CN114656432B - Self-assembled organic optical nonlinear chromophore, and synthesis method and application thereof - Google Patents
Self-assembled organic optical nonlinear chromophore, and synthesis method and application thereof Download PDFInfo
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- CN114656432B CN114656432B CN202210338231.8A CN202210338231A CN114656432B CN 114656432 B CN114656432 B CN 114656432B CN 202210338231 A CN202210338231 A CN 202210338231A CN 114656432 B CN114656432 B CN 114656432B
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 120
- 150000001875 compounds Chemical class 0.000 claims description 70
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
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- 230000002102 hyperpolarization Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- LXWVMXSKHOPXBJ-UHFFFAOYSA-M tetrakis(2-methylpropyl)azanium;fluoride Chemical compound [F-].CC(C)C[N+](CC(C)C)(CC(C)C)CC(C)C LXWVMXSKHOPXBJ-UHFFFAOYSA-M 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
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Abstract
The invention provides an organic optical nonlinear chromophore based on a novel single-donor self-assembly structure, which belongs to the field of optical materials, wherein the chromophore has a structural formula shown in an abstract drawing, OH groups are introduced into a single donor and an electronic bridge of a second-order nonlinear optical chromophore through nucleophilic reaction, the two OH groups provide connection sites for further modification, different self-assembly isolation functional groups are connected, and meanwhile, the test of an electro-optic coefficient proves that after the materials are self-assembled, the electro-optic coefficient is higher than that of other non-self-assembly materials.
Description
Technical Field
The invention relates to the field of organic optical materials, in particular to a self-assembled organic optical nonlinear chromophore, a synthesis method and application thereof.
Background
With the rapid development of information and communication technology, the demands of people on high-speed data transmission, processing and large-capacity information calculation are also increasing, and compared with the traditional electronic information carrier, the photon communication information carrier has the advantages of good parallelism, high speed, large bandwidth, high frequency, strong electronic interference resistance, good confidentiality and the like. Among many communication technologies, the interconversion of electrical signals and optical signals, which are closely related to devices such as electro-optical modulators, optical switches, optical information storage devices, etc., has become an important component of the present communication technology. In the future age of high-speed information transmission, integrated electro-optical technology will be a major trend, and electro-optical modulators are mainly based on this technology. Meanwhile, it is also an indispensable important device in optical communication. Nonlinear optical materials have also become a core component of modulators, and have attracted considerable attention. The chromophore is a structure (D-pi-A structure) composed of an electron donor (D), an electron acceptor (A) and an electron bridge (pi), and various types of donors, bridges and acceptors have been developed in the prior art to enhance the first order hyperpolarization of the chromophoreThe ratios, e.g. anilino donors (triarylamino, alkylaniline, etc.), heterocyclic or polyene bridges, TCF or CF 3 TCF derivative receptors are the most common chromophore structures, and a reasonable combination of strong donor, acceptor and suitable electron bridge will produce a large first order hyperpolarizability.
In order to obtain a larger electro-optic coefficient, a larger chromophore primary hyperpolarizability is required. However, chromophores with large first order hyperpolarizabilities typically have large dipole moments, which result in strong electrostatic interactions between molecules during polarization of the chromophore, thus impeding molecular orientation. Ultimately resulting in aggregation of the molecules and low polarization efficiency of the chromophore. Many researches report that by introducing some isolation groups into the donor, acceptor and bridging parts of the chromophore, the dipole interaction between molecules can be reduced, the solubility of the chromophore and the electro-optic coefficient of the material are improved, and the CLD bridge in the NLO chromophore is functionalized by using macromolecular substituents such as alkyl chains, silane, carbazole and the like and various dendritic structures, so that the dipole-dipole interaction can be effectively reduced, and the polarization efficiency of the NLO is improved.
Glass transition temperature (T) of most dendritic chromophore films g ) Typically lower than the high molecular weight polymer EO material. The long-term stability of EO materials is another challenge for second order nonlinear optics. Based on Diels-Alder cycloaddition reaction or ArH-ArF interaction, the electro-optic coefficient and high long-term stability are successfully improved by adopting a lattice hardening or intermolecular hydrogen bonding method of sequential polarization, crosslinking or self-assembly. However, the design, synthesis, polarization and crosslinking processes of crosslinked electro-optic materials are very complex.
Disclosure of Invention
In view of the above problems, the present invention provides a new self-assembled mono-donor structure, in which OH groups are introduced into a mono-donor and an electron bridge of a second order nonlinear optical chromophore by nucleophilic reaction, two OH groups connected at a donor end and an electron bridge end provide a connection site for further modification, and a new dendrimer, a main chain and a side chain self-assembled EO polymer is formed by introducing a highly efficient self-assembled group containing an aromatic phenyl dendrite (HD), a pentafluorophenyl dendrite (PFD) or a trifluorophenyl dendrite (TFD), thereby having an ultra-large electro-optic coefficient and high long-term stability.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides an organic optical nonlinear chromophore based on a single donor self-assembled structure, wherein the chromophore comprises H1, H2, H3 and H4, and the specific molecular structural formula is as follows:
wherein the molecular structural general formula of the chromophores H1, H2 and H3 is shown as follows:
wherein R is
In a second aspect, the invention provides a method for synthesizing an organic optical nonlinear chromophore based on a single-donor self-assembled structure, comprising synthesizing chromophores H1-H3 and synthesizing chromophore H4.
