,5.79; test value C,82.71; h,7.10; n,5.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 725.40; experimental values 725.4 (M + )。
3.3 in a 100mL single neck flask under argon atmosphere, weighing m-9 (725 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-10 (430 mg, 62%) by column.
Elemental analysis structure (C) 50 H 47 N 3 ): theoretical value C,87.04; h,6.87; n,6.09; test value C,87.10; h,6.90; n,6.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 689.38; experimental values 689.4 (M + )。
3.4 in a 50mL one-neck flask under argon atmosphere, m-10 (689 mg,1 mmol), m-11 (356 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 1-35 (580 mg, 60%) was isolated by column separation.
Elemental analysis structure (C) 68 H 60 N 3 OP): theoretical value C,84.53; h,6.26; n,4.35; test value C,84.50; h,6.30; n,4.38. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 965.45; experimental values 965.5 (M + )。
Example 4
The reaction formula is as follows:
4.1 to a MeCN solution of 5-methylindole (m-12) N-bromosuccinimide was gradually added in portions. After stirring at room temperature for 3 hours, the solid crude product was obtained by filtration, washed with MeCN and then dissolved in methanol. Triethylamine, formic acid and 10% Pd/C were added, and the mixture was heated under reflux for 30 minutes. After the reaction system was cooled to room temperature, the mixture was filtered. The filtrate was diluted with dichloromethane and washed with 10% aqueous hcl and brine. The organic layer was collected and separated by column to give m-13 (960 mg, 24%).
Elemental analysis structure (C) 27 H 21 N 3 ): theoretical value C,83.69; h,5.46; n,10.84; test value C,83.71; h,5.40; n,10.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 387.17; experimental value 387.2 (M+).
4.2 in a 100mL two-necked flask under argon atmosphere, m-13 (3.87 g,10 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB), 8mL methyl o-iodobenzoate (50 mmol) were added, heated to 220℃and stirred for 50 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-14 (900 mg, yield: 13%) was isolated by column separation.
Elemental analysis structure (C) 43 H 33 N 3 O 4 ): theoretical value C,78.76; h,5.07; n,6.41; test value C,78.30; h,5.00; n,6.40. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 655.25; experimental values 655.3 (M + )。
4.3 in a 100mL two-necked flask under argon atmosphere, m-14 (1.3 g,2 mmol) was introduced into 18mL tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of methylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12h, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-15 was obtained by column separation (830 mg, yield: 64%).
Elemental analysis structure (C) 45 H 41 N 3 O 2 ): theoretical value C,82.41; h,6.30; n,6.41; test value C,82.71; h,6.20; n,6.40. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 655.32; experimental values 655.3 (M + )。
4.4 in a 100mL single neck flask under argon atmosphere, weighing m-15 (655 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-16 (530 mg, 85%) by column.
Elemental analysis structure (C) 45 H 37 N 3 ): theoretical value C,87.20; h,6.02; n,6.78; test values C,87.10, H,6.00, N,6.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 619.30; experimental value 619.3 (M + )。
4.5 under argon atmosphere, m-port flask was weighed out in a 50mL one-port flask16(619mg，1mmol)，m-17(408mg，1mmol)，Pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 1-43 (680 mg, 72%) was isolated by column separation.
Elemental analysis structure (C) 67 H 54 N 4 O 2 ): theoretical value C,84.96; h,5.75; n,5.92; test value C,84.90; h,5.70; n,5.98. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 946.42; experimental values 946.4 (M + )。
Example 5
The reaction formula is as follows:
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5.1 in a 100mL two-necked flask under argon atmosphere, m-2 (1.2 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of phenylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-18 was obtained by column separation (700 mg, yield: 41%).
Elemental analysis structure (C) 62 H 43 N 3 O 2 ): theoretical value C,86.39; h,5.03; n,4.87; test value C,86.41; h,5.10; n,4.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 861.34; experimental values 861.3 (M + )。
5.2 in a 100mL single neck flask under argon atmosphere, weighing m-18 (861 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, removing the solvent from the organic phase obtained by filtration, and separating the product m-19 (600 mg, 73%) by column separation.
Elemental analysis structure (C) 62 H 39 N 3 ): theoretical value C,90.15; h,4.76; n,5.09; test value C,90.10; h,4.78; n,5.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 825.31; experimental values 825.3 (M + )。
5.3 in a 50mL one-neck flask under argon atmosphere, m-19 (823mg, 1 mmol), m-20 (402 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 2-5 (800 mg, 66%) was isolated by column separation.
Elemental analysis structure (C) 84 H 54 N 6 ): theoretical value C,87.93; h,4.74; n,7.32; test value C,87.90; h,4.88; n,7.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1146.44; experimental values 1146.4 (M + )。
Example 6
The reaction formula is as follows:
6.1 in a 100mL two-necked flask under argon atmosphere, m-2 (1.2 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of 4-tert-butylphenyl magnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-21 (600 mg, yield: 27%) was obtained by column separation.
Elemental analysis structure (C) 78 H 75 N 3 O 2 ): theoretical value C,86.23; h,6.96; n,3.87; test value C,86.41; h,6.70; n,3.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS)) Theoretical value 1085.59; experimental values 1085.6 (M + )。
6.2 in a 100mL single neck flask under argon atmosphere, weighing m-21 (1085 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-22 (600 mg, 57%).
Elemental analysis structure (C) 78 H 71 N 3 ): theoretical value C,89.19; h,6.81; n,4.00; test value C,89.30; h,6.40; n,4.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1049.56; experimental values 1049.6 (M + )。
6.3 in a 50mL one-neck flask under argon atmosphere, m-22 (1049 mg,1 mmol), m-23 (416 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 m g,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product was isolated by column separation (700 mg, 51%).
Elemental analysis structure (C) 101 H 88 N 6 ): theoretical value C,87.54; h,6.40; n,6.06; test value C,87.50; h,6.20; n,6.05. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1384.71; experimental values 1384.7 (M + )。
Example 7
The reaction formula is as follows:
7.1 in a 100mL two-necked flask under argon atmosphere, m-2 (1.2 g,2 mmol) was introduced into 18mL tetrahydrofuran, stirred at room temperature, 20mL (20 mmol) of biphenylmagnesium bromide was then added dropwise, the temperature was raised to 80℃for reaction for 12h, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-24 was obtained by column separation (900 mg, yield: 38%).
Elemental analysis structure (C) 86 H 59 N 3 O 2 ): theoretical value C,88.56; h,5.10; n,3.60; test value C,88.41; h,5.10; n,3.60. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1165.46; experimental values 1165.5 (M + )。
7.2 in a 100mL single neck flask under argon atmosphere, weighing m-24 (1165 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating an organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove a solvent, and separating a column to obtain a product m-25 (770 mg, 68%).
Elemental analysis structure (C) 86 H 55 N 3 ): theoretical value C,91.38; h,4.90; n,3.72; test value C,91.30; h,4.90; n,3.73. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1129.44; experimental values 1129.4 (M + )。
7.3 in a 50mL one-neck flask under argon atmosphere, m-25 (1129 mg,1 mmol), m-26 (261 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 2-33 (760 mg, 58%) was isolated by column separation.
Elemental analysis structure (C) 99 H 63 N 3 O): theoretical value C,90.73; h,4.85; n,3.21; test value C,90.70; h,4.80; n,3.15. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1309.50; experimental values 1309.5 (M + )。
Example 8
The reaction formula is as follows:
8.1 in a 100mL two-necked flask under argon atmosphere, m-1 (3.45 g,10 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB), 8mL methyl 4-methoxyo-iodobenzoate (50 mmol) were added, the temperature was raised to 220℃and stirred for 50 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the obtained organic phase by filtration, and the product m-27 (900 mg, yield: 13%) was isolated from the column.
Elemental analysis structure (C) 42 H 31 N 3 O 6 ): theoretical value C,74.88; h,4.64; n,6.24; test value C,74.89; h,4.80; n,6.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 673.22; experimental values 673.2 (M + )。
8.2 in a 100mL two-necked flask under argon atmosphere, m-27 (1.5 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, 20mL (20 mmol) of fluorenylmagnesium bromide was then added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-28 was obtained by column separation (920 mg, yield: 33%).
Elemental analysis structure (C) 100 H 79 N 3 O 4 ): theoretical value C,86.61; h,5.74; n,3.03; test value C,86.71; h,5.80; n,3.00. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1385.61; experimental values 1385.6 (M + )。
8.3 in a 100mL single neck flask under argon atmosphere, weighing m-28 (1.4 g,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-29 (830 mg, 61%) by column.
Elemental analysis structure (C) 100 H 75 N 3 O 2 ): theoretical value C,88.92; h,5.60; n,3.11; test value C,88.90; h,5.50; n,3.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1349.59; experimental values 1349.6 (M + )。
8.4 in a 50mL one-neck flask under argon atmosphere, m-29 (1.35 g,1 mmol), m-30 (294 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 2-41 (780 mg, 50%) was isolated by column separation.
Elemental analysis structure (C) 112 H 83 N 3 O 4 S): theoretical value C,85.85; h,5.34; n,2.68; s,2.05; test value C,85.80; h,5.30; n,2.58; s,2.05; matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1565.61; experimental values 1565.6 (M + )。
Example 9
The reaction formula is as follows:
9.1 to a MeCN solution of 5-methoxyindole (m-31) N-bromosuccinimide was added gradually in portions. After stirring at room temperature for 3 hours, the solid crude product was obtained by filtration, washed with MeCN and then dissolved in methanol. Triethylamine, formic acid and 10% Pd/C were added, and the mixture was heated under reflux for 30 minutes. After the reaction system was cooled to room temperature, the mixture was filtered. The filtrate was diluted with dichloromethane and washed with 10% aqueous hcl and brine. The organic layer was collected and separated by column to give the product m-32 (3.2 g, yield: 18%).
Elemental analysis structure (C) 27 H 21 N 3 O 3 ): theoretical value C,74.47; h,4.86; n,9.65; o,11.02;test value C,74.51; h,4.80; n,9.63.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 435.16; experimental values 435.2 (M + )。
9.2 in a 100mL two-necked flask under argon atmosphere, m-32 (4.35 g,10 mmol), methyl 5-tert-butyliodobenzoate (16 g,50 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220℃and stirred for 36 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was separated to give the product m-33 (3.9 g, yield 48%).
Elemental analysis structure (C) 51 H 49 N 3 O 7 ): theoretical value C,75.07; h,6.05; n,5.15; test value C,75.11; h,6.00; n,5.23.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 815.36; experimental values 815.4 (M + )。
9.3 in a 100mL two-necked flask under argon atmosphere, m-33 (1.63 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 20mL (20 mmol) of phenyl magnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-34 was obtained by column separation (800 mg, yield: 40%).
Elemental analysis structure (C) 73 H 65 N 3 O 5 ): theoretical value C,82.38; h,6.16; n,3.95; test value C,82.31; h,6.10; n,4.00. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1063.49; experimental value 1063.5 (M + )。
9.4 in a 100mL single neck flask under argon atmosphere, m-34 (1063 mg,1 mmol) was weighed, 20mL glacial acetic acid was added, 3mL concentrated hydrochloric acid was further added, the mixture was heated to 130℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-35 (850 mg, 82%) was obtained by column separation.
Elemental analysis structure (C) 73 H 61 N 3 O 3 ): theoretical value C,85.27; h,5.98; n,4.09; test value C,85.30; h,5.90; n,4.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1027.47; experimental values 1027.5 (M + )。
9.5 in a 50mL one-neck flask under argon atmosphere, m-35 (1027 mg,1 mmol), m-36 (383 mg,1 mmol), pd were weighed out 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were added, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added to extract, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 2-51 (460 mg, 52%) was isolated by column separation.
Elemental analysis structure (C) 93 H 67 N 7 O 3 ): theoretical value C,83.95; h,5.08; n,7.37; test value C,83.90; h,5.02; n,7.48. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1329.53; experimental values 1329.5 (M + )。
Example 10
The reaction formula is as follows:
10.1A mixture of m-8 (725 mg), ethanol (30 mL), water (30 mL) and NaOH was heated at 100deg.C for 3 hours. After cooling to room temperature, dilute hydrochloric acid was added to the mixture until a white solid appeared. The suspension was filtered off, the solid was washed with water and the resulting mixture of solid and polyphosphoric acid was heated at 180℃for 4 hours. After cooling to room temperature, the mixture was poured into hot water. After cooling to room temperature, the mixture was extracted with dichloromethane and washed with water. The solvent was removed from the organic phase obtained by filtration, and the product m-37 (450 mg, yield: 62%) was obtained by column separation.
Elemental analysis structure (C) 46 H 35 N 3 O 2 ): theoretical value C,83.48; h,5.33; n,6.35; test value C,83.51; h,5.40; n,6.33.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 661.27; experimental values 661.3 (M + )。
10.4 in a 50mL one-neck flask under argon atmosphere, m-37 (661 mg,1 mmol), m-38 (413 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 3-9 (490 mg, 52%) was isolated by column separation.
Elemental analysis structure (C) 68 H 47 N 7 O 2 ): theoretical value C,82.15; h,4.77; n,9.86; test value C,82.20; h,4.82; n,9.88. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 993.38; experimental values 993.4 (M + )。
Example 11
The reaction formula is as follows:
11.1 m-1 (3.45 g,10 mmol), 4-tert-butyl-2-bromoiodobenzene (16.9 g,50 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220℃and stirred for 50 hours under argon, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent was removed from the organic phase obtained by filtration, and the product m-39 (900 mg, yield: 12%) was obtained by column separation.
Elemental analysis structure (C) 44 H 37 Br 2 N 3 ): theoretical value C,68.85; h,4.86; n,5.47; test value C,68.41; h,4.80; n,5.60.Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 765.14; experimental values 765.1 (M + )。
11.2 in a 100mL two-necked flask, m-39 (765 mg,1 mmol) was added under argon atmosphere, 20mL of anhydrous Tetrahydrofuran (THF) was added, and the apparatus was then placed in a dry ice/acetone bath at-78deg.C and cooled for 15min. 5mL (2 mmol) of n-hexane solution of n-butyllithium was measured by a syringe, and the mixture was added dropwise to a reaction flask, reacted at-78℃for 1 hour, then diphenylchlorosilane was added to the reaction system, and the reaction was carried out at room temperature for 12 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-40 was obtained by column separation (600 mg, yield: 62%).
Elemental analysis structure (C) 68 H 59 N 3 Si 2 ): theoretical value C,83.82; h,6.10; n,4.31; test value C,83.41; h,6.20; n,4.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 973.42; experimental values 973.4 (M + )。
11.3 in a 100mL two-necked flask, m-40 (973 mg,1 mmol), 3-dimethyl-1-butene (0.64 mL,5 mmol), rhCl (PPh) 3 ) 3 (9.2 mg,0.01 mmol) was added 20mL of 1, 4-dioxane and the mixture was heated to 135℃to react for 24 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-41 (820 mg, 84%) was obtained by column separation.
Elemental analysis structure (C) 68 H 55 N 3 Si 2 ): theoretical value C,84.17; h,5.71; n,4.33; test value C,84.20; h,5.80; n,4.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 969.39; experimental values 969.4 (M + )
11.4 in a 50mL one-neck flask under argon atmosphere, m-41 (969 mg,1 mmol), m-17 (408 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), was introduced into 20mL of toluene, heated to 110 ℃,the reaction was allowed to react for 4 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by filtration to give the product 4-13 (890 mg, 63%) by column separation.
Elemental analysis structure (C) 90 H 72 N 4 O 2 Si 2 ): theoretical value C,83.59; h,5.97; n,3.11; s,4.64; test value C,83.60; h,5.58; n,4.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1296.52; experimental values 1296.5 (M + )。
Example 12
The reaction formula is as follows:
12.1 m-1 (3.45 g,10 mmol), 4-tert-butyl-o-nitrobromobenzene (12.9 g,50 mmol), copper iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220℃and stirred for 36 hours under argon, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was separated to give the product m-42 (3.8 g, 54% yield).
Elemental analysis structure (C) 44 H 37 N 5 O 4 ): theoretical C,75.52; h,5.33; n,10.01; test value C,75.51; h,5.30; n,10.10.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 699.28; experimental values 699.3 (M + )。
12.2 in a 50mL single neck flask under argon atmosphere, m-42 (699 mg,1 mmol), triphenylphosphine (1.3 g,5 mmol) were weighed, 20mL o-dichlorobenzene was added, heated to 180℃for 8 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-43 (420 mg, 66%) was obtained by column separation.
Elemental analysis structure (C) 44 H 37 N 5 ): theoretical value C,83.12; h,5.87; n,11.01; test value C,83.23; h,5.90; n,11.13.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 635.30; experimental value 635.3 (m+).
12.3 in a 50mL one-neck flask under argon atmosphere, m-43 (635 mg,1 mmol), bromobenzene (314 mg,2 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-44 (530 mg, 67%) was obtained by column separation.
Elemental analysis structure (C) 56 H 45 N 5 ): theoretical value C,85.36; h,5.76; n,8.89; test value C,85.30; h,5.80; n,8.80.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 787.37; experimental value 787.4 (M + )。
12.4 in a 50mL one-neck flask under argon atmosphere, m-44 (787 mg,1 mmol), m-45 (331 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product was isolated by column separation (790 mg, 76%).
