CN109438459B - Organic second-order nonlinear optical chromophore and synthetic method and application thereof - Google Patents

Organic second-order nonlinear optical chromophore and synthetic method and application thereof Download PDF

Info

Publication number
CN109438459B
CN109438459B CN201811413720.5A CN201811413720A CN109438459B CN 109438459 B CN109438459 B CN 109438459B CN 201811413720 A CN201811413720 A CN 201811413720A CN 109438459 B CN109438459 B CN 109438459B
Authority
CN
China
Prior art keywords
organic
chromophore
order nonlinear
formula
tricyanofuran
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.)
Expired - Fee Related
Application number
CN201811413720.5A
Other languages
Chinese (zh)
Other versions
CN109438459A (en
Inventor
张琦
邓国伟
王洁雪
陶果
赵紫羽
韩涛
张小玲
李仲辉
孙康
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.)
Chengdu Normal University
Original Assignee
Chengdu Normal 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 Chengdu Normal University filed Critical Chengdu Normal University
Priority to CN201811413720.5A priority Critical patent/CN109438459B/en
Publication of CN109438459A publication Critical patent/CN109438459A/en
Application granted granted Critical
Publication of CN109438459B publication Critical patent/CN109438459B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3611—Organic materials containing Nitrogen
    • G02F1/3612—Heterocycles having N as heteroatom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3613—Organic materials containing Sulfur
    • G02F1/3614—Heterocycles having S as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to an organic second-order nonlinear optical chromophore, a synthetic method and application thereof, wherein the chromophore has a structure shown in a formula I:
Figure 141083DEST_PATH_IMAGE001
in the formula I, the formula I is shown in the specification,
Figure 100949DEST_PATH_IMAGE002
is a conjugated electron bridge, R1、R2Each independently selected from the group consisting of substituted or unsubstituted: c1‑6Alkyl of (C)1‑6Alkoxy group of (C)4‑12Any of aryl or heteroaryl of (a). The chromophore of the invention adopts julolidine derivatives as electron donors and tricyanofurans as electron acceptors, has a proper structure, and can effectively reduce intermolecular interactionAnd (4) the first-order hyperpolarizability (beta value) is higher when force is applied. Meanwhile, the chromophore has proper conjugate length and good stability, the thermal decomposition temperature can reach more than 250 ℃, and the chromophore has excellent optical performance, and the electro-optic coefficient can reach more than 76 pm/V.