Preferably, the method for synthesizing chromophores H1-H3 comprises the following steps:
s1, 4- ((2- ((tert-butyl dimethyl silicon based) oxy) ethyl) (methyl) amino) benzaldehyde (namely a compound (2 a)) and isophorone (a compound 1) are subjected to Knoevenagel condensation reaction in sodium ethoxide and 2-mercaptoethanol to obtain a compound (3 a);
s2, connecting a tert-butyl dimethylsilyl group protecting group to the alcoholic hydroxyl group of the compound (3 a) to obtain a compound (4 a);
s3, reacting the compound (4 a) with diethyl cyanomethylphosphonate through a Wittig-Hornor reaction to obtain a compound (5 a);
s4, reducing cyano groups in the compound (5 a) into aldehyde through diisobutyl aluminum hydride to obtain a compound (6 a);
s5, performing acid hydrolysis on the compound (6 a) to obtain a compound (7 a);
s6, connecting different functional isolation groups on the alcoholic hydroxyl groups of the compound (7 a) through nucleophilic substitution or Steglich esterification to obtain the compounds (8 a-8 c);
s7, condensing the compounds (8 a-8 c) with receptor molecules to prepare chromophores H1-H3;
wherein the compounds (1) - (H3) have the following structures:
preferably, the method for synthesizing chromophore H4 comprises the steps of:
p1, using 4- (methyl (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethyl) amino) benzaldehyde (i.e. compound (2 b)) and isophorone (compound 1), obtaining compound (3 b) by knoevenagel condensation under sodium ethoxide and 2-mercaptoethanol conditions;
p2, connecting a tert-butyl diphenyl silicon-based protecting group to the alcoholic hydroxyl of the compound (3 b) to obtain a compound (4 b);
p3, the compound (4 b) and diethyl cyanomethylphosphonate react to obtain a compound (5 b) through a Wittig-Hornor reaction;
p4, reducing cyano groups in the compound (5 b) through diisobutylaluminum hydride to obtain aldehyde compounds (6 b);
p5, removing the protecting group of the compound (6 b) through alkaline hydrolysis to obtain a compound (7 b);
p6, connecting a self-assembled isolating group on the alcoholic hydroxyl group of the compound (7 b) through nucleophilic substitution or Steglich esterification to obtain a compound (8 d);
p7, the compound (8 d) is hydrolyzed by acid to obtain a compound (9);
p8, connecting a tri-furcation isolation group on the alcoholic hydroxyl group of the compound (9) through nucleophilic substitution or Steglich esterification to obtain a compound (10);
p9, the compound (10) is condensed with an acceptor molecule to prepare the chromophore H4;
wherein, the compounds (1) - (H4) have the following structures and synthesis steps:
more preferably, the method for synthesizing H1, H2 and H3 specifically comprises the following steps:
s1, slowly dissolving metal sodium in ethanol under the protection of argon, adding 2-mercaptoethanol under the ice bath condition, adding the compound (1) for reaction for 1 hour after fully mixing and stirring, adding the compound (2 a), refluxing at 65 ℃ overnight, extracting and concentrating with ethyl acetate after the reaction is finished, purifying by silica gel chromatography, and using ethyl acetate and petroleum ether as eluent to obtain the compound (3 a);
s2, slowly adding the mixture into an N, N-dimethylamide solution of the compound (3 a) in a flask filled with imidazole and tert-butyldimethyl chlorosilane, reacting for 3 hours at room temperature under the protection of argon, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (4 a);
s3, slowly adding diethyl cyanomethylphosphate into tetrahydrofuran solution of sodium hydride under the condition of ice bath in an argon protection environment, adding the compound (4 a), carrying out reflux reaction at 68 ℃ overnight, carrying out vacuum spin-drying solvent after the reaction is finished, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound (5 a);
s4, slowly adding a hexane solution of diisobutyl aluminum hydride into a dichloromethane solution of the compound (5 a), reacting for a period of time at the temperature of 78 ℃ below zero under the protection of argon, adding a certain amount of dichloromethane and water for quenching at the temperature of 0 ℃, carrying out suction filtration after the reaction is finished, extracting filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (6 a);
s5, removing dimethyl tertiary butyl silicon based from the compound (6 a) through acid hydrolysis, extracting with dichloromethane, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (7 a);
s6, slowly adding the mixture into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 3, 5-bis (benzyloxy) benzoic acid or 3, 5-bis ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid or 3, 5-bis ((perfluorophenyl) methoxy) benzoic acid), reacting for a period of time at 0 ℃ and in a protective atmosphere, slowly adding the dichloromethane solution of the compound (7 a), refluxing at 40 ℃ for overnight, extracting an organic phase with dichloromethane, evaporating the solvent, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (8 a-8 c);
s7, reacting the compound (8 a-8 c) with a receptor molecule under the protection of argon at 65 ℃, concentrating a product, purifying by silica gel chromatography, and eluting with ethyl acetate and petroleum ether to obtain the chromophore H1-H3;
wherein the acceptor molecule is 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile.
More preferably, the method for synthesizing H4 specifically comