CN116947758A - Compound based on anthracene group, and preparation method and application thereof - Google Patents

Compound based on anthracene group, and preparation method and application thereof Download PDF

Info

Publication number
CN116947758A
CN116947758A CN202310799561.1A CN202310799561A CN116947758A CN 116947758 A CN116947758 A CN 116947758A CN 202310799561 A CN202310799561 A CN 202310799561A CN 116947758 A CN116947758 A CN 116947758A
Authority
CN
China
Prior art keywords
compound
solvent
group
formula
ethyl acetate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310799561.1A
Other languages
Chinese (zh)
Inventor
王会
原怡
徐能妮
栾新军
张源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NORTHWEST UNIVERSITY
Original Assignee
NORTHWEST UNIVERSITY
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NORTHWEST UNIVERSITY filed Critical NORTHWEST UNIVERSITY
Priority to CN202310799561.1A priority Critical patent/CN116947758A/en
Publication of CN116947758A publication Critical patent/CN116947758A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/225—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application relates to a compound based on a anthracene group, a preparation method and application thereof, wherein the compound has a structure shown in a formula (1) or (2):the organic luminescent material based on the anthracene group has the following luminescent characteristics under different external stimuli: by adjusting different solvent systems, polymorphism depending on different conformations can be formed in a single molecule, friction luminescence, mechanochromism and thermochromism can be realized among different polymorphism, and three-dimensional response is realized. The organic luminescent material has high fluorescence quantum yield in solid state, especially the solid state fluorescence quantum yield can reach 82%, and the solid obtained in different solvents shows different luminescent colors, and the change of the solid fluorescence color is visible to naked eyes after heating or mechanical grinding, and the process is reversible. The organic luminescent material can be applied to the optical field and/or the anti-counterfeiting and/or security field.

Description

Compound based on anthracene group, and preparation method and application thereof
Technical Field
The application relates to the technical field of organic luminescent materials, in particular to a compound based on a heteroanthracene group, a preparation method and application thereof, and particularly relates to application in the fields of electroluminescent devices, stress sensing, anti-counterfeiting marks, encryption and the like.
Background
In recent years, organic luminescent materials are widely applied to the fields of stimulus response, information anti-counterfeiting, organic luminescent devices, biomedical imaging and the like by virtue of the characteristics of easiness in separation and purification, wide luminescent range, various types, excellent photoelectric properties and the like, and are deeply concerned by scientific researchers. Theoretically, luminescence is characterized by the radiative decay process of singlet or triplet excitons when they transition from an excited state to a ground state, and when an organic compound emits light upon excitation (X-ray, ultraviolet light, visible light, force, etc.) by some energy source, it can be classified into: photoluminescence, mechanoluminescence, electroluminescence, thermoluminescence, triboluminescence, and bioluminescence.
The stimulus-responsive color-changing material refers to a functional material of which the fluorescence intensity and emission wavelength of molecules can be changed along with external stimulus under the action of external stimulus such as mechanical force (scraping, pressure, shearing force and the like), heating or solvent fumigation and the like. According to the external stimulus, the method can be divided into: thermally responsive, force responsive, solvent responsive, acid-base responsive, and the like.
Materials developed in recent years with stimulus-responsive color-changing fluorescence properties are: anthracene derivatives, tetraphenyl ethylene derivatives, anthraquinone derivatives, phenothiazine derivatives, and the like, and are widely used in mechanical sensors, fluorescent probes, optical switches, data storage, biological imaging, and the like.
CN113443994a discloses an organic luminescent material, a preparation method and application thereof, the preparation method of the organic luminescent material is as follows: dissolving a compound containing a quaternary ammonium structure in an alcohol solvent, standing until crystals are separated out, filtering and separating, and vacuum drying to obtain an organic luminescent material; wherein the quaternary ammonium structure-containing compound comprises one or more of tetramethyl ammonium bromide (TMAB), cetyl Trimethyl Ammonium Bromide (CTAB), cetyl Trimethyl Ammonium Chloride (CTAC) or Cetyl Trimethyl Ammonium Iodide (CTAI), and further comprises a double-headed quaternary ammonium salt compound, and the material is applied to the optical field and/or the anti-counterfeiting and/or security field.
CN115385949a discloses a silane organic luminescent material, a preparation method and a mixed solvent thereof, the silane organic luminescent material has a structure shown as formula (I),
n is a natural number of 1 to 4; r is R 1 Is a fluorescent group and R is 1 Is a tetraarylvinyl group. The silane organic luminescent material has high light stability and strong luminous efficiency, maintains the original color of a fluorescent group, and has the functions of solid state luminescence and solid state photochromic behavior.
In recent years, a large number of organic luminescent materials have been reported to focus on fluorescence signal changes caused by single stimulus changes, however, in the process of performing omnibearing monitoring on a complex external environment, development of organic luminescent materials with multiple stimulus responses is required.
Disclosure of Invention
In view of the above background, the present application provides a multi-stimulus response organic luminescent material based on a hybrid anthracene group. The luminescent characteristics of the material under different external stimuli are as follows: by adjusting different solvent systems of the material, polymorphic forms depending on different conformations can be formed in a single molecule, and the different polymorphic forms can realize triboluminescence, mechanochromism and thermochromism, thereby realizing three-dimensional response. The material has simple synthesis method and good luminous performance, and can be applied to the fields of electroluminescent devices, stress sensing, anti-counterfeiting marks, encryption and the like.
The primary aim of the application is to provide an organic luminescent material based on a hybrid anthracene group.
Another object of the present application is to provide a method for preparing the organic luminescent material based on the anthracene group, which is simple to prepare and easy to purify.
The third purpose of the application is to apply the organic luminescent material based on the above-mentioned hetero anthracene group to the fields of electroluminescent device, anti-counterfeiting mark, encryption, etc.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
a compound based on a xanthene group, which is a compound of the following general formula (1) and/or (2):
in the formulas (1) and (2), X is-NH-, -O-, -S-, a divalent group containing P, a divalent group containing silicon, a divalent group containing B or a C=C double bond; each R is independently selected from one of a hydrogen atom, a halogen (F, cl, br, I), a cyano group, an aldehyde group (preferably a C1-C6 aldehyde group), an aryl group (preferably a C6-C30 aryl group), a heteroaryl ring group (preferably a C6-C30 heteroaryl group); r is R 1 、R 2 Each selected from one of a hydrogen atom, a halogen, a cyano group, an aldehyde group (preferably a C1-C6 aldehyde group), and a phenyl group. Each R in formula (1) (i.e. R on each phenyl ring) may be present (on the corresponding phenyl ring) 1, 2, 3 or 4, preferably 1 or 2, each R in formula (2) (i.e. R on each phenyl ring) may be present (on the corresponding phenyl ring) 1, 2 or 3, preferably 1 or 2, each R may be the same or different, preferably the same. The divalent radicals containing P are, for example, selected from the group consisting of-P (O) Ph-, the divalent radicals containing B are, for example, selected from the group consisting of-BPh-, and the divalent radicals containing Si are, for example, -Si (CH) 3 ) 2 -。
Further, R is selected from one of hydrogen atom, halogen, cyano, aldehyde group, aryl group and heteroaryl ring group; r is R 1 、R 2 And is selected from one of hydrogen atom, halogen, cyano, aldehyde group and phenyl. Preferably, the aryl group from which R is selected is an aryl or substituted aryl group of 6 to 30 carbon atoms, further 6 to 24 carbon atoms, further 6 to 20 carbon atoms, further 6 to 15 carbon atoms, more preferably an aryl or substituted aryl group of 6 to 12 carbon atoms (e.g., a halogen, alkyl-substituted aryl group, etc.); the heteroaromatic ring group selected from R is an aromatic heterocycle or substituted aromatic heterocycle of 6 to 30, further 6 to 24, further 6 to 20 or 6 to 15, further 6 to 12 carbon atoms (for example, halogen, alkyl or the like substituted heteroaromatic ring).
Further, the organic luminescent material based on the anthracene group is one of the following structures:
wherein R of a particular compound herein is H.
Further, the aryl or substituted aryl of 6 to 30 carbon atoms selected from R is: phenyl, naphthyl, pyrenyl, aralkyl, aralkenyl, fluorenyl;
the aromatic heterocycle or substituted aromatic heterocycle with 6-30 carbon atoms selected from R is: phenoxazinyl, phenothiazinyl, acridinyl, carbazolyl, aromatic amino, aromatic phosphine.
The application provides a preparation method of a compound based on a anthracene group, which comprises the following steps:
step S1, mixing the ketone compound of formula (3) with a Grignard reagent (such as methyl magnesium bromide) under the protection of inert atmosphere such as nitrogen, adding a solvent (preferably an aprotic polar solvent, such as 5-10 molar equivalents of tetrahydrofuran and toluene, in a volume ratio of about 5:1-10:1), refluxing the mixture, cooling the mixture, extracting the mixture (such as ethyl acetate and saturated ammonium chloride aqueous solution (in a volume ratio of about 5:1-10:1) for three times), concentrating the organic layer, and spin-drying the organic layer to obtain a crude product, and dehydrating the crude product (such as 30 min) under acidic conditions (such as pH 2-6.5) to obtain an intermediate I.
Wherein R is as defined above;
step S2, dissolving the intermediate I and N-bromosuccinimide (NBS) obtained in the step S1 in a solvent (such as chloroform or glacial acetic acid (about 10-15M)), refluxing (such as refluxing at 70 ℃ for 3-6 hours, preferably about 4 hours), cooling, extracting (such as extracting three times with ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio is 5:1-10:1), concentrating the organic layer, spin-drying the solvent, and passing through a column to obtain an intermediate II.
Step S3, mixing the intermediate II, catalyst, phosphine ligand (catalyst is selected from one of bis triphenylphosphine palladium dichloride, palladium acetate, palladium chloride and tetra triphenylphosphine palladium), preferably mono phosphine ligand (such as tri (4-methoxyphenyl) phosphine, tricyclohexylphosphine, etc.), wherein the molar ratio of the intermediate II, palladium catalyst and phosphine ligand is 1-2:0.01-0.05:0.02-0.10), alkali (alkali carbonate such as sodium carbonate, potassium carbonate, cesium carbonate, etc., 1-4 equivalent, relative to the intermediate II) and organic solvent (such as toluene, one or more of ethers), refluxing, cooling, extracting (such as three times with ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio of 5:1-10:1, for example), concentrating the organic layer, spin drying the solvent, passing through a column to obtain the compound of the target product formula (1 a) (or intermediate III or R therein) 1 、R 2 A compound of formula (1) both of which are hydrogen.
Optional step S4.1, the compound of formula (1 a) (intermediate III) obtained in step S3 is reacted with a bromide, e.g.NBS, bromobenzene, R 1 Br、R 2 Br (wherein R 1 、R 2 As defined above) and the like in a molar ratio of 1:1.5 to 1:3 in a solvent such as a polar solvent such as chloroform or glacial acetic acid, refluxing (e.g., reflux at 70 ℃ for 3 to 6 hours, preferably about 4 hours), cooling, extracting (e.g., three times with ethyl acetate and saturated aqueous ammonium chloride (e.g., in a volume ratio of 5:1 to 10:1)), concentrating the organic layer, spin-drying the solvent, and passing through a column to obtain wherein R is 1 、R 2 At least one substituted (non-hydrogen) target product of formula (1) comprising R 1 And R is 2 A compound of formula (1) which is bromine or benzene.
Alternatively, optionally S4.2. The compound of formula (1 a) is combined with palladium tetraphenylphosphine, zn (CN) 2 In a molar ratio of 1:0.01 to 0.2:1 to 5, preferably 1:0.05:3 in aprotic polar solvent such as DMF, at 100-120deg.C, preferably about 110deg.C for 6-24h, preferably about 12h, cooling the reaction solution after complete reaction, extracting (for example, three times with ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio of 5:1-10:1)), mixing the extracted organic phases, drying, concentrating the organic phase under reduced pressure to obtain crude product, purifying by silica gel column chromatography to obtain R therein 1 And R is 2 A compound of formula (1) both cyano;
alternatively, optionally S4.3. R obtained from S4.1 1 And R is 2 The compound of formula (1) being bromine is dissolved with N-BuLi in a molar ratio of 1:1.5-3, preferably 1:2.2 equivalents in an aprotic polar solvent such as tetrahydrofuran, 1-3 h, preferably 2h later, 2-4 equivalents, preferably 3 equivalents of N, N-dimethylformamide are added, the reaction is carried out for 1-3 h, preferably 2h at-80 to-85 ℃ preferably-78 ℃, after the complete reaction, the reaction solution is cooled, the post-treatment (the post-treatment is preferably extraction, drying, re-concentration, and finally concentration of the organic phase under reduced pressure, more preferably extraction with ethyl acetate and/or saturated ammonium chloride aqueous solution for three times, the organic phases obtained by extraction are combined, then drying with anhydrous sodium sulfate, finally concentration of the organic phase under reduced pressure, column chromatography purification) is carried out, and R is obtained 1 And R is 2 A compound represented by the formula (1) which is CHO (formyl).
The preparation method of the compound shown in the formula (2) further comprises the following steps:
step S5, the compound of formula (1 a) (or intermediate III) obtained in step S3 is mixed with an alkyllithium reagent such as n-BuLi in a molar ratio of 1: 2-1:4 equivalents are dissolved in an aprotic solvent such as toluene, then alkyne bromine is added, for example after 0.3-1h, preferably after about 0.5h 1.2-4 equivalents, further 1.5-2.5 equivalents, preferably 2.2 equivalents alkyne bromine, the spot plate is detected to be completely reacted with intermediate III, cooling is carried out, extraction (for example, extraction is carried out three times with ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio is for example 5:1-10:1)) and the organic layer is concentrated, the solvent is dried by spin-drying and column passing is carried out to obtain intermediate IV;
step S6, dissolving the intermediate IV prepared in the step S5 and ferric trichloride in an aprotic polar solvent such as dichloromethane according to a molar ratio of 1:2-1:10 (preferably 1:2), then adding 0.2-0.5 (preferably 0.2) equivalent of nitromethane, detecting the intermediate IV by using a dot plate until the intermediate IV is completely reacted, cooling, extracting (for example, extracting three times by using ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio is 5:1-10:1)) and concentrating an organic layer, spin-drying the solvent, and passing through a column to obtain the compound of the formula (2).
Preferably, the molar ratio of ketone compound to grignard reagent in step S1 is 1:1 to 1:3, preferably 1:2.
Preferably, the molar ratio of intermediate I to NBS in step S2 is 1:1-1:3, preferably 1:2, and the reaction solvent is one of chloroform or glacial acetic acid, preferably glacial acetic acid.
Preferably, the catalyst in step S3 is a palladium catalyst, preferably selected from one of bis (triphenylphosphine) palladium dichloride, palladium acetate, palladium chloride, and tetra (triphenylphosphine) palladium, and the base is preferably a carbonate such as sodium carbonate, potassium carbonate, cesium carbonate, etc., and the ligand is preferably selected from phosphine ligands (e.g. tris (4-methoxyphenyl) phosphine, tricyclohexylphosphine). Wherein, the mole ratio of the intermediate II, the carbonate, the palladium catalyst and the phosphine ligand can be 1-2: 1 to 4:0.01 to 0.05:0.02 to 0.10, preferably 1.2 to 1.6:1.5 to 3:0.02 to 0.04:0.04 to 0.08, and the reaction solvent may be one of aprotic solvents such as toluene or ether.
Preferably, the cooling, extraction, concentration involved in steps S1, S2 and S3 are in particular: and cooling the reacted solution to room temperature, extracting the obtained mixed solution with ethyl acetate and saturated ammonium chloride aqueous solution (volume ratio of 5:1-10:1) for three times, combining organic phases obtained by the three extractions, drying with anhydrous sodium sulfate, concentrating the organic phases under reduced pressure to obtain a crude product, and finally performing silica gel column chromatography on ethyl acetate and petroleum ether serving as eluent (the volume ratio of petroleum ether to ethyl acetate in the eluent is 100:1-10:1) to separate the organic luminescent material of the target compound based on the heteroanthracene group.
The application further provides an organic luminescent material which is prepared from the compound based on the anthracene group, has aggregation-induced luminescence property, can form different single crystal solid stacking modes by different solvent systems, and can generate obvious fluorescence change under the stimulation of heat, force and the like. The solid state fluorescence quantum yield of the organic luminescent material can reach more than 43 percent and even 82 percent.
The application further provides application of the organic luminescent material based on the anthracene group in the optical field, in particular in the fields of electroluminescent devices, anti-counterfeiting marks, encryption and the like.
In the present application, "optional" means the presence or absence of a subsequent step or substance.
Compared with the prior art, the application has the beneficial effects that:
the application provides a multi-stimulus response organic luminescent material based on a anthracene group. The luminescent characteristics of the material under different external stimuli are as follows: by adjusting different solvent systems of the material, polymorphic forms depending on different conformations can be formed in a single molecule, and the different polymorphic forms can realize triboluminescence, mechanochromism and thermochromism, thereby realizing three-dimensional response of the three properties. The material has simple synthesis method and good luminous performance, and can be applied to the fields of electroluminescent devices, stress sensing, anti-counterfeiting marks, encryption and the like.
Drawings
FIG. 1 is a fluorescence spectrum of aggregation-induced emission of the compound (c 1) of the present application (acetonitrile was selected as a good solvent (molar concentration of the compound c 1: 5X 10) -5 M) taking water as a poor solvent, preparing acetonitrile solutions of the compound with different water contents, and performing fluorescence spectrum test to prove that the compound has aggregation-induced emission property;
FIG. 2 is a confocal microscopic image of compound (c 1) of the application in acetonitrile and water in different proportions (the inset is an SEM image, wherein percentages indicate the concentration of water in acetonitrile in water; floccules produced in solutions of different water contents in FIG. 1 are filtered with filter paper and then photographed directly;
FIG. 3 is a graph showing the fluorescence of crystals of the compounds (a 1), (c 1) and (g 1) of the present application, which have fluorescence quantum yields of 43%,82% and 65%, respectively (leftmost example a1, middle example c1, rightmost example g 1);
FIG. 4 is a mechanical force (mortar-grinding) fluorescence-induced color change chart of the compound (c 1) of the present application (mortar-grinding for a while, then observation with an ultraviolet lamp at 365nm, photographing, showing that the compound has a mechanochromic fluorescence property);
FIG. 5 is a thermal (melting point apparatus heating) fluorogenic color-change plot of the compounds (a 1), (c 1) and (g 1) of the present application (indicating that the compounds have mechanochromatic fluorescent properties, with example a1 on the far left, example c1 in the middle, and example g1 on the far right;
FIG. 6 is a triboluminescence graph (mortar-polished) of the compound (c 1) of the application (showing that the compound has triboluminescence properties);
FIG. 7 is a "letter fluorescence variable image" and a thermal image fluorescence image of the compound (c 1) of the present application (first, a simple "color-changing letter" device was made by placing black paper on a glass slide, and three polymorphs of c1 were dispersed in the blank area of the paper sheet surface, respectively. When force was applied to different letters, the change as shown in FIG. 7 (a) could be observed;
FIG. 8 is a solid fluorescence spectrum of the compound (a 6) of the present application.
Detailed Description
In order to more clearly and completely describe the technical scheme of the application, the application is further described in detail through specific examples.
The medicine used in the application is purchased from An Naiji, enoKai and pichia platforms, and is directly used without further purification (purity is more than 97 percent); solvents were purchased by the exploration platform.
By Bruker Avance III-400 nuclear magnetic resonance 1 H NMR 13 C NMR test, deuterated chloroform (CDCl) 3 ) Is a solvent; high resolution mass spectrometry data were measured using a Bruker Daltonics MicroTof-Q II type mass spectrometer ESI ionization source; fluorescence spectra were measured using a iri F-4500 (fig. 1,3,8 were taken directly with the instrument; fig. 6 was prepared by placing a sample in the instrument, shielding the light source with a black cardboard, grinding with a spatula, and taking a quick photograph; fluorescence quantum yield (phi) F ) The absolute fluorescence quantum yield of the compound is the FLS920, and the instrument model is tested by an integrating sphere system; confocal imaging uses a Nikon laser scanning confocal microscope; scanning electron microscopy a scanning electron microscope of the SU 3500 type (first fixing the sample on a stage with black conductive glue, metal spraying treatment, scanning taking pictures) was used.
Example 1
Synthesis of xanthene compound (a 1):
synthesis of 9-methylene-9H-azaanthracene: mixing acridone compound with Grignard reagent methyl magnesium bromide (molar ratio 1:2) under the protection of nitrogen, then adding a mixed solvent of tetrahydrofuran and toluene (volume ratio of the two is about 6:1) with 6 molar equivalents, refluxing, cooling, extracting with ethyl acetate and saturated ammonium chloride aqueous solution three times, concentrating an organic layer, spin-drying the solvent, and passing through a silica gel column, and dehydrating the obtained crude product under an acidic condition (pH 4) for 30min to obtain an intermediate I.
Synthesis of 9-bromomethyl-9H-azaanthracene: intermediate i and N-bromosuccinimide (NBS) (molar ratio 1:2) were dissolved in chloroform (concentration of intermediate i in solvent about 10M), refluxed for 4h at 70 ℃, cooled, extracted three times with ethyl acetate and saturated aqueous ammonium chloride, the organic layer was concentrated, the solvent was dried by spin-drying, and passed through a silica gel column (eluent PE: ea=50:1) to give intermediate ii.
Synthesis of compound a 1: under the protection of nitrogen, 9-bromomethyl-9H-azaanthracene: palladium chloride: tris (4-methoxyphenyl) phosphine in a molar ratio of 1:0.03:0.06, into a previously baked sealed tube, anhydrous anaerobic THF was injected, and then 2 equivalents of cesium carbonate dried were added thereto, and reacted at 100℃overnight. After complete reaction, the reaction solution was cooled, extracted three times with ethyl acetate and saturated aqueous ammonium chloride, the organic layer was concentrated, the solvent was spin-dried, and passed through a silica gel column with an eluent ratio of PE: ea=50:1 to give compound a1 in 77% yield. 1 H NMR(400MHz,CDCl 3 )δ9.23(s,2H),7.70–7.66(m,4H),7.20–7.17(m,6H),6.95–6.92(m,4H),6.90–6.87(m,2H),6.78(s,2H). 13 C NMR(101MHz,CDCl 3 )δ139.6,139.5,136.2,131.5,128.9,125.3,124.8,124.4,123.8,123.0,122.9,122.5,116.7,116.2.HRMS(ESI)m/z C 28 H 21 N 2 [M+H] + Calculated 385.1699, found 385.1711.
The synthetic route is as follows:
the crystal fluorescence diagram of the synthetic xanthene compound (a 1) is shown in fig. 3.
Example 2
Synthesis of xanthene compound (b 1):
as in example 1, 9-bromomethyl-9H-xanthene was used instead of 9-bromomethyl-9H-azaxanthene to obtain compound b1 in about 82% yield. 1 H NMR(400MHz,CDCl 3 )(d,J＝7.8Hz,2H),7.68(d,J＝7.9Hz,2H),7.42(t,J＝7.6Hz,2H),7.32(d,J＝7.8Hz,2H),7.27(d,J＝8.3Hz,3H),7.23(d,J＝7.4Hz,3H),7.20–7.14(m,4H). 13 C NMR(101MHz,CDCl 3 )δ152.6,151.4,129.2,128.6,128.5,128.0,125.1,123.9,123.1,123.0,122.8,120.7,116.8,116.8.HRMS(ESI)m/z C 28 H 19 O 2 [M+H] + Calculated 387.1307, found 387.1319. The synthetic route is as follows:
example 3
Synthesis of xanthene compound (c 1):
as in example 1, 9-bromomethyl-9H-azaanthracene was replaced with 9-bromomethyl-9H-thianthrene to obtain a compound c1 in about 89% yield. 1 H NMR(400MHz,CDCl 3 )δ7.83(dd,J＝7.7,1.4Hz,2H),7.56(dd,J＝7.7,1.5Hz,2H),7.52(dd,J＝7.8,1.4Hz,2H),7.47–7.38(m,4H),7.37–7.31(m,2H),7.31–7.27(m,2H),7.23(td,J＝7.5,1.5Hz,2H),7.07(s,2H). 13 C NMR(101MHz,CDCl 3 )δ137.9,137.6,133.7,133.5,131.8,129.8,127.7,127.0,127.0,126.9,126.7,126.0,125.9,125.3.HRMS(ESI)m/z C 28 H 19 S 2 [M+H] + Calculated 420.0923, found 420.0932.
The synthetic route is as follows:
the fluorescence spectrum of the aggregation-induced emission of the synthetic xanthene compound (c 1) is shown in fig. 1, the confocal microscopic imaging in acetonitrile and water at different ratios is shown in fig. 2, the crystal fluorescence is shown in fig. 3, the mechanical force (mortar-ground) electrochromic is shown in fig. 4, the thermal (melting point apparatus heating) electrochromic is shown in fig. 5, the friction (mortar-ground) emission is shown in fig. 6, and the "alphabetical fluorescence variable imaging" and thermal imaging fluorescence are shown in fig. 7.
Example 4
Synthesis of xanthene compound (d 1):
as in example 1, 9-bromomethyl-9H-azaanthracene was replaced with 9-bromomethyl-9H-phosphaanthracene to give compound d1 in about 71% yield. 1 H NMR(400MHz,CDCl 3 )δ7.73(td,J＝7.0,1.3Hz,8H),7.66–7.54(m,10H),7.50–7.45(m,8H),6.75(s,2H). 13 C NMR(101MHz,CDCl 3 )δ135.4,133.5,132.7,132.2,131.9,131.3,131.2,130.6,130.5,128.9,128.5,124.6.HRMS(ESI)m/z C 40 H 29 O 2 P 2 [M+H] + Calculated 603.1565, found 603.1557.
The synthetic route is as follows:
example 5
Synthesis of xanthene compound (e 1):
as in example 1, 9-bromomethyl-9H-silaxanthene was used instead of 9-bromomethyl-9H-azaxanthene to give compound e1 in about 80% yield. 1 H NMR(400MHz,CDCl 3 )δ7.61–7.51(m,4H),7.43–7.30(m,12H),6.72(s,2H),0.83(s,12H). 13 C NMR(101MHz,CDCl 3 )δ141.2,141.1,141.0,141.0,135.8,134.5,134.5,134.4,132.9,132.8,132.2,129.3,127.1,123.5,123.4,121.8.HRMS(ESI)m/z C 32 H 31 Si 2 [M+H] + Calculated 471.1986, found 471.1990.
The synthetic route is as follows:
example 6
Synthesis of xanthene compound (f 1):
as in example 1, 9-bromomethyl-9H-azaanthracene was replaced with 9-bromomethyl-9H-azaanthracene to obtain a compound f1 in about 75% yield. 1 H NMR(400MHz,CDCl 3 )δ7.87(dd,J＝7.0,1.3Hz,4H),7.75–7.69(m,4H),7.41–7.32(m,8H),7.28–7.16(m,8H),7.13(ddt,J＝8.4,6.6,1.5Hz,2H),6.72(s,2H). 13 C NMR(101MHz,CDCl 3 )δ141.4,140.4,140.0,139.8,138.4,137.8,137.3,135.3,131.3,131.1,129.1,128.4,125.9.HRMS(ESI)m/z C 40 H 29 B 2 [M+H] + Calculated 531.2377, found 531.2386.
The synthetic route is as follows:
example 7
Synthesis of xanthene compound (g 1):
as in example 1, 9-bromomethyl-9H-dibenzocycloheptene was used instead of 9-bromomethyl-9H-azaanthracene to obtain compound g1 in about 81% yield. 1 H NMR(400MHz,CDCl 3 )δ7.61(dd,J＝7.9,1.6Hz,4H),7.57(dd,J＝8.0,1.6Hz,4H),7.42(td,J＝7.8,1.5Hz,8H),7.36(td,J＝7.9,1.7Hz,4H),6.87(s,2H). 13 C NMR(101MHz,CDCl 3 )δ142.2,142.1,139.4,139.4,139.2,139.1,138.0,137.9,132.2,129.7,129.3,128.1,127.2.HRMS(ESI)m/z C 32 H 23 [M+H] + Calculated 406.1722, found 406.1730.
The synthetic route is as follows:
g1
the crystal fluorescence diagram of the synthetic xanthene compound (g 1) is shown in fig. 3.
Example 8
Synthesis of xanthene compound (a 2):
compound a1 and NBS are mixed in mole ratioThe ratio is 1:2, adding the mixture into a reaction bottle, adding chloroform, carrying out reflux reaction for 4 hours, cooling the reaction liquid after complete reaction, extracting the reaction liquid with ethyl acetate and saturated ammonium chloride aqueous solution for three times, concentrating an organic layer, spin-drying a solvent, passing through a silica gel column, and eluting with the ratio of PE: EA=50:1 to obtain the compound a2 with the yield of 75%. 1 H NMR(400MHz,CDCl 3 )δ9.01(s,2H),7.74–7.66(m,4H),7.19(dd,J＝5.8,3.5Hz,8H),6.95(dd,J＝5.8,3.4Hz,2H),6.91(dd,J＝5.8,3.4Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ140.5,140.3,128.9,128.6,123.7,123.4,123.4,123.1,123.0,122.4,121.8,121.2,115.6,115.3.HRMS(ESI)m/zC 28 H 19 Br 2 N 2 [M+H] + Calculated 540.9890, found 540.9899.
The synthetic route is as follows:
example 9
Synthesis of xanthene compound (c 2):
as in example 8, c1 was used instead of a1, to obtain compound c2 in about 79% yield. 1 H NMR(400MHz,CDCl 3 )δ7.77–7.71(m,6H),7.57–7.51(m,4H),7.54–7.47(m,4H),7.46–7.38(m,2H). 13 C NMR(101MHz,CDCl 3 )δ133.2,132.3,131.3,130.4,129.8,129.0,128.3,128.2,126.8,126.7,126.6,126.5,125.9.HRMS(ESI)m/z C 28 H 17 Br 2 S 2 [M+H] + Calculated 574.9113, found 574.9121.
The synthetic route is as follows:
example 10
Synthesis of xanthene compound (e 2):
as in example 8, substituting e1 for a1, compound e2 was obtained in about 68% yield. 1 H NMR(400MHz,CDCl 3 )δ7.61–7.52(m,4H),7.44–7.41(m,4H),7.41–7.36(m,6H),7.36–7.30(m,2H),0.83(s,12H). 13 C NMR(101MHz,CDCl 3 )δ139.2,139.2,138.2,138.1,132.9,132.8,132.8,132.8,129.2,128.7,128.7,127.3,124.8,124.7.HRMS(ESI)m/z C 32 H 29 Br 2 Si 2 [M+H] + Calculated 627.0096, found 627.0104.
The synthetic route is as follows:
example 11
Synthesis of xanthene compound (g 2):
as in example 8, substituting g1 for a1, compound g2 was obtained in about 63% yield. 1 H NMR(400MHz,CDCl 3 )δ7.64(td,J＝7.8,1.5Hz,8H),7.49–7.41(m,8H),7.36(td,J＝8.0,1.6Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ135.8,133.0,132.3,131.7,131.7,131.3,129.3,128.7,127.9,127.7.HRMS(ESI)m/zC 32 H 21 Br 2 [M+H] + Calculated 563.9985, found 563.9990.
The synthetic route is as follows:
example 12
Synthesis of xanthene compound (a 3):
combining compound a1 with tetrakis (triphenylphosphine) palladium, zn (CN) 2 The molar ratio is 1:0.05:3 in DMF at 110 deg.c for 12 hr, cooling the reaction liquid, extracting with ethyl acetate and saturated ammonium chloride solution three times, concentrating the organic layer, spin drying the solvent, and silica gel column with eluent in the ratio of PE: EA=10: 1, compound a3 was obtained in 62% yield. 1 H NMR(400MHz,CDCl 3 )δ9.18(s,2H),7.76(ddd,J＝7.6,3.7,2.1Hz,4H),7.26–7.16(m,8H),6.93(ddd,J＝24.8,7.4,1.9Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ140.2,138.7,138.5,128.8,124.8,124.6,124.6,124.5,124.5,124.4,122.0,121.6,117.2,115.5,115.3.HRMS(ESI)m/z C 30 H 19 N 4 [M+H] + Calculated 435.1531, found 435.1540.
The synthetic route is as follows:
example 13
Synthesis of xanthene compound (c 3):
as in example 12, c1 was used instead of a1, to give compound c3 in about 71% yield. 1 H NMR(400MHz,CDCl 3 )δ8.04(dd,J＝7.3,1.5Hz,2H),7.56–7.49(m,10H),7.49–7.41(m,4H). 13 C NMR(101MHz,CDCl 3 )δ151.9,131.1,131.0,130.9,130.8,130.7,128.4,127.5,127.4,126.5,126.4,126.1,117.2,106.4.HRMS(ESI)m/z C 30 H 17 N 2 S 2 [M+H] + Calculated 469.0755, found 469.0763.
The synthetic route is as follows:
example 14
Synthesis of xanthene compound (e 3):
as in example 12, substituting e1 for a1, compound e3 was obtained in about 64% yield. 1 H NMR(400MHz,CDCl 3 )δ7.60(m,4H),7.46–7.43(m,4H),7.40–7.36(m,6H),7.33–7.30(m,2H),1.05-0.95(s,12H). 13 C NMR(101MHz,CDCl 3 )δ147.5,141.3,141.3,141.1,141.1,132.9,132.9,129.7,129.7,129.3,127.2,125.8,125.6,117.3,100.4.HRMS(ESI)m/z C 30 H 29 N 2 Si 2 [M+H] + Calculated 520.1791, found 520.1791.
The synthetic route is as follows:
example 15
Synthesis of xanthene compound (g 3):
as in example 12, substituting g1 for a1 gave compound g3 in about 70% yield. 1 H NMR(400MHz,CDCl 3 )δ7.77(dd,J＝8.0,1.6Hz,4H),7.66(dd,J＝8.0,1.4Hz,4H),7.50–7.43(m,8H),7.36(td,J＝7.8,1.5Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ156.0,135.4,135.2,134.4,131.1,130.3,129.3,127.9,127.8,121.7,117.2.HRMS(ESI)m/z C 34 H 21 N 2 [M+H] + Calculated 457.1626, found 457.1634.
The synthetic route is as follows:
example 16
Synthesis of xanthene compound (a 4):
compound a2 and n-BuLi were combined in a molar ratio of 1:2.5 equivalents are dissolved in tetrahydrofuran, 3 equivalents of N, N-dimethylformamide are added after 2 hours, the reaction is carried out for 2 hours at the temperature of minus 78 ℃, after the complete reaction, the reaction liquid is cooled, the ethyl acetate and saturated ammonium chloride aqueous solution are used for extraction for three times, the organic layer is concentrated, the solvent is dried by spin, and the solvent is filtered through a silica gel column, wherein the eluent ratio is PE, wherein the ratio of EA=10: 1, compound a4 was obtained in 49% yield. 1 H NMR(400MHz,CDCl 3 )δ8.95(s,2H),7.87–7.77(m,4H),7.31–7.23(m,8H),7.06–6.99(m,4H),6.99–6.96(m,2H). 13 C NMR(101MHz,CDCl 3 )δ191.7,151.2,140.5,140.2,140.0,128.8,125.9,125.9,125.3,125.2,123.5,123.4,121.7,115.5,115.2.HRMS(ESI)m/zC 30 H 21 N 2 O 2 [M+H] + Calculated 441.1525, found 441.1534.
The synthetic route is as follows:
example 17
Synthesis of xanthene compound (c 4):
as in example 16, c2 was used instead of a2, to give compound c4 in about 53% yield. 1 H NMR(400MHz,CDCl 3 )δ7.66–7.58(m,4H),7.57(d,2H),7.57–7.55(d,4H),7.5–7.52(m,6H),7.47(td,2H). 13 C NMR(101MHz,CDCl 3 )δ191.4,153.0,149.0,132.8,132.7,132.0,131.7,131.5,131.1,128.3,126.7,126.5,125.8.HRMS(ESI)m/z C 30 H 19 O 2 S 2 [M+H] + Calculated 475.0748, found 475.0759.
The synthetic route is as follows:
example 18
Synthesis of xanthene compound (e 4):
as in example 16, substituting e2 for a2, compound e4 was obtained in about 45% yield. 1 H NMR(400MHz,CDCl 3 )δ7.60(ddd,J＝11.8,8.5,1.5Hz,4H),7.54–7.42(m,8H),7.40–7.36(m,4H),7.34–7.30(m,2H),0.90(s,12H). 13 C NMR(101MHz,CDCl 3 )δ147.5,141.3,141.3,141.1,141.1,132.9,132.9,129.7,129.7,129.3,127.2,125.8,125.6,117.3,100.4.HRMS(ESI)m/z C 34 H 31 O 2 Si 2 [M+H] + Calculated 527.1784, found 527.1784.
The synthetic route is as follows:
example 19
Synthesis of xanthene compound (g 4):
as in example 16, f2 was used instead of a2, to obtain compound g4 in a yield of about 41%. 1 H NMR(400MHz,CDCl 3 )δ7.69(dd,J＝7.9,1.4Hz,4H),7.63(dd,J＝8.0,1.6Hz,6H),7.53(td,J＝7.9,1.4Hz,4H),7.47(s,4H),7.44(td,J＝7.8,1.5Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ192.6,163.6,147.7,136.3,136.1,135.6,131.4,129.3,128.4,127.7,127.6.HRMS(ESI)m/z C 34 H 23 O 2 [M+H] + Calculated 463.1620, found 463.1634.
The synthetic route is as follows:
example 20
Synthesis of xanthene compound (a 5):
compound a1 and benzyl bromide were combined in a molar ratio of 1:2.2, adding chloroform into a reaction bottle, carrying out reflux reaction for 4 hours, cooling the reaction liquid after complete reaction, extracting with ethyl acetate and saturated ammonium chloride aqueous solution for three times, concentrating an organic layer, spin-drying a solvent, passing through a silica gel column, and eluting with PE (polyethylene) with EA=50:1 to obtain a compound a5 with the yield of 73%. 1 H NMR(400MHz,CDCl 3 )δ8.88(s,2H),7.67(ddd,J＝8.9,7.8,1.8Hz,4H),7.53–7.38(m,10H),7.26–7.15(m,8H),6.97(ddd,J＝23.7,7.6,1.6Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ139.6,139.4,137.7,137.0,132.1,128.8,128.5,128.3,127.2,125.4,125.4,125.3,125.3,124.6,124.5,121.7,115.6,115.3.HRMS(ESI)m/z C 40 H 29 N 2 [M+H] + Calculated 537.2252, found 537.2257.
The synthetic route is as follows:
example 21
Synthesis of xanthene compound (c 5):
as in example 20, c1 was used instead of a1, to obtain compound c5 in about 83% yield. 1 H NMR(400MHz,CDCl 3 )δ7.76(ddd,J＝9.1,7.3,1.7Hz,4H),7.58–7.52(m,4H),7.52–7.47(m,8H),7.40–7.32(m,6H),7.22–7.20(m,4H). 13 C NMR(101MHz,CDCl 3 )δ150.8,138.1,137.5,132.0,131.9,131.0,130.9,130.8,130.8,128.5,128.3,127.2,126.7,126.6,126.3,126.2,126.0.HRMS(ESI)m/z C 40 H 27 S 2 [M+H] + Calculated 570.1476, found 570.1485.
The synthetic route is as follows:
example 22
Synthesis of xanthene compound (e 5):
as in example 20, substituting e1 for a1, compound e5 was obtained in about 86% yield. 1 H NMR(400MHz,CDCl 3 )δ7.64–7.55(m,4H),7.51–7.45(m,4H),7.45–7.41(m,14H),7.41–7.33(m,4H),0.82(s,12H). 13 C NMR(101MHz,CDCl 3 )δ146.0,141.5,141.5,141.2,141.1,138.2,136.7,132.7,132.6,130.6,130.4,129.1,128.5,128.4,127.2,127.2,124.3.HRMS(ESI)m/z C 40 H 39 Si 2 [M+H] + Calculated 622.1512, found 622.1512.
The synthetic route is as follows:
example 23
Synthesis of xanthene compound (g 5):
as in example 20, substituting g1 for a1 gave compound g5 in about 84% yield. 1 H NMR(400MHz,CDCl 3 )δ7.66–7.61(m,4H),7.53–7.47(m,12H),7.46–7.38(m,10H),7.35(ddd,J＝7.9,6.2,3.0Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ146.6,145.0,137.7,137.7,136.8,134.6,131.3,129.3,128.5,128.3,128.3,128.2,127.9,127.9,127.2.HRMS(ESI)m/z C 44 H 31 [M+H] + Calculated 559.2348, found 559.2352.
The synthetic route is as follows:
example 24
Synthesizing an intermediate IV:
the molar ratio of the compound a1 to n-BuLi is 1:2.2 equivalents of the organic layer are dissolved in toluene, 2.2 equivalents of acetylene bromide are added after 2 hours, ethyl acetate and saturated ammonium chloride aqueous solution are used for extraction for three times after complete reaction, the organic layer is concentrated, the solvent is dried by spin, the solvent is passed through a silica gel column, the eluent proportion is PE: EA=50:1, and the nitrogenous intermediate IV is obtained, and the yield is 62%. 1 H NMR(400MHz,CDCl 3 )δδ9.18(s,2H),7.75(ddd,J＝7.6,3.1,2.0Hz,4H),7.34–7.14(m,8H),6.93(ddd,J＝24.8,7.4,1.9Hz,4H),3.46(s,2H). 13 C NMR(101MHz,CDCl 3 )δ138.9,138.7,128.8,126.1,125.1,122.5,122.0,115.8,115.4,87.5,77.3.HRMS(ESI)m/z C 32 H 21 N 2 [M+H] + Calculated 433.1626, found 433.1633.
The synthetic route is as follows:
example 25
Synthesis of xanthene compound (a 6):
the molar ratio of the nitrogen-containing intermediate IV to the ferric trichloride is 1:2 equivalents were dissolved in dichloromethane, followed by addition of 0.2 equivalents of nitromethane, after complete reaction, extraction with ethyl acetate and saturated aqueous ammonium chloride solution three times, concentration of the organic layer, spin-drying of the solvent, passage through a silica gel column, eluent ratio PE: ea=100:1, gave compound a6 in 73% yield. 1 H NMR(400MHz,CDCl 3 )δ9.58(s,2H),9.14(d,J＝2.6Hz,2H),8.32–8.27(m,2H),7.79(ddd,J＝7.5,2.2,1.2Hz,2H),7.53(t,J＝7.6Hz,2H),7.45(t,J＝7.7Hz,2H),6.98(dd,J＝7.8,1.2Hz,2H),6.93(dd,J＝7.8,1.2Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ137.9,137.8,133.9,129.8,129.7,129.5,128.7,128.3,125.4,122.7,121.3,120.7,120.2,115.1,114.5,114.3,113.9,113.3.HRMS(ESI)m/z C 32 H 17 N 2 [M+H] + A value 429 is calculated.1313, found 429.1324.
The synthetic route is as follows:
the solid fluorescence spectrum of the synthetic xanthene compound (a 6) is shown in fig. 8.
Example 26
Synthesis of xanthene compound (c 6):
as in example 25, the nitrogen-containing intermediate IV was replaced with the sulfur-containing intermediate IV to give compound c6 in about 79% yield. 1 H NMR(400MHz,CDCl 3 )δ9.16(d,J＝2.2Hz,2H),8.43–8.37(m,2H),7.98(ddd,J＝7.5,2.2,1.2Hz,2H),7.89(dd,J＝7.0,1.1Hz,2H),7.62(dd,J＝7.6,6.9Hz,2H),7.56(dd,J＝7.6,6.9Hz,2H),7.41(dd,J＝6.8,1.1Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ131.1,130.5,129.3,128.3,127.9,127.7,127.3,125.9,125.3,124.8,123.4,122.9.HRMS(ESI)m/z C 32 H 15 S 2 [M+H] + Calculated 462.0537, found 462.0548.
The synthetic route is as follows:
example 27
Synthesis of xanthene compound (e 6):
as in example 25, silicon-containing intermediate IV was used in place of nitrogen-containing intermediate IV to give compound e6 in about 73% yield. 1 H NMR(400MHz,CDCl 3 )δ9.19(d,J＝2.1Hz,2H),8.60(dd,J＝6.5,2.3Hz,2H),8.13(ddd,J＝7.7,2.4,1.3Hz,2H),7.78–7.69(m,6H),7.64–7.57(m,2H),0.81(s,12H). 13 C NMR(101MHz,CDCl 3 )δ132.4,132.3,132.2,132.0,131.4,131.2,130.9,130.8,130.4,129.2,128.0,128.0,127.9,127.5,125.0,124.4,124.4,120.7.HRMS(ESI)m/z C 36 H 27 Si 2 [M+H] + Calculated 515.1573, found 515.1580.
The synthetic route is as follows:
example 28
Synthesis of xanthene compound (g 6):
as in example 25, silicon-containing intermediate IV was used in place of nitrogen-containing intermediate IV to give compound g6 in about 73% yield. 1 H NMR(400MHz,CDCl 3 )δ9.18(d,2H),8.22–8.17(m,2H),8.17–8.11(m,2H),7.70(dd,J＝7.5,2.9Hz,4H),7.62–7.53(m,6H),7.53–7.47(m,2H). 13 C NMR(101MHz,CDCl 3 )δ135.9,135.3,133.3,132.3,132.0,131.5,130.9,130.1,128.1,127.8,127.1,126.6,126.4,126.2,125.3,120.5.HRMS(ESI)m/z C 36 H 19 [M+H] + Calculated 451.1409, found 451.1421.
The synthetic route is as follows:
in summary, the present application provides a multi-stimulus response organic luminescent material based on a hybrid anthracene group. The luminescent characteristics of the material under different external stimuli are as follows: by adjusting different solvent systems of the material, polymorphic forms depending on different conformations can be formed in a single molecule, and the different polymorphic forms can realize triboluminescence, mechanochromism and thermochromism, thereby realizing three-dimensional response. The material has simple synthesis method and good luminous performance, and can be applied to the fields of electroluminescent devices, stress sensing, anti-counterfeiting marks, encryption and the like.

Claims (10)

1. A compound based on a anthracene group, the compound having a structure represented by formula (1) or (2):
in the formulas (1) and (2), X is-NH-, -O-, -S-, and a divalent group containing P (e.g., aryl-substituted phosphinyloxy such as-P (O) Ph-), silicon-containing divalent radicals (e.g. -Si (CH) 3 ) 2 (-), a divalent group containing B (e.g. -BPh-) or a c=c double bond; r is independently selected from one of hydrogen atom, halogen, cyano, aldehyde group, aryl group and heteroaryl ring group; r is R 1 、R 2 Respectively selected from one of hydrogen atom, halogen, cyano, aldehyde group and phenyl;
preferably, the method comprises the steps of, X is selected from-NH-, -O-, -S-; r is selected from one of hydrogen atom, halogen, cyano, aldehyde group, aryl group and heteroaryl ring group, preferably hydrogen atom and halogen; r is R 1 、R 2 One selected from the group consisting of a hydrogen atom, halogen, cyano, aldehyde, and phenyl, respectively, is preferably a hydrogen atom and halogen.
2. The anthracene group-based compound according to claim 1, characterized in that the anthracene group-based compound is one or more of the following structures:
wherein R in the structural formula is H.
3. The heteroanthracene group-based compound according to claim 1, characterized in that,
the aryl group selected by R is aryl or substituted aryl of 6-30 carbon atoms, preferably aryl or substituted aryl of 6-12 carbon atoms;
the heteroaromatic ring group selected by R is an aromatic heterocycle or substituted heteroaromatic ring of 6-30 carbon atoms, preferably an aromatic heterocycle or substituted aromatic heterocycle of 6-12 carbon atoms.
4. The heteroanthracene group-based compound according to claim 1, characterized in that,
the aryl or substituted aryl of 6-30 carbon atoms selected from R is: phenyl, naphthyl, pyrenyl, aralkyl, aralkenyl, fluorenyl;
the heteroaromatic ring or substituted heteroaromatic ring of 6 to 30 carbon atoms selected from R is: phenoxazinyl, phenothiazinyl, acridinyl, carbazolyl, aromatic amino, aromatic phosphine.
5. A process for the preparation of a compound based on a heteroanthracene group according to any one of claims 1 to 4, characterized in that: the preparation method of the compound shown in the formula (1) comprises the following steps:
s1, mixing a ketone compound of the following formula (3), namely a ketone substrate, with a Grignard reagent (such as methyl magnesium bromide) under the protection of inert atmosphere (such as nitrogen), then adding a solvent (such as an aprotic solvent, preferably 5-10 molar equivalents of tetrahydrofuran and toluene mixed solvent (the volume ratio of the aprotic solvent to the toluene is about 5:1-10:1)), refluxing, cooling, post-treating (such as extraction with ethyl acetate and saturated ammonium chloride water solution for three times), concentrating an organic layer, and spin-drying the organic solvent), and dehydrating the obtained crude product under an acidic condition to obtain an intermediate I;
wherein R is independently selected from one of hydrogen atom, halogen, cyano, aldehyde group, aryl and heteroaryl ring group;
s2, dissolving the intermediate I and a bromide (such as N-bromosuccinimide (NBS)) prepared in the step S1 in a solvent (such as a polar solvent, preferably chloroform or glacial acetic acid (the concentration of the intermediate I in the solvent is about 10-15M), refluxing (such as refluxing at 70 ℃ for 4 hours), cooling, post-treating (such as extraction with ethyl acetate and saturated ammonium chloride water solution for three times), concentrating an organic layer, spin-drying the solvent, and passing through a column) to obtain an intermediate II;
s3, under the protection of nitrogen, theMixing intermediate II, catalyst, phosphine ligand, alkali (carbonate, 1-4 equivalent) and organic solvent (such as toluene or ether) prepared in step S2, refluxing, cooling, post-treating (e.g. extracting, for example, by ethyl acetate and saturated ammonium chloride aqueous solution, concentrating organic layer, spin drying solvent, passing through column) to obtain compound of target product formula (1 a), namely R 1 And R is 2 A compound of formula (1) which is hydrogen;
optionally S4.1. Dissolving the compound of formula (1 a) prepared in step S3 (i.e. intermediate III) to bromide (e.g. NBS, one or more of bromobenzene) in a molar ratio of about 1:1.5 to 1:3 equivalent in a polar solvent (e.g. chloroform or glacial acetic acid), refluxing (e.g. reflux for 4h at 70 ℃), cooling, working up (e.g. extraction (e.g. three extractions with ethyl acetate and saturated aqueous ammonium chloride), concentrating the organic layer, spin drying the solvent, passing through a column) to give R 1 And R is 2 Compounds of formula (1) which are non-hydrogen substituents, e.g. wherein R 1 And R is 2 A compound of formula (1) each independently being bromo or phenyl;
alternatively, optionally S4.2. The compound of formula (1 a) is combined with palladium tetraphenylphosphine, zn (CN) 2 Adding the mixture into aprotic polar solvent such as DMF at a molar ratio of 1:0.01-0.2:1-5, preferably 1:0.05:3, reacting at 100-120deg.C, preferably about 110deg.C for 6-24h, preferably about 12h, cooling the reaction solution after complete reaction, post-treating (for example, extracting three times with ethyl acetate and saturated ammonium chloride aqueous solution), mixing the extracted organic phases, drying, concentrating the organic phase under reduced pressure to obtain crude product, purifying by silica gel column chromatography), and obtaining R 1 And R is 2 A compound of formula (1) which is CN;
alternatively, optionally S4.3. R obtained from S4.1 1 And R is 2 The molar ratio of the compound of formula (1) to n-BuLi, which is bromine, is 1:1.5 to 3, preferably 1:2.2 equivalents are dissolved in an aprotic polar solvent such as tetrahydrofuran, and after 1 to 3 hours, preferably 2 hours, 2 to 4 equivalents, preferably 3 equivalents, of N, N-dimethylformamide are added, from-80 to-85The reaction is carried out for 1 to 3 hours, preferably 2 hours at the temperature of-78 ℃ preferably, after the complete reaction, the reaction solution is cooled, and the post-treatment (the post-treatment is preferably extraction, drying, concentration and decompression concentration of the organic phase, more preferably extraction with ethyl acetate and/or saturated ammonium chloride aqueous solution for three times, the organic phases obtained by extraction are combined, then the organic phases are dried with anhydrous sodium sulfate, decompression concentration of the organic phase and column chromatography purification) are carried out, thus obtaining the catalyst, wherein R is 1 And R is 2 Is a compound represented by the formula (1) of CHO.