Description

Organic second-order nonlinear optical chromophore and synthetic method and application thereof
Technical Field
The invention relates to the field of organic second-order nonlinear optical materials, in particular to a novel organic second-order nonlinear chromophore containing a julolidine derivative electron donor and a tricyanofuran electron acceptor and having a D-pi-A structure, and a synthetic method and application thereof.
Background
The nonlinear optical material can perform light wave frequency conversion and light signal processing, for example, amplification of weak light signals is realized by using a frequency mixing phenomenon, optical recording and operation functions are realized by using nonlinear response, and the like, so that the nonlinear optical material has important application values in the fields of laser, communication, electronic instruments, medical equipment and the like. Nonlinear optical materials can be classified into five major classes, i.e., inorganic nonlinear optical materials, organic low-molecular nonlinear optical materials, high-molecular nonlinear optical materials, inorganic/organic composite nonlinear optical materials, and metal-organic nonlinear optical materials, according to the composition. Compared with inorganic materials, the organic low-molecular nonlinear optical material has the following remarkable characteristics: (1) a large nonlinear optical coefficient; (2) the high optical damage threshold density can be considered as the design and synthesis of organic crystals according to the required physical properties; (3) a wide range of transmission wavelengths; (4) the low dielectric constant optical response is fast. Therefore, organic nonlinear optical materials have been the focus of research.
The response performance of the organic nonlinear optical material is closely related to the structure of the chromophore thereof. Theoretical studies indicate that the performance of organic nonlinear optical materials is associated with a high degree of delocalization of electrons. The chromophore electron with the D-pi-A structure is highly delocalized, is easy to polarize and has a larger nonlinear optical coefficient. Such conjugated molecules having charge transfer properties are the most effective components in organic nonlinear optical materials. On one hand, the intensity of an electron donor and an electron acceptor in the chromophore structure is regulated and controlled, so that the nonlinear optical performance of the chromophore can be effectively optimized; on the other hand, dipole-dipole interaction force exists among chromophores, which can influence the orientation arrangement processing (and further the macroscopic performance) of the nonlinear optical chromophores, and introduction of a spacer group on the chromophores or reasonable adjustment of the chromophore structure can help to inhibit the dipole-dipole interaction of the chromophores. Therefore, the development of electron donor materials with novel structures has an important influence on the improvement of the macroscopic properties of the materials.
Disclosure of Invention
Problems to be solved by the invention
In order to overcome the technical problems, the invention aims to provide a novel organic second-order nonlinear chromophore with a D-pi-A structure, which has the advantages of relatively simple structure, low price, good atom economy, good stability and excellent optical performance.
Means for solving the problems
The technical scheme adopted by the invention is as follows:
the invention provides an organic second-order nonlinear chromophore with a D-pi-A structure, which is characterized in that the chromophore has a structure shown in a formula I:
Figure 731776DEST_PATH_IMAGE001
，
formula I
Wherein the content of the first and second substances,
Figure 438701DEST_PATH_IMAGE002
is a conjugated electron bridge, R1、R2Each independently selected from the group consisting of substituted or unsubstituted: c1-6Alkyl of (C)1-6Alkoxy group of (C)4-12Any of aryl or heteroaryl of (a).
Preferably, the conjugated electron bridge may be a linking group having a conjugated structure as is conventional in the art, preferably selected from any one of the following structures:
Figure 629511DEST_PATH_IMAGE003
。
preferably, said substitution is by a halogen atom, cyano, nitro, C1-3Is substituted with one or more of alkyl or alkoxy, C4-12The aryl or heteroaryl of (a) is selected from one or more of phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrrolyl, pyrazolyl, thiazolyl.
Preferably, the halogen atom is fluorine, chlorine, bromine or iodine, preferably fluorine.
More preferably, R is as defined above1、R2Each independently selected from hydrogen, methyl, trifluoromethyl and phenyl.
Preferably, the chromophore is of the structure:
Figure 322660DEST_PATH_IMAGE004
or is or
Figure 243212DEST_PATH_IMAGE005
More preferably, it is
Figure 58721DEST_PATH_IMAGE006
。
Secondly, the invention also provides a method for preparing any organic second-order nonlinear chromophore with D-pi-A structure, which comprises the following steps:
the method comprises the following steps:
dissolving a julolidine derivative and a tricyanofuran electron acceptor in an ethanol solution, reacting at 50-80 ℃ under the action of an organic base catalyst to obtain the novel organic second-order nonlinear chromophore with the D-pi-A structure,
wherein the structure of the julolidine derivative is as follows:
Figure 940090DEST_PATH_IMAGE007
，
the tricyanofuran electron acceptor has any structure as follows:
Figure 233668DEST_PATH_IMAGE008
，
the mol ratio of the julolidine derivative to the tricyanofuran electron acceptor is 1: 1.1-1: 1.2;
or the second method:
1) mixing the julolidine derivative, the phosphonium salt and the sodium hydride in a 1, 2-dichloroethane solvent, reacting at the temperature of 20-50 ℃, carrying out post-treatment after the reaction to obtain an intermediate compound with a structure shown as a formula II,
Figure 743146DEST_PATH_IMAGE009
formula II
Wherein the julolidine derivative: the mol ratio of the phosphine salt is 0.8: 1-1.2: 1,
wherein the structure of the julolidine derivative is as follows:
Figure 932819DEST_PATH_IMAGE007
the structure of the phosphonium salt is as follows:
Figure 894959DEST_PATH_IMAGE010
2) mixing an intermediate compound shown in a formula II with phosphorus oxychloride in an organic solvent, stirring and refluxing at 70-90 ℃, performing post-treatment after the reaction is finished to obtain an intermediate compound shown in a formula III,
Figure 726649DEST_PATH_IMAGE011
formula III
Wherein the intermediate compound of formula II: the molar ratio of phosphorus oxychloride is 1: 1 to 1.2;
3) dissolving a compound shown in a formula III and a tricyanofuran electron acceptor in ethanol, reacting at 50-80 ℃, and after the reaction is finished, carrying out post-treatment to obtain a novel organic second-order nonlinear optical chromophore with a D-pi-A structure,
wherein, the tricyanofuran electron acceptor has any structure as follows:
Figure 827985DEST_PATH_IMAGE008
，
the molar ratio of the intermediate compound shown in the formula III to the tricyanofuran electron acceptor is 1: 1.1-1: 1.5.
preferably, the organic base catalyst may be any condensation catalyst conventional in the art, more preferably one or more selected from triethylamine, pyridine and piperidine.
The invention further provides an application of any one of the organic second-order nonlinear chromophores with the D-pi-A structure, and the organic second-order nonlinear optical chromophores are doped with amorphous polymers to prepare films.
Finally, the invention also provides an application of the organic second-order nonlinear chromophore with the D-pi-A structure in the field of photoelectricity.
ADVANTAGEOUS EFFECTS OF INVENTION
1. The invention firstly prepares the julolidine derivative tabletThe segment structure is introduced into an organic second-order nonlinear chromophore, and the julolidine segment structure can be connected with a simple conjugated electronic bridge, such as
Figure 719717DEST_PATH_IMAGE003
And further, the organic second-order nonlinear chromophore with novel structure, good atom economy, low price and simple structure can be obtained.
2. The coumarin of tetramethyl-jillionidine has four methyl groups in the structure, and can be used as a steric hindrance group to effectively isolate a nonlinear optical chromophore, so that dipole-dipole interaction is inhibited to a certain degree, and meanwhile, the better electron donating capability of the coumarin is also beneficial to improving the microscopic nonlinear optical performance of the chromophore. Meanwhile, the chromophore has proper conjugation length and good stability, and the thermal decomposition temperature can reach more than 250 ℃.
3. The chromophore of the invention has excellent optical performance, and the electro-optic coefficient of the chromophore can reach more than 76 pm/V.
4. The method for preparing the novel organic second-order nonlinear chromophore with the D-pi-A structure is simple, the raw materials are cheap and easy to obtain, the operation is simple, the yield of the product is high, the processing and the forming are easy, the device formation is convenient, and the application and the popularization of the novel organic second-order nonlinear chromophore are more convenient.
Detailed Description
The invention provides an organic second-order nonlinear chromophore with a D-pi-A structure, which is characterized in that the chromophore has a structure shown in a formula I:
Figure 44519DEST_PATH_IMAGE001
，
formula I
Wherein the content of the first and second substances,
Figure 679900DEST_PATH_IMAGE002
is a conjugated electron bridge，R1、R2Each independently selected from the group consisting of substituted or unsubstituted: c1-6Alkyl of (C)1-6Alkoxy group of (C)4-12Any of aryl or heteroaryl of (a).
In a preferred embodiment, the conjugated electronic bridge may be a linking group having a conjugated structure as is conventional in the art, preferably selected from any one of the following structures:
Figure 226288DEST_PATH_IMAGE003
。
in a preferred embodiment, the substitution is by a halogen atom, cyano, nitro, C1-3Is substituted with one or more of alkyl or alkoxy, C4-12The aryl or heteroaryl of (a) is selected from one or more of phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrrolyl, pyrazolyl, thiazolyl.
In a more preferred embodiment, the halogen atom is fluorine, chlorine, bromine, iodine, preferably fluorine.
In a more preferred embodiment, R is as defined above1、R2Each independently selected from hydrogen, methyl, trifluoromethyl and phenyl.
In a more preferred embodiment, the chromophore is structured as:
Figure 288922DEST_PATH_IMAGE004
or is or
Figure 694495DEST_PATH_IMAGE005
More preferably, it is
Figure 71250DEST_PATH_IMAGE006
。
Secondly, the invention also provides a method for preparing any organic second-order nonlinear chromophore with D-pi-A structure, which comprises the following steps:
the method comprises the following steps:
dissolving a julolidine derivative and a tricyanofuran electron acceptor in an ethanol solution, reacting at 50-80 ℃ under the action of an organic base catalyst to obtain the novel organic second-order nonlinear chromophore with the D-pi-A structure,
wherein the structure of the julolidine derivative is as follows:
Figure 347511DEST_PATH_IMAGE007
，
the tricyanofuran electron acceptor has any structure as follows:
Figure 643363DEST_PATH_IMAGE008
，
the mol ratio of the julolidine derivative to the tricyanofuran electron acceptor is 1: 1.1-1: 1.2;
or the second method:
1) mixing the julolidine derivative, the phosphonium salt and the sodium hydride in a 1, 2-dichloroethane solvent, reacting at the temperature of 20-50 ℃, carrying out post-treatment after the reaction to obtain an intermediate compound with a structure shown as a formula II,
Figure 208336DEST_PATH_IMAGE009
formula II
Wherein the julolidine derivative: the mol ratio of the phosphine salt is 0.8: 1-1.2: 1,
wherein the structure of the julolidine derivative is as follows:
Figure 185519DEST_PATH_IMAGE007
the structure of the phosphonium salt is as follows:
Figure 644183DEST_PATH_IMAGE010
2) mixing an intermediate compound shown in a formula II with phosphorus oxychloride in an organic solvent, stirring and refluxing at 70-90 ℃, performing post-treatment after the reaction is finished to obtain an intermediate compound shown in a formula III,
Figure 986302DEST_PATH_IMAGE011
formula III
Wherein the intermediate compound of formula II: the molar ratio of phosphorus oxychloride is 1: 1 to 1.2;
3) dissolving a compound shown in a formula III and a tricyanofuran electron acceptor in ethanol, reacting at 50-80 ℃, and after the reaction is finished, carrying out post-treatment to obtain a novel organic second-order nonlinear optical chromophore with a D-pi-A structure,
wherein, the tricyanofuran electron acceptor has any structure as follows:
Figure 163206DEST_PATH_IMAGE008
，
the molar ratio of the intermediate compound shown in the formula III to the tricyanofuran electron acceptor is 1: 1.1-1: 1.5.
in a preferred embodiment, the organic base catalyst may be any condensation catalyst conventional in the art, more preferably selected from one or more of triethylamine, pyridine and piperidine.
The invention further provides an application of any one of the organic second-order nonlinear chromophores with the D-pi-A structure, and the organic second-order nonlinear optical chromophores are doped with amorphous polymers to prepare films.
Finally, the invention also provides an application of the organic second-order nonlinear chromophore with the D-pi-A structure in the field of photoelectricity.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Synthesizing a novel organic second-order nonlinear chromophore with a D-pi-A structure as shown in the specification:
Figure 147342DEST_PATH_IMAGE012
the synthetic route is as follows:
Figure 132616DEST_PATH_IMAGE013
the synthesis method comprises the following steps:
adding 0.5g (1.60mmol) of julolidine derivative and 0.35g (1.76 mmol) of tricyanofuran into a round-bottom flask, dissolving in 20-25 ml of ethanol, adding 2 drops of triethylamine into the solution, stirring and refluxing at the temperature of 60 ℃, and removing ethanol by rotary evaporation after the reaction is finished to obtain a crude product. And (3) performing column chromatography (the stationary phase is silica gel with 200-300 meshes, and the mobile phase is a mixed solution of petroleum ether and ethyl acetate) to obtain 0.66g of a product, wherein the yield is 81%.1H NMR (300 MHz, CDCl3) δ 10.11 (s, 1H), 8.17 (s, 1H), 7.20 (s, 1H), 3.50 – 3.38 (m, 2H), 3.37 – 3.25 (m, 2H), 1.88 – 1.69 (m, 4H), 1.55 (s, 6H), 1.29 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 187.95, 161.86, 155.17, 148.93, 145.60, 129.38, 126.39, 114.78, 112.75, 108.67, 47.76, 47.17, 38.62, 34.91, 32.11, 32.02, 29.74, 28.47. MS (ESI) (M+, C31H32N4O3): calcd: 508.25; found: 508.55。
Example 2
Synthesizing a novel organic second-order nonlinear chromophore with a D-pi-A structure as shown in the specification:
Figure 239112DEST_PATH_IMAGE014
the synthetic route is as follows:
Figure 575415DEST_PATH_IMAGE015
the synthesis method comprises the following steps:
0.5g (1.60mmol) of julolidine derivative and 0.55g (1.75 mmol) of trifluoromethyl phenyl tricyanofuran are added into a round-bottom flask and dissolved in 20-25 ml of ethanol, 2 drops of triethylamine are added into the solution, the solution is stirred and refluxed at the temperature of 60 ℃, and after the reaction is finished, the ethanol is removed by rotary evaporation to obtain a crude product. And (3) performing column chromatography (the stationary phase is silica gel with 200-300 meshes, and the mobile phase is a mixed solution of petroleum ether and ethyl acetate) to obtain 0.79g of a product, wherein the yield is 79%.1H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 15.4 Hz, 1H), 7.77 (d, J = 15.5 Hz, 1H), 7.74 (s, 1H), 7.58 (s, 2H), 7.54 (s, 3H), 7.18 (s, 1H), 3.52 (t, J = 5.9 Hz, 2H), 3.42 (d, J = 5.1 Hz, 2H), 1.88 – 1.82 (m, 2H), 1.80 (m, 2H), 1.56 (s, 3H), 1.55 (s, 3H), 1.33 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 176.07, 164.12, 159.13, 153.94, 150.10, 146.77, 131.24, 130.47, 129.73, 129.67, 126.41, 125.87, 114.86, 111.98, 111.58, 111.23, 110.81, 110.74, 60.41, 57.91, 48.26, 47.60, 38.27, 34.60, 32.07, 30.94, 29.56, 28.27, 21.10, 14.19. MS (ESI) (M+, C36H31F3N4O3): calcd: 624.23; found: 624.60。
Example 3
Synthesizing a novel organic second-order nonlinear chromophore with a D-pi-A structure as shown in the specification:
Figure 434349DEST_PATH_IMAGE006
the synthetic route is as follows:
Figure 539708DEST_PATH_IMAGE016
synthesis method
1) Synthesis of Compound 2
0.5g (1.60mmol) of julolidine derivative and 0.84g (1.9mmol) of thiophenephosphine salt are added into a round-bottom flask, dissolved in 20-25 ml of 1, 2-dichloroethane solvent, added with a proper amount of sodium hydride and stirred at room temperature. After the reaction is finished, pouring the reaction liquid into water, separating liquid, extracting a water phase by dichloromethane, combining organic phases, drying the organic phases by anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating by column chromatography (the stationary phase is silica gel with 200-300 meshes, and the mobile phase is a mixed liquid of petroleum ether and ethyl acetate) to obtain 0.55g of compound 2, wherein the yield is 85%.1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 16.2 Hz , 1H), 7.53 (s, 1H), 7.17 (d, J = 5.0 Hz, 1H), 7.09 (s, 1H), 7.06 (d, J = 3.4 Hz, 1H), 6.99 (dd, J = 5.0, 3.6 Hz, 1H), 6.85 (d, J = 16.0 Hz, 1H), 3.32 – 3.28 (m, 2H), 3.24 – 3.20 (m, 2H), 1.84 – 1.79 (m, 2H), 1.78 – 1.74 (m, 2H), 1.57 (s, 6H), 1.30 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 160.78, 151.71, 145.21, 143.67, 139.27, 128.42, 127.63, 126.04, 124.17, 123.29, 116.30, 115.01, 109.72, 47.35, 46.91, 39.42, 35.82, 32.24, 32.19, 30.75, 29.70, 28.96。
2) Synthesis of Compound 3
Mixing 0.25g (1.65 mmol) of phosphorus oxychloride and 5ml of N, N-dimethylformamide at 0 ℃, carrying out nitrogen protection, reacting at 0 ℃ for 2 hours, adding 0.55g (1.35mmol) of dichloromethane solution of compound 2, stirring and refluxing at 70-90 ℃, cooling after the reaction is finished, pouring into sodium carbonate aqueous solution, extracting a water phase with dichloromethane, separating the liquid, combining the organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation (the stationary phase is 200-300 meshes of silica gel, and the mobile phase is petroleum etherAnd ethyl acetate) to obtain 0.42g of compound 3 in a yield of 72%.1H NMR (400 MHz, CDCl3) δ 9.83 (s, 1H), 7.79 (d, J = 15.8, 1H), 7.65 (d, J = 3.9, 1H), 7.58 (s, 1H), 7.13 (d, J = 3.7, 1H), 7.12 (s, 1H), 7.01 (d, J = 15.8 Hz, 1H), 3.36-3.30 (m, 3H), 3.27-3.23 (m, 2H), 1.85 – 1.79 (m, 2H), 1.78-1.74 (m, 2H), 1.56 (s, 6H), 1.31 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 182.38, 160.39, 153.82, 152.11, 146.00, 142.02, 140.99, 137.49, 128.68, 128.38, 126.44, 123.69, 122.12, 114.53, 109.48, 47.39, 46.91, 39.19, 35.55, 32.17, 32.14, 30.49, 28.83。
3) Synthesis of Compound 4
Adding 0.42g (1.0mmol) of compound 3 and 0.21g (1.1mmol) of tricyanofuran into a round-bottom flask, dissolving in 20-25 ml of ethanol, adding 2 drops of triethylamine into the solution, stirring and refluxing at the temperature of 60 ℃, and removing ethanol by rotary evaporation after the reaction is finished to obtain a crude product. Column chromatography (stationary phase is 200-300 mesh silica gel, mobile phase is the mixture of petroleum ether and ethyl acetate) gave 0.49g of compound 4, 79% yield.1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 15.8 Hz, 1H)， 7.78 (d, J = 15.7 Hz, 1H)，7.59 (s, 1H), 7.38 (d, J = 3.3 Hz, 1H), 7.12 (s, 1H), 7.11 (d, J = 3.4 Hz, 1H), 7.01 (d, J = 15.8 Hz, 1H), 6.61 (d, J= 15.7 Hz, 1H), 3.40 – 3.18 (m, 4H), 1.90-1.7 (m, 10H), 1.57 (s, 6H), 1.30 (s, 10H). 13C NMR (100 MHz, CDCl3) δ 175.67, 172.98, 160.36, 153.70, 152.29, 150.22, 146.38, 142.33, 139.34, 138.36, 137.27, 129.47, 128.92, 128.16, 123.86, 121.82, 118.07, 114.83, 114.52, 112.34, 109.65, 97.16, 56.30, 47.50, 47.00, 39.14, 35.50, 32.20, 32.18, 30.39, 28.81, 26.54。
Example 4
Synthesizing a novel organic second-order nonlinear chromophore with a D-pi-A structure as shown in the specification:
Figure 817106DEST_PATH_IMAGE017
the synthetic route is as follows:
Figure 234181DEST_PATH_IMAGE018
synthesis method
1) Synthesis of Compound 2
0.5g (1.60mmol) of julolidine derivative and 0.81g (1.9mmol) of furan phosphine salt are added into a round-bottom flask, dissolved in 20-25 ml of 1, 2-dichloroethane solvent, added with a proper amount of sodium hydride and stirred at room temperature. After the reaction is finished, pouring the reaction liquid into water, separating liquid, extracting a water phase by dichloromethane, combining organic phases, drying the organic phases by anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating by column chromatography (the stationary phase is silica gel with 200-300 meshes, and the mobile phase is a mixed liquid of petroleum ether and ethyl acetate) to obtain 0.54g of compound 2, wherein the yield is 87%.1H NMR (400 MHz, CDCl3) δ 7.51 (s, 1H), 7.44 (d, J = 16.0 Hz, 1H), 7.39 (d, J = 1.5 Hz, 1H), 6.92 (d, J = 16.1 Hz, 1H), 6.41 (dd, J = 3.3, 1.8 Hz, 1H), 6.34 (d, J = 3.3 Hz, 1H), 3.32 – 3.27 (m, 2H), 3.24 – 3.19 (m, 2H), 1.82 – 1.79 (m, 2H), 1.77 – 1.73 (m, 2H), 1.56 (s, 6H), 1.30 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 160.83, 153.86, 151.68, 145.18, 142.02, 139.75, 128.40, 123.30, 122.22, 118.10, 116.37, 114.99, 111.79, 109.76, 108.73, 47.34, 46.90, 39.43, 35.84, 32.23, 32.19, 30.75, 28.97。
2) Synthesis of Compound 3
Mixing 0.26g (1.7mmol) of phosphorus oxychloride and 5ml of N, N-dimethylformamide at 0 ℃, carrying out nitrogen protection, reacting at 0 ℃ for 2 hours, adding 0.54g (1.4 mmol) of dichloromethane solution of compound 2, stirring and refluxing at 70-90 ℃, cooling after the reaction is finished, pouring into sodium carbonate aqueous solution, extracting a water phase with dichloromethane, separating the liquid, combining the organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation (the stationary phase is silica gel with 200-300 meshes, and the mobile phase is petroleum ether and acetic acidA mixture of ethyl esters) to obtain 0.41g of compound 3 in 70% yield.1H NMR (400 MHz, CDCl3) δ 9.56 (s, 1H), 7.58 (d, J = 15 Hz, 1H), 7.57 (s, 1H), 7.26 (d, J = 3.7 Hz, 1H), 7.22 (d, J = 15 Hz, 1H), 7.11 (s, 1H), 6.50 (d, J = 3.7 Hz, 1H), 3.39 – 3.30 (m, 2H), 3.29 – 3.14 (m, 2H), 1.86 – 1.70 (m, 4H), 1.56 (s,6H), 1.31 (s, 6H).13C NMR (100 MHz, CDCl3) δ 160.30, 159.72, 152.15, 151.57, 146.03, 142.95, 128.86, 128.70, 123.76, 116.29, 114.78, 110.90, 109.55, 47.42, 46.93, 39.21, 35.59, 32.18, 32.16, 30.49, 28.84。
3) Synthesis of Compound 4
Adding 0.41g (1.0mmol) of compound 3 and 0.38g (1.2mmol) of trifluoromethyl phenyl tricyanofuran into a round-bottom flask, dissolving in 20-25 ml of ethanol, adding 2 drops of triethylamine into the solution, stirring and refluxing at the temperature of 60 ℃, and removing ethanol by rotary evaporation after the reaction is finished to obtain a crude product. Column chromatography (stationary phase is 200-300 mesh silica gel, mobile phase is the mixture of petroleum ether and ethyl acetate) gave 0.54g of compound 4, 76% yield.1H NMR (500 MHz, CDCl3) δ 7.62 (s, 1H), 7.53 (d, J = 15.8 Hz, 1H), 7.50 – 7.42 (m, 5H), 7.20 – 7.12 (m, 1H), 7.15 (d, J = 15.8 Hz, 1H), 7.10 (s, 1H), 6.90 (s,1H), 6.88 (d, J = 15.1 Hz, 1H), 6.53 (d, J = 3.5 Hz, 1H), 3.30 (t, J = 5.8 Hz, 2H), 3.21 (d, J = 5.0 Hz, 2H), 1.75 (d, J = 5.0 Hz, 2H), 1.70 (t, J = 5.8 Hz, 2H), 1.49 (s, 6H), 1.24 (s, 6H)。
Example 5
5 mg of the nonlinear optical chromophore obtained in example 1 were taken and analyzed on a thermogravimetric analyzer, under the following test conditions: the thermal decomposition temperature of the nonlinear optical chromophore obtained in example 1 was determined to be 228 ℃ under nitrogen protection at a temperature rise rate of 10 ℃ per minute.
Example 6
5 mg of the nonlinear optical chromophore obtained in example 2 were taken and analyzed on a thermogravimetric analyzer, under the following test conditions: the thermal decomposition temperature of the nonlinear optical chromophore obtained in example 2 was measured to be 203 ℃ under nitrogen protection at a temperature rise rate of 10 ℃ per minute.
Example 7
5 mg of the nonlinear optical chromophore obtained in example 3 were taken and analyzed on a thermogravimetric analyzer, under the following test conditions: the thermal decomposition temperature of the nonlinear optical chromophore obtained in example 3 was determined to be 250 ℃ under nitrogen protection at a temperature rise rate of 10 ℃ per minute.
Example 8
5 mg of the nonlinear optical chromophore obtained in example 4 were taken and analyzed on a thermogravimetric analyzer, under the following test conditions: the thermal decomposition temperature of the nonlinear optical chromophore obtained in example 4 was measured to be 256 ℃ under nitrogen protection at a temperature rise rate of 10 ℃ per minute.
Performance testing
The organic second order nonlinear chromophores prepared in the examples were tested as follows.
1. Adding 0.08 g of polymethyl methacrylate (PMMA) into 1.00ml of dibromomethane, stirring for 3-5 hours until the PMMA is completely dissolved, adding 0.02 g of the nonlinear optical chromophore synthesized in the example 1 to obtain a mixed solution, filtering, and coating on an ITO glass substrate by using a spin coating method. The rotating speed is controlled to be 500-1000 r/min, and the obtained film is dried in a vacuum drying oven at the temperature of 60 ℃ for 24 hours. The thickness of the film is 1 to 5 μm. Polarizing the film obtained from the step 1 by a contact polarization method, wherein the polarizing temperature is 108 ℃, the polarizing time is 5-20 minutes, the polarizing voltage is 60-130V/mum, and the electro-optic coefficient (r)33) Measurement was performed by Simple Reflection Method (Simple Reflection Method, also known as the Teng-Man Method, see Teng C., Man H. T., Simple Reflection technique for measuring the electro-optical coeffective of poled polymers, Applied Physics Letters, 1990, 56 (18), 1734-1736.). The highest value of the measured electro-optic coefficient was 40 pm/V.
2. Adding 0.08 g of polymethyl methacrylate (PMMA) into 1.00ml of dibromomethane, stirring for 3-5 hours until the PMMA is completely dissolved, adding 0.02 g of the nonlinear optical chromophore synthesized in the embodiment 2 to obtain a mixed solution, filtering, and coating on an ITO glass substrate by using a spin coating method. The rotation speed is controlled to be 500-1000 rpm,the resulting film was dried in a vacuum oven at 60 ℃ for 24 hours. The thickness of the film is 1 to 5 μm. Polarizing the film obtained from the step 1 by a contact polarization method, wherein the polarizing temperature is 110 ℃, the polarizing time is 5-20 minutes, the polarizing voltage is 60-130V/mum, and the electro-optic coefficient (r)33) Measurement was performed by Simple Reflection Method (Simple Reflection Method, also known as the Teng-Man Method, see Teng C., Man H. T., Simple Reflection technique for measuring the electro-optical coeffective of poled polymers, Applied Physics Letters, 1990, 56 (18), 1734-1736.). The highest value of the measured electro-optic coefficient was 76 pm/V.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. An organic second-order nonlinear chromophore having a D-pi-A structure, wherein said chromophore has the structure of formula I:
Figure FDA0002843996980000011
wherein the content of the first and second substances,
Figure FDA0002843996980000012
is a conjugated electron bridge, R1、R2Each independently selected from the group consisting of substituted or unsubstituted: c1-6Alkyl of (C)1-6Alkoxy group of (C)4-12Any of the aryl or heteroaryl of (a), said conjugated electron bridge being any of the following structures:
Figure FDA0002843996980000013
2. the organic second-order compound of claim 1 having a D-pi-A structureNonlinear chromophores, characterised in that said substitution is by halogen atoms, cyano groups, nitro groups, C1-3Is substituted with one or more of alkyl or alkoxy, C4-12The aryl or heteroaryl of (a) is selected from one or more of phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyrrolyl, pyrazolyl, thiazolyl.
3. The organic second-order nonlinear chromophore having a structure of D-pi-a of claim 2, wherein the halogen atom is fluorine, chlorine, bromine, or iodine.
4. The organic second-order nonlinear chromophore having a structure of D-pi-a of claim 2, wherein the halogen atom is fluorine.
5. The organic second-order nonlinear chromophore having a D-pi-A structure of claim 2, wherein R is R1、R2Each independently selected from methyl, trifluoromethyl and phenyl.
6. The organic second-order nonlinear chromophore with D-pi-A structure of claim 1, wherein the chromophore has the structure:
Figure FDA0002843996980000021
7. a process for the preparation of an organic second-order nonlinear chromophore with a D- π -A structure according to any of claims 1-6, said process comprising the steps of:
the method comprises the following steps:
dissolving a julolidine derivative and a tricyanofuran electron acceptor in an ethanol solution, reacting at 50-80 ℃ under the action of an organic base catalyst to obtain the novel organic second-order nonlinear chromophore with the D-pi-A structure,
wherein the structure of the julolidine derivative is as follows:
Figure FDA0002843996980000031
the tricyanofuran electron acceptor has any structure as follows:
Figure FDA0002843996980000032
the mol ratio of the julolidine derivative to the tricyanofuran electron acceptor is 1: 1.1-1: 1.2;
or the second method:
1) mixing the julolidine derivative, the phosphonium salt and the sodium hydride in a 1, 2-dichloroethane solvent, reacting at the temperature of 20-50 ℃, carrying out post-treatment after the reaction to obtain an intermediate compound with a structure shown as a formula II,
Figure FDA0002843996980000041
wherein the julolidine derivative: the mol ratio of the phosphine salt is 0.8: 1-1.2: 1,
wherein the structure of the julolidine derivative is as follows:
Figure FDA0002843996980000042
the structure of the phosphonium salt is as follows:
Figure FDA0002843996980000043
2) mixing an intermediate compound shown in a formula II with phosphorus oxychloride in an organic solvent, stirring and refluxing at 70-90 ℃, performing post-treatment after the reaction is finished to obtain an intermediate compound shown in a formula III,
Figure FDA0002843996980000044
wherein the intermediate compound of formula II: the molar ratio of phosphorus oxychloride is 1: 1 to 1.2;
3) dissolving a compound shown in a formula III and a tricyanofuran electron acceptor in ethanol, reacting at 50-80 ℃, and after the reaction is finished, carrying out post-treatment to obtain an organic second-order nonlinear optical chromophore with a D-pi-A structure,
wherein, the tricyanofuran electron acceptor has any structure as follows:
Figure FDA0002843996980000051
the molar ratio of the intermediate compound shown in the formula III to the tricyanofuran electron acceptor is 1: 1.1-1: 1.5.
8. the process of claim 7, wherein the organic base catalyst is selected from one or more of triethylamine, pyridine and piperidine.
9. Use of an organic second-order nonlinear chromophore with a D-pi-a structure according to any of claims 1 to 6, characterized in that: the organic second-order nonlinear optical chromophore is doped with an amorphous polymer to prepare a film.
10. Use of an organic second-order nonlinear chromophore with a D-pi-A structure according to any of claims 1-6 in the field of photovoltaics.
CN201811413720.5A 2018-11-26 2018-11-26 Organic second-order nonlinear optical chromophore and synthetic method and application thereof Expired - Fee Related CN109438459B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811413720.5A CN109438459B (en) 2018-11-26 2018-11-26 Organic second-order nonlinear optical chromophore and synthetic method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811413720.5A CN109438459B (en) 2018-11-26 2018-11-26 Organic second-order nonlinear optical chromophore and synthetic method and application thereof

Publications (2)

Publication Number Publication Date
CN109438459A CN109438459A (en) 2019-03-08
CN109438459B true CN109438459B (en) 2021-03-19

Family

ID=65554246

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811413720.5A Expired - Fee Related CN109438459B (en) 2018-11-26 2018-11-26 Organic second-order nonlinear optical chromophore and synthetic method and application thereof

Country Status (1)

Country Link
CN (1) CN109438459B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022550872A (en) 2019-10-04 2022-12-05 ユニバーシティ オブ ワシントン organic electro-optical chromophore
CN115960093A (en) * 2021-10-09 2023-04-14 香港城市大学深圳研究院 Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device
CN114369112B (en) * 2021-11-26 2024-04-09 广州大学 Organic optical nonlinear chromophore based on double-donor structure, and synthesis method and application thereof
CN114516865B (en) * 2022-03-09 2023-06-23 成都师范学院 D-pi-A type organic conjugated molecule, and preparation method and application thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062802A1 (en) * 2001-02-02 2002-08-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Coumarin derivative, process for producing the same, and luminescent agent and luminescent element each containing the same
JP2002234892A (en) * 2000-11-07 2002-08-23 Hayashibara Biochem Lab Inc Pyran derivative
JP2004043646A (en) * 2002-07-11 2004-02-12 Hayashibara Biochem Lab Inc Organoelectroluminescent element
KR20110054119A (en) * 2009-11-17 2011-05-25 경북대학교 산학협력단 Novel solvatochromic dye and detection method of volatile organic compounds using the same
CN102875546A (en) * 2011-07-13 2013-01-16 中国科学院理化技术研究所 Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof
CN103834000A (en) * 2012-11-23 2014-06-04 中国科学院理化技术研究所 Polycarbonate containing nonlinear optical chromophores, synthesis method and application thereof
CN104558004A (en) * 2013-10-11 2015-04-29 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore with D-pi-A structure and its synthesis method and use
CN104974151A (en) * 2014-04-14 2015-10-14 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof
CN107880052A (en) * 2017-11-02 2018-04-06 济南大学 A kind of fluorescence probe for detecting hydrazine and its application
CN108148574A (en) * 2018-02-06 2018-06-12 中国刑事警察学院 Visualize fluorescence probe of burst fire residue and its preparation method and application
CN108409750A (en) * 2018-01-29 2018-08-17 成都师范学院 A kind of compound and its preparation method and application with D- π-A structures
CN108864154A (en) * 2017-05-11 2018-11-23 中国科学院理化技术研究所 A kind of organic second-order non-linear optical double-chromophore and its preparation method and application using Cu (I) catalysis preparation

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002234892A (en) * 2000-11-07 2002-08-23 Hayashibara Biochem Lab Inc Pyran derivative
WO2002062802A1 (en) * 2001-02-02 2002-08-15 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Coumarin derivative, process for producing the same, and luminescent agent and luminescent element each containing the same
JP2004043646A (en) * 2002-07-11 2004-02-12 Hayashibara Biochem Lab Inc Organoelectroluminescent element
KR20110054119A (en) * 2009-11-17 2011-05-25 경북대학교 산학협력단 Novel solvatochromic dye and detection method of volatile organic compounds using the same
CN102875546A (en) * 2011-07-13 2013-01-16 中国科学院理化技术研究所 Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof
CN103834000A (en) * 2012-11-23 2014-06-04 中国科学院理化技术研究所 Polycarbonate containing nonlinear optical chromophores, synthesis method and application thereof
CN104558004A (en) * 2013-10-11 2015-04-29 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore with D-pi-A structure and its synthesis method and use
CN104974151A (en) * 2014-04-14 2015-10-14 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof
CN108864154A (en) * 2017-05-11 2018-11-23 中国科学院理化技术研究所 A kind of organic second-order non-linear optical double-chromophore and its preparation method and application using Cu (I) catalysis preparation
CN107880052A (en) * 2017-11-02 2018-04-06 济南大学 A kind of fluorescence probe for detecting hydrazine and its application
CN108409750A (en) * 2018-01-29 2018-08-17 成都师范学院 A kind of compound and its preparation method and application with D- π-A structures
CN108148574A (en) * 2018-02-06 2018-06-12 中国刑事警察学院 Visualize fluorescence probe of burst fire residue and its preparation method and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Site-isolation of nonlinear optical chromophores to suppress the dipole-dipole interactions for improved electro-optic performance;Jieyun Wu et al.;《Materials Letters》;20170412;第199卷;第72-74页 *
Synthesis and comparative studies of coumarin-based nonlinear optical chromophores with diferent conjugated electron bridge;Guowei Deng et al.;《Journal of Materials Science: Materials in Electronics》;20200427;第9224-9230页 *
Synthesis and properties of a new second-order NLO chromophore containing the benzo[b]furan moiety for electro-optical materials;Maolin Zhang et al.;《RSC Advances》;20140717;第4卷;第33312-33318页 *
以芳胺为电子给体的D-π-A有机光敏染料-染料敏化太阳电池中的应用;宋晓睿等;《化学进展》;20081031;第20卷(第10期);第1524-1533页 *

Also Published As

Publication number Publication date
CN109438459A (en) 2019-03-08

Similar Documents

Publication Publication Date Title
CN109438459B (en) Organic second-order nonlinear optical chromophore and synthetic method and application thereof
EP1313729B1 (en) Design and synthesis of thiophene derived nlo materials for electro-optic applications
CN101845039B (en) Second-order nonlinear optical chromophore with D-pai-A structure and synthetic method and use thereof
US7307173B1 (en) Pyrroline chromophores
US6393190B1 (en) Chromophores for polymeric thin films and optical waveguides and devices comprising the same
CN104558004B (en) Organic second order non-linear optical chromophore and preparation method and use with D π A structures
CN101845040A (en) Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof
Liu et al. Synthesis of julolidine-containing nonlinear optical chromophores: Achieving excellent electro-optic activity by optimizing the bridges and acceptors
US7019453B2 (en) Polymers having pendant nonlinear optical chromophores and electro-optic devices therefrom
US7601849B1 (en) Nonlinear optical compounds and related macrostructures
CN102875546A (en) Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof
CN108409750B (en) A kind of compound and its preparation method and application with D- π-A structure
CN103304721A (en) Polymethacrylate cross-linked electro-optic polymer system and synthesis method and application thereof
WO2023107680A1 (en) Nonlinear optical chromophores having tetrahydrocarbazole donor groups, lyotropic compositions containing the same, and methods of poling such compositions
He et al. Enhanced electro-optic activity of two novel bichromophores which are synthesized by Cu (I) catalyzed click-reaction
US5453220A (en) Calixarene-based transition metal complexes and photonic devices comprising the same
CN103373990B (en) Chromophore molecule containing triptycene rigid three-dimensional arrangement and synthetic method thereof and application
WO2011071119A1 (en) Method for producing conjugated polymer
US8648332B2 (en) Phenyltetraene-based nonlinear optical chromophores
CA2411963A1 (en) Novel chromophores for polymeric thin films and optical waveguides and devices comprising the same
WO2023231528A1 (en) Chromophore compound, preparation method therefor, and use of chromophore compound
Li et al. Synthesis and nonlinear optical properties of novel conjugated small molecules based on coumarin donor
Chen et al. Preparation and nonlinear optical properties of hybrid sol–gel films doped with triphenylamino-substituted chromophores
KR100332495B1 (en) Octupolar Molecules for Nonlinear Optics and the Method Producing Thereof
CA3239292A1 (en) Nonlinear optical chromophores having tetrahydrocarbazole donor groups, lyotropic compositions containing the same, and methods of poling such compositions

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
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210319

Termination date: 20211126