Elemental analysis structure (C) 72 H 49 N 9 ): theoretical value C,83.13; h,4.75; n,12.12; test value C,83.10; h,4.78; n,12.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1039.41; experimental values 1039.4 (M + )。
Example 13
The reaction formula is as follows:
13.1 an ether solution of intermediate m-39 (767 mg,1 mmol) was cooled to-78℃under a nitrogen stream, and then an n-hexane solution of n-butyllithium was slowly added dropwise thereto, followed by stirring for 3 hours. To the reaction solution was slowly added dropwise dichlorophenyl phosphorus. The reaction mixture was brought to room temperature and stirred for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The crude product is refined by silica gel column chromatography. Intermediate m-46 (600 mg, yield: 73%) was obtained.
Elemental analysis structure (C) 56 H 45 N 3 P 2 ): theoretical value C,81.83; h,5.52; n,5.11; p,7.54; test value C,81.34; h,5.50; n,5.60. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 821.31; experimental values 821.3 (M + )。
13.2A mixture of compound m-46 (0.82 g,1 mmol), glacial acetic acid (20 ml) and 34% hydrogen peroxide (100 ml) was reacted at 120℃for 2 hours, then cooled and poured into cold water. The precipitate was collected by vacuum filtration, washed with water and dried in a vacuum oven to give m-47 (520 mg, yield: 61%).
Elemental analysis structure (C) 56 H 45 N 3 O 2 P 2 ): theoretical C,78.77; h,5.31; n,4.92; o,3.75; p,7.25; test value C,78.58; h,5.33; n,4.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 853.30; experimental values 853.3 (M + )。
13.3 in a 50mL one-neck flask under argon atmosphere, m-47 (0.86 g,1 mmol), m-48 (387 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hoursAfter cooling to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 6-16 (800 mg, 69%) was obtained by column separation.
Elemental analysis structure (C) 78 H 59 N 5 O 2 P 2 ): theoretical value C,80.74; h,5.13; n,6.04; test value C,80.60; h,5.10; n,6.25. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1159.41; experimental values 1159.4 (M + )。
Example 14
The reaction formula is as follows:
14.1 m-1 (3.45 g,10 mmol), m-49 (15 g,50 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, heated to 220℃and stirred under argon for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-50 (780 mg, yield: 10%) was isolated by column separation.
Elemental analysis structure (C) 52 H 51 N 3 O 4 ): theoretical value C,79.87; h,6.57; n,5.37; o,8.18; test value C,79.89; h,6.58; n,5.41. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 781.39; experimental values 781.4 (M + )。
14.2 intermediate m-50 (781 mg,1 mmol) and CF 3 SO 3 H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours, then with a mixture of water and pyridine (8:1 by volume) for 30 minutes. The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by a column to obtain intermediate m-51 (189 mg, yield: 29%).
Elemental analysis structure (C) 44 H 35 N 3 O 2 ): theoretical value C,82.86; h,5.53; n,6.59; o,5.02; test value C,82.88; h,5.50; n,6.70. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 637.27; experimental values 637.3 (M + )。
14.3 in a 50mL one-neck flask under argon atmosphere, m-51 (637 mg,1 mmol), m-52 (275 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 7-12 (550 mg, 66%) was obtained by column separation.
Elemental analysis structure (C) 57 H 41 N 3 O 4 ): theoretical value C,82.29; h,4.97; n,5.05; test value C,82.30; h,5.00; n,5.15. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 831.31; experimental values 831.3 (M + )。
Example 15
The reaction formula is as follows:
15.1 m-1 (3.45 g,10 mmol), m-53 (14 g,50 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, heated to 220℃and stirred under argon for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-54 (800 mg, yield: 11%) was isolated by column separation.
Elemental analysis structure (C) 46 H 43 N 3 O 2 S 2 ): theoretical C,75.27; h,5.91; n,5.73; o,4.36; s,8.74 testValues C,75.30; h,5.90; n,5.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 733.28; experimental values 733.3 (M + )。
15.2 intermediate m-54 (733 mg,1 mmol) and CF 3 SO 3 H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours, then with a mixture of water and pyridine (8:1 by volume) for 30 minutes. The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by a column to obtain intermediate m-55 (400 mg, yield: 60%).
Elemental analysis structure (C) 44 H 35 N 3 S 2 ): theoretical value C,78.89; h,5.27; n,6.27; s,9.57; test value C,78.63; h,5.33; n,6.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 669.23; experimental value 669.2 (M + )。
15.3 in a 50mL one-neck flask under argon atmosphere, m-55 (669 mg,1 mmol), s-56 (416 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 8-10 (580 mg, 58%) was isolated by column separation.
Elemental analysis structure (C) 67 H 52 N 6 S 2 ): theoretical value C,80.05; h,5.21; n,8.36; s,6.38; test value C,80.00; h,5.20; n,8.35. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1004.37; experimental values 1004.4 (M + )。
Example 16
The reaction formula is as follows:
16.1 Compound m-55 (0.67 g,1 mmol) was dissolved in 20mL dichloromethane and stirred at room temperature for 24h, then poured into cold water. The precipitate was collected by vacuum filtration, washed with water and dried in a vacuum oven to give m-57 (420 mg, yield: 60%).
Elemental analysis structure (C) 44 H 35 N 3 O 2 S 2 ): theoretical value C,75.29; h,5.03; n,5.99; o,4.56; s,9.14; test value C,75.30; h,5.10; n,6.00. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 701.22; experimental value 701.2 (M + )。
16.2 in a 50mL one-neck flask under argon atmosphere, m-57 (701 mg,1 mmol), m-58 (387 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 9-11 (480 mg, 48%) was obtained by column separation.
Elemental analysis structure (C) 66 H 49 N 5 O 2 S 2 ): theoretical value C,78.62; h,4.90; n,6.95; s,6.36; test value C,78.40; h,4.88; n,6.95. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1007.33; experimental values 1007.3 (M + )。
Example 17
The reaction formula is as follows:
17.1A mixture of compound m-55 (0.67 g,1 mmol), glacial acetic acid (20 ml) and 34% hydrogen peroxide (100 ml) was reacted at 120℃for 2 hours, then cooled and poured into cold water. The precipitate was collected by vacuum filtration, washed with water, and dried in a vacuum oven to give m-59 (430 mg, yield: 59%).
Elemental analysis structure (C) 44 H 35 N 3 O 4 S 2 ): theoretical value C,72.01; h,481; n,5.73; s,8.74; test value C,72.08; h,4.83; n,5.70. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 733.21; experimental values 733.2 (M + )。
17.2 in a 50mL one-neck flask under argon atmosphere, m-59 (733 mg,1 mmol), m-60 (380 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 10-15 (580 mg, 56%) was obtained by column separation.
Elemental analysis structure (C) 64 H 48 N 4 O 6 S 2 ): theoretical value C,74.40; h,4.68; n,5.42; s,6.21; test value C,74.50; h,4.68; n,5.45. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1032.30; experimental values 1032.3 (M + )。
Example 18
The reaction formula is as follows:
18.1 m-1 (3.45 g,10 mmol), m-61 (16 g,50 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, heated to 220℃and stirred under argon for 50 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-62 (880 mg, yield: 14%) was isolated by column separation.
Elemental analysis structure (C) 46 H 43 N 3 O 2 Se 2 ): theoretical value C,66.74; h,5.24; n,5.08; test value C,66.65; h,5.30; n,5.00. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 829.17; experimental values 829.2 (M + )。
18.2 intermediate m-62 (829 mg,1 mmol) and CF 3 SO 3 H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours, then with a mixture of water and pyridine (8:1 by volume) for 30 minutes. The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by a column to obtain intermediate m-63 (430 mg, yield: 56%).
Elemental analysis structure (C) 44 H 35 N 3 Se 2 ): theoretical C,69.20; h,4.62; n,5.50; test value C,69.33; h,4.63; n,5.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 765.12; experimental values 765.1 (M + )。
18.3 in a 50mL one-neck flask under argon atmosphere, m-63 (765 mg,1 mmol), m-64 (261 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 11-13 (660 mg, 70%) was obtained by column separation.
Elemental analysis structure (C) 57 H 41 N 3 O 3 SSe 2 ): theoretical value C,68.06; h,4.11; n,4.18; s,3.19; test value C,68.10; h,4.28; n,4.20; s,3.29. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1007.12; experimental values 1007.1 (M + )。
Example 19
The reaction formula is as follows:
19.1 m-1 (3.45 g,10 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB), 8mL methyl o-iodobenzoate (50 mmol) were added, heated to 220℃and stirred under argon for 50 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-65 (500 mg, yield: 10%) was isolated from the column.
Elemental analysis structure (C) 32 H 21 N 3 O 2 ): theoretical value C,80.15; h,4.41; n,8.76; test value C,80.20; h,4.40; n,8.80. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 479.16; experimental values 479.2 (M + )。
19.2 m-65 (0.96 g,2 mmol) was added to a 100mL two-necked flask under argon atmosphere, 18mL of tetrahydrofuran was introduced, stirred at room temperature, 10mL (10 mmol) of methylmagnesium bromide was then added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-66 was obtained by column separation (600 mg, yield: 62%).
Elemental analysis structure (C) 33 H 25 N 3 O): theoretical value C,82.65; h,5.25; n,8.76; o,3.34; test value C,82.51; h,5.30; n,8.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 479.20; experimental values 479.2 (M + )。
19.3 in a 100mL single neck flask under argon atmosphere, m-66 (479 mg,1 mmol) was weighed, 20mL glacial acetic acid was added, 3mL concentrated hydrochloric acid was further added, the mixture was heated to 130℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-67 (330 mg, 71%) was obtained by column separation.
Elemental analysis structure (C) 33 H 23 N 3 ): theoretical value C,85.87; h,5.02; n,9.10 test value C,85.80; h,5.00; n,9.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 461.19; experimental value 461.2 (M + )。
19.4 in a 50mL one-neck flask under argon atmosphere, m-67 (463mg, 1 mmol), m-38 (8236 mg,2 mmol), pd were weighed out 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 12-2 (610 mg, 50%) was obtained by column separation.
Elemental analysis structure (C) 77 H 47 N 11 ): theoretical value C,82.11; h,4.21; n,13.68; test value C,82.10; h,4.20; n,13.70. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1125.40; experimental values 1125.4 (M + )。
Example 20
The reaction formula is as follows:
20.1 in a 100mL two-necked flask under argon atmosphere, m-65 (0.96 g,2 mmol) was introduced into 18mL tetrahydrofuran, stirred at room temperature, then 10mL (10 mmol) of phenylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-68 was obtained by column separation (750 mg, yield: 62%).
Elemental analysis structure (C) 43 H 29 N 3 O): theoretical value C,85.55; h,4.84; n,6.96; o,2.65; test value C,85.41; h,4.80; n,6.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 603.23; experimental value 603.2 (M + )。
20.2 in a 100mL single neck flask under argon atmosphere, m-68 (603 mg,1 mmol) was weighed, 20mL glacial acetic acid was added, 3mL concentrated hydrochloric acid was further added, the mixture was heated to 130℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-69 (420 mg, 72%) was obtained by column separation.
Elemental analysis structure (C) 43 H 27 N 3 ): theoretical C,88.18; h,4.65; n,7.17; test value C,88.10; h,4.68; n,7.10. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 585.22; experimental values 585.2 (M + )。
20.3 in a 50mL one-neck flask under argon atmosphere, m-69 (585 mg,1 mmol), m-70 (788 mg,2 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 13-3 (870 mg, 72%) was obtained by column separation.
Elemental analysis structure (C) 85 H 65 N 9 ): theoretical C,84.20; h,5.40; n,10.40 test value C,84.22; h,5.40; n,10.39; matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1211.54; experimental values 1211.5 (M + )。
Example 21
The reaction formula is as follows:
21.1 in a 100mL two-necked flask under argon atmosphere, m-1 (3.45 g,10 mmol), cuprous iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed, 50mL o-dichlorobenzene (o-DCB), 8mL methyl 4-methoxyo-iodobenzoate (50 mmol) were added, the temperature was raised to 220℃and stirred for 50 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the obtained organic phase by filtration, and the product m-71 (900 mg, yield: 13%) was isolated from the column.
Elemental analysis structure (C) 33 H 23 N 3 O 3 ): theoretical C,77.78; h,4.55; n,8.25; test value C,77.89; h,4.60; n,8.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 509.17; experimental value 509.2 (M + )。
21.2 in a 100mL two-necked flask under argon atmosphere, m-71 (1.1 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, 20mL (20 mmol) of fluorenylmagnesium bromide was then added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-72 was obtained by column separation (920 mg, yield: 33%).
Elemental analysis structure (C) 62 H 47 N 3 O 2 ): theoretical value C,85.98; h,5.47; n,4.85; test value C,86.01; h,5.50; n,4.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 865.37; experimental values 865.4 (M + )。
21.3 in a 100mL single neck flask under argon atmosphere, weighing m-72 (0.87 g,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-73 (830 mg, 61%) by column.
Elemental analysis structure (C) 62 H 45 N 3 O): theoretical value C,87.81; h,5.35; n,4.95; test value C,87.90; h,5.40; n,4.90. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 847.36; experimental values 847.4 (M + )。
21.4 in a 50mL one-neck flask under argon atmosphere, m-73 (0.85 g,1 mmol), m-74 (287 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene was introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the mixture was separated by column separationProduct 13-22 (780 mg, 72%).
Elemental analysis structure (C) 90 H 57 N 3 O 5 ): theoretical value C,85.76; h,4.56; n,3.33; test value C,85.80; h,4.30; n,3.58; matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1259.43; experimental values 1259.4 (M + )。
Example 22
The reaction formula is as follows:
22.1 in a 50mL one-neck flask under argon atmosphere, m-1 (345 mg,1 mmol), 4-tert-butylbromobenzene (212 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-75 (320 mg, 69%) was isolated by column separation.
Elemental analysis structure (C) 34 H 27 N 3 ): theoretical value C,85.50; h,5.70; n,8.80; test value C,85.50; h,5.50; n,8.90.
Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 477.22; experimental value 477.2 (M + )。
22.2 m-75 (4.8 g,10 mmol), copper iodide, (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB), 8mL methyl 4-tert-butylo-iodobenzoate (50 mmol) were added, warmed to 220℃and stirred for 50 hours under argon protection, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the obtained organic phase by filtration, and the product m-76 (980 mg, yield: 14%) was isolated from the column.
Elemental analysis structure (C) 46 H 41 N 3 O 2 ): theoretical value C,82.73; h,6.19; n,6.29; test value C,82.60; h,6.20; n,6.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 667.32; experimental values 667.32 (M + )。
22.3 in a 100mL two-necked flask under argon atmosphere, m-76 (1.33 g,2 mmol) was introduced into 18mL of tetrahydrofuran, stirred at room temperature, then 10mL (10 mmol) of phenylmagnesium bromide was added dropwise, the temperature was raised to 80℃for reaction for 12 hours, then cooled to room temperature, ethyl acetate and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-77 was obtained by column separation (800 mg, yield: 50%).
Elemental analysis structure (C) 57 H 49 N 3 O): theoretical value C,86.44; h,6.24; n,5.31; test value C,86.41; h,6.20; n,5.40. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 791.39; experimental values 791.4 (M + )。
22.4 in a 100mL single neck flask under argon atmosphere, weighing m-77 (791 mg,1 mmol), adding 20mL glacial acetic acid, adding 3mL concentrated hydrochloric acid, heating to 130 ℃, reacting for 4 hours, cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, adding anhydrous sodium sulfate for drying, filtering the obtained organic phase to remove the solvent, and separating the product m-78 (530 mg, 68%) by column.
Elemental analysis structure (C) 57 H 47 N 3 ): theoretical C,88.45; h,6.12; n,5.43; test value C,88.50; h,6.18; n,5.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 773.38; experimental values 773.4 (M + )。
22.5 in a 50mL one-neck flask under argon atmosphere, m-78 (773 mg,1 mmol), m-79 (319 mg,1 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene was introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product was obtained by column separation 13-16(760mg，74％)。
Elemental analysis structure (C) 77 H 57 N 5 ): theoretical value C,87.88; h,5.46; n,6.66; test value C,87.90; h,5.50; n,6.50. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1051.46; experimental values 1051.5 (M + )。
Example 23
The reaction formula is as follows:
23.1 m-1 (3.45 g,10 mmol), 4-tert-butyl-2-bromoiodobenzene (16.9 g,50 mmol), cuprous iodide (190 mg,1 mmol), copper powder (2.5 g,40 mmol) and potassium carbonate (5.5 g,40 mmol) were weighed in a 100mL two-neck flask under argon atmosphere, 50mL o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220℃and stirred for 50 hours under argon, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent was removed from the organic phase obtained by filtration, and the product m-80 (990 mg, yield: 18%) was obtained by column separation.
Elemental analysis structure (C) 34 H 26 BrN 3 ): theoretical C,73.38; h,4.71; n,7.55; test value C,73.41; h,4.80; n,7.60. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 555.13; experimental values 555.1 (M + )。
23.2 in a 100mL two-necked flask, m-80 (555 mg,1 mmol) was added under argon atmosphere, 20mL of anhydrous Tetrahydrofuran (THF) was added, and the apparatus was then placed in a dry ice/acetone bath at-78deg.C and cooled for 15min. 5mL (2 mmol) of n-hexane solution of n-butyllithium was measured by a syringe, and the mixture was added dropwise to a reaction flask, reacted at-78℃for 1 hour, then diphenylchlorosilane was added to the reaction system, and the reaction was carried out at room temperature for 12 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product m-81 was obtained by column separation (720 mg, yield: 68%).
Element separationAnalysis structure (C) 43 H 37 N 3 Si 1 ): theoretical value C,83.72; h,5.65; n,6.37; test value C,83.41; h,5.60; n,6.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 659.28; experimental value 659.3 (M + )。
23.3 in a 100mL two-necked flask, m-81 (659 mg,1 mmol), 3-dimethyl-1-butene (0.64 mL,5 mmol), rhCl (PPh) 3 ) 3 (9.2 mg,0.01 mmol) was added 20mL of 1, 4-dioxane and the mixture was heated to 135℃to react for 24 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product m-82 (820 mg, 84%) was obtained by column separation.
Elemental analysis structure (C) 46 H 35 N 3 Si): theoretical value C,83.98; h,5.36; n,6.39; test value C,84.20; h,5.40; n,6.30. Matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 657.26; experimental values 657.3 (M + )。
23.4 in a 50mL one-neck flask under argon atmosphere, m-82 (657 mg,1 mmol), m-83 (534 mg,2 mmol), pd 2 dba 3 (91mg，0.1mmol)，t-Bu 3 PHBF 4 (90 mg,0.3 mmol), t-Buona (288 mg,3 mmol), 20mL of toluene were introduced, heated to 110℃and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 15-1 (690 mg, 63%) was obtained by column separation.
Elemental analysis structure (C) 76 H 53 N 9 Si): theoretical value C,81.47; h,4.77; n,11.25; test value C,81.60; h,4.98; n,11.10; matrix assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theory 1119.42; experimental values 1119.4 (M + )。
And (3) testing:
photophysical properties of the condensed trimeric indole conjugated molecules prepared in 23 examples of the present invention were examined as shown in table 1.
TABLE 1 photophysical Properties of conjugated molecules obtained in examples 1 to 23
Note that: ΔE in table ST By bringing the compound to 10 as the difference between the singlet energy level and the triplet energy level -5 The concentration of mol/L is dissolved in an anaerobic toluene solution to prepare a tested sample, and the difference between the initial (onset) value of the measured fluorescence spectrum and the phosphorescence spectrum is measured, and the testing instrument is HORIBA FluoroMax spectrofluorometer (Japan); the delayed fluorescence lifetime is obtained by doping a compound into polystyrene at a concentration of 10wt% to obtain a sample to be tested, and testing the sample by using a time-resolved fluorescence spectrometer, wherein the testing instrument is Edinburgh fluorescence spectrometer (FLS-980, UK); PLQY is the photoluminescence quantum yield by combining the compounds at 10 -5 The concentration of mol/L is dissolved in an anaerobic toluene solution to prepare a tested sample, and an absolute PLQY value is obtained through an integrating sphere test.
As can be seen from Table 1, the fused ring conjugated molecules in the examples provided herein have a smaller ΔE ST (<0.3 eV), exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 1 to 10 μs; meanwhile, the luminescent compound provided by the invention also shows higher PLQY (70% -99%).
Device embodiment
The organic light-emitting layer adopts the solution processing technology to prepare the device as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and then spin-coated the conjugated molecules obtained in examples 1 to 23 with mCP at a mass ratio of 1:9, and annealing at 100℃for 30 minutes, followed by 4X 10 -4 Sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under Pa vacuum degree to obtain organic electroluminescent device, wherein mCP, TSPO1 and TmPyPB are respectively used asThe host material, exciton blocking layer and electron transport layer have the following structural formulas:
the specific device structure is as follows:
ITO/PEDOT：PSS(40nm)/EML(30nm)/TSPO1(8nm)/TmPyPB(42nm)/LiF(1nm)/Al(100nm)。
example 24
Taking the compound 1-2 obtained in the example 1 as an implementation object, the compound 1-2 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 1-2 provided herein.
Example 25
Taking the compounds 1-24 obtained in the example 2 as implementation targets, the mass ratio of the compounds 1-24 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 1-24 provided herein.
Example 26
Taking the compounds 1-35 obtained in the example 3 as implementation targets, the compounds 1-35 and mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 1-35 provided herein.
Example 27
Taking the compounds 1-43 obtained in example 4 as implementation targets, the compounds 1-43 and mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 1-43 provided herein.
Example 28
Taking the compound 2-5 in the example 5 as an implementation object, the compound 2-5 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 2-5 provided herein.
Example 29
Taking the compounds 2-25 in the example 6 as implementation targets, the mass ratio of the compounds 2-25 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 2-25 provided herein.
Example 30
Taking the compounds 2-33 in the example 7 as implementation targets, the mass ratio of the compounds 2-33 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 2-33 provided herein.
Example 31
Taking the compounds 2-41 in the example 8 as implementation targets, the mass ratio of the compounds 2-41 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 2-41 provided herein.
Example 32
Taking the compounds 2-51 in the example 9 as implementation targets, the mass ratio of the compounds 2-51 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 2-51 provided herein.
Example 33
Taking the compounds 3-9 in the example 10 as implementation targets, the mass ratio of the compounds 3-9 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 3-9 provided herein.
Example 34
Taking the compounds 4-13 in the example 11 as implementation targets, the mass ratio of the compounds 4-13 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 4-13 provided herein.
Example 35
Taking the compounds 5-15 in the example 12 as implementation targets, the mass ratio of the compounds 5-15 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 5-15 provided herein.
Example 36
Taking the compound 6-16 in the example 13 as an implementation object, the compound 6-16 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 6-16 provided herein.
Example 37
Taking the compounds 7-12 in the example 14 as implementation targets, the mass ratio of the compounds 7-12 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 7-12 provided herein.
Example 38
Taking the compounds 8-10 in the example 15 as implementation targets, the mass ratio of the compounds 8-10 to mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 8-10 provided herein.
Example 39
Taking the compound 9-11 in the example 16 as an implementation object, the compound 9-11 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 9-11 provided herein.
Example 40
Taking the compounds 10-15 in the example 17 as implementation targets, the mass ratio of the compounds 10-15 to mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 10-15 provided herein.
Example 41
Taking the compounds 11-13 in the example 18 as implementation targets, the mass ratio of the compounds 11-13 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 10-13 provided herein.
Example 42
Taking the compound 12-2 in the example 19 as an implementation object, the compound 12-2 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compound 12-2 provided herein.
Example 43
Taking the compound 13-3 in the example 20 as an implementation object, the compound 13-3 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with the compounds 13-3 provided herein.
Example 44
Taking the compounds 13-22 in the example 21 as implementation targets, the mass ratio of the compounds 13-22 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 13-22 provided herein.
Example 45
Taking the compounds 13-16 in the example 22 as implementation targets, the mass ratio of the compounds 13-16 to the mCP is 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compounds 13-16 provided herein.
Example 46
Taking the compound 15-1 in the example 23 as an implementation object, the compound 15-1 and the mCP are mixed according to the mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with compound 15-1 provided herein.
Comparative example 1
Taking a trimerization indole conjugated molecule TAT-BP which is not subjected to fused cyclization as an implementation object, and mixing the TAT-BP and mCP according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with TAT-BP.
Comparative example 2
Taking a trimerization indole conjugated molecule TAT-2BP which is not subjected to fused cyclization as an implementation object, and mixing the TAT-2BP and mCP according to a mass ratio of 1:9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, the device structure is utilized to prepare an organic electroluminescent device, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of electroluminescent devices prepared with TAT-2 BP.
TABLE 2 Performance test results of electroluminescent devices
Note that: the luminance of the panel is 1cd m -2 The driving voltage of the device; the maximum external quantum efficiency is obtained from the current-voltage curve and the electroluminescence spectrum of the device according to the calculation method described in literature (jpn.j.appl.Phys.2001, 40, l 783).
As can be seen from Table 2, the device prepared by the condensed ring trimerization indole conjugated molecule provided by the invention is obviously improved compared with the device prepared by the non-condensed trimerization indole conjugated molecule, and has higher device efficiency.
As can be seen from the device performance data, the above embodiment of the present invention achieves the following technical effects: the phenyl of the phenyl trimerization indole is locked through a bridging structure to form a condensed ring donor unit, so that the rigidity of the donor unit can be obviously enhanced, non-radiative transition of molecules caused by rotation or vibration is inhibited, and the luminous efficiency of the material is improved. The condensed ring donor unit has intramolecular steric hindrance effect, is easy to realize intramolecular distortion, not only can reduce quenching effect caused by intermolecular aggregation, but also can directly connect different electron acceptors through coupling reaction to obtain a highly distorted D-A structure, so that HOMO and LUMO are effectively separated, thereby obtaining lower delta E ST The fluorescent light has the property of thermal activation delay, so that higher exciton utilization rate is realized, and efficient light emission of multiple colors from deep blue light to near infrared light is realized.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (7)

1. Conjugated molecules based on trimeric indole condensed ring structures, as shown in formula (I) or formula (II):
wherein, -X-is selected from-C (R) 1 R 2 )-、-Si(R 1 R 2 )-、-N(R 1 )-、-PO(R 1 )-、-BR 1 -、-O-、-S-、-Se-、/>-or-SO 2 -；
R 1 And R is R 2 Each independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group;
L 1 ～L 5 each independently selected from H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group;
m 1 ～m 5 Each independently is an integer of 0 to 4;
the substituted C1-C30 branched hydrocarbon group, substituted C3-C30 cycloalkyl group, substituted C1-C30 alkoxy group and substituted C6-C60The substituents in the aromatic groups and the substituted C5-C60 heteroaromatic groups are each independently selected from D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 One or more of C1-C5 alkyl, C6-C20 aromatic group, C1-C5 alkoxy, C3-C10 cycloalkyl and C5-C20 heteroaromatic group;
the A and the A' are respectively and independently selected from one of structures shown in formulas a1-1 to a 16-4:
。
2. the conjugated molecule according to claim 1, wherein R 1 And R is R 2 Each independently selected from H, D, substituted or unsubstituted C1-C10 straight chain hydrocarbyl, substituted or unsubstituted C1-C10 branched hydrocarbyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C20 aromatic group, substituted or unsubstituted C5-C20 heteroaromatic group;
L 1 ～L 5 each independently selected from H, D, F, cl, br, I, CN, NO 2 、CF 3 、OH、SH、NH 2 A substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aromatic group, and a substituted or unsubstituted C5-C20 heteroaromatic group.
3. The conjugated molecule according to claim 1, wherein one of the compounds of formulae (1-1) to (22-6):
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
。
4. use of a conjugated molecule based on a trimeric indole fused ring structure according to any one of claims 1 to 3 as a thermally activated delayed fluorescence material.
5. An electroluminescent device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode; the organic thin film layer comprises the conjugated molecule based on the condensed ring structure of trimeric indole according to any one of claims 1 to 3.
6. The electroluminescent device of claim 5, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer comprises the conjugated molecule based on a condensed ring structure of trimeric indole according to any one of claims 1 to 3.
7. The electroluminescent device of claim 6, wherein the mass of the conjugated molecule based on the trimeric indole fused ring structure is 5% to 30% of the mass of the light emitting layer.
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CN112592363A (en) * 2020-12-21 2021-04-02 中国科学院长春应用化学研究所 Fused ring compound containing boron atoms and selenium/tellurium atoms and organic electroluminescent device
CN112592362A (en) * 2020-12-21 2021-04-02 中国科学院长春应用化学研究所 Condensed ring compound containing boron, nitrogen and sulfur atoms and five-membered aromatic heterocycle and organic electroluminescent device

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CN112592363A (en) * 2020-12-21 2021-04-02 中国科学院长春应用化学研究所 Fused ring compound containing boron atoms and selenium/tellurium atoms and organic electroluminescent device
CN112592362A (en) * 2020-12-21 2021-04-02 中国科学院长春应用化学研究所 Condensed ring compound containing boron, nitrogen and sulfur atoms and five-membered aromatic heterocycle and organic electroluminescent device

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