6. A method for producing the compound based on a heteroanthracene group according to any one of claims 1 to 4, characterized in that the method for producing the compound represented by the formula (2) comprises the steps of:
s1, mixing a ketone compound of the following formula (3), namely a ketone substrate, with a Grignard reagent (such as methyl magnesium bromide) under the protection of inert atmosphere (such as nitrogen), then adding a solvent (such as an aprotic solvent, preferably 5-10 molar equivalents of tetrahydrofuran and toluene mixed solvent (the volume ratio of the aprotic solvent to the toluene is about 5:1-10:1)), refluxing, cooling, post-treating (such as extraction with ethyl acetate and saturated ammonium chloride water solution for three times), concentrating an organic layer, and spin-drying the organic layer), and dehydrating the obtained crude product under an acidic condition to obtain an intermediate I;
wherein R is independently selected from one of hydrogen atom, halogen, cyano, aldehyde group, aryl and heteroaryl ring group;
s2, dissolving the intermediate I and a bromide (such as N-bromosuccinimide (NBS)) prepared in the step S1 in a solvent (such as a polar solvent, preferably chloroform or glacial acetic acid (the concentration of the intermediate I in the solvent is about 10-15M), refluxing (such as refluxing at 70 ℃ for 4 hours), cooling, post-treating (such as extraction with ethyl acetate and saturated ammonium chloride water solution for three times), concentrating an organic layer, spin-drying the solvent, and passing through a column) to obtain an intermediate II;
s3, mixing the intermediate II, the catalyst, the phosphine ligand, the alkali (carbonate, 1-4 equivalent) and the organic solvent (such as toluene, ethanol and the like) which are prepared in the step S2 under the protection of nitrogen, refluxing, cooling, and post-treating (for example, extracting, for example, extracting with ethyl acetate and saturated ammonium chloride aqueous solution, concentrating the organic layer, spin-drying the solvent and passing through a column) to obtain a compound of a formula (1 a);
s5, dissolving the compound (i.e. the intermediate III) of the formula (1 a) prepared in the step S3 and an alkyl lithium reagent such as n-BuLi in a molar ratio of 1:2-1:4 in a solvent (such as an aprotic solvent such as toluene), then adding alkyne bromine (such as 1.2-3 equivalents, preferably 2.2 equivalents of alkyne bromine after 2 hours), (such as spot plate detection) until the intermediate III is completely reacted, cooling, post-treating (such as extraction three times with ethyl acetate and saturated ammonium chloride aqueous solution), concentrating an organic layer, spin drying the solvent, passing through a column) to obtain an intermediate IV;
s6, dissolving the intermediate IV prepared in the step S5 and ferric trichloride in a molar ratio of 1:2-1:10 (preferably 1:2), then adding 0.2-0.5 equivalent (preferably 0.2 equivalent) of nitromethane (for example, spot plate detection) until the intermediate IV is completely reacted, cooling, post-treating (for example, extracting with ethyl acetate and saturated ammonium chloride aqueous solution for three times), concentrating an organic layer, spin-drying a solvent and passing through a column) to obtain a target product (2);
preferably, the catalyst in the step S3 is selected from one of bis triphenylphosphine palladium dichloride, palladium acetate, palladium chloride and tetra triphenylphosphine palladium, and the ligand is preferably a monophosphine ligand, wherein the molar ratio of the intermediate II to the palladium catalyst to the phosphine ligand is 1-2: 0.01 to 0.05:0.02 to 0.10.
7. The method for preparing a compound based on a hybrid anthracene group according to claim 5 or 6, characterized in that the molar ratio of ketone compound to grignard reagent in step S1 is 1:1 to 1:3, preferably 1:2; and/or the molar ratio of the intermediate I to NBS in the step S2 is 1-3, preferably 1:2, and the reaction solvent is one of chloroform or glacial acetic acid.
8. The method for preparing the compound based on the anthracene group according to claim 5 or 6, wherein in the step S3, the catalyst is one selected from bis triphenylphosphine palladium dichloride, palladium acetate, palladium chloride and tetra triphenylphosphine palladium, and the molar ratio of the intermediate II to the carbonate to the palladium catalyst to the phosphine ligand is 1-2: 1 to 4:0.01 to 0.05: 0.02-0.10, wherein the reaction solvent is toluene or ether.
9. An organic light-emitting material prepared using the compound based on a anthracene group according to any one of claims 1 to 4 or the compound based on a anthracene group obtained by the preparation method according to any one of claims 5 to 8.
10. Use of the compound based on a heteroanthracene group according to any one of claims 1-4 in the optical field, anti-counterfeit marking, or encryption field.
CN202310799561.1A 2023-06-30 2023-06-30 Compound based on anthracene group, and preparation method and application thereof Pending CN116947758A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310799561.1A CN116947758A (en) 2023-06-30 2023-06-30 Compound based on anthracene group, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310799561.1A CN116947758A (en) 2023-06-30 2023-06-30 Compound based on anthracene group, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116947758A true CN116947758A (en) 2023-10-27

Family

ID=88461199

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310799561.1A Pending CN116947758A (en) 2023-06-30 2023-06-30 Compound based on anthracene group, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116947758A (en)

Similar Documents

Publication Publication Date Title
CN105073737B (en) Compound, luminescent material and organic illuminating element
CN110218220B (en) Functionalized metal-organic framework compound, complex formed by functionalized metal-organic framework compound, and preparation method and application of functionalized metal-organic framework compound
CN107011183B (en) Compounds and organic electronic device comprising it
CN111875602B (en) Cyano-modified pyridino-imidazole derivative and preparation method and application thereof
KR101252603B1 (en) Deep-Blue Phosphorescent Iridium(III) Complexes Utilizing N-Methylimidazolyltriazoles
Chen et al. Multifunctional behavior of a novel tetraphenylethylene derivative: Mechanochromic luminescence, detection of fluoride ions and trace water in aprotic solvents
CN102491936B (en) Conjugated compound with yellow-green fluorescence and preparation method and use thereof
TWI553003B (en) Synthesis method of the 2,6 - bis [3 '- (n- carbazolyl) phenyl] pyridine compounds
Chen et al. Binaphthanol-based organic fluorophores with color tunability and their optical properties
EP2663554B1 (en) Carbazole end capped bipyridine compounds and process for preparation thereof
CN107759504B (en) Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof
CN113387905A (en) Organic room temperature phosphorescent material, preparation method and application
CN116947758A (en) Compound based on anthracene group, and preparation method and application thereof
JP2009234915A (en) Compound or its salt, method of producing the same, aromatic azo compound, and fluorescent material
Lu et al. Dithienylethene-bridged gold (I) isocyanide complexes: Synthesis, photochromism and “turn-on” fluorescent switching behavior
CN110183476A (en) Double boron oxa- dibenzo [A, J] anthracene derivants and its application
CN103194213B (en) Aggregation-induced emission material with long alkyl chain toluylene carbazole structure, synthesizing method and application thereof
CN116262728A (en) Pure organic room temperature phosphorescent material regulated and controlled through flexible chains, and preparation method and application thereof
WO2015199141A1 (en) Coumalin-based condensed ring compound exhibiting luminescence/semiconductor properties, and method for manufacturing same
JP7254298B2 (en) organic optical materials
JP2012176928A (en) Pyrene derivative, production method of pyrene derivative, complex, catalyst, electronic material, light-emitting material and pigment
EP3590919B1 (en) Enamine compound and use thereof
CN112384518B (en) Rare earth complex, luminescent material, luminescent device, interlayer for laminated glass, windshield for vehicle, wavelength conversion material, and security material
CN111875636B (en) Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof
CN112876412B (en) Doped luminescent material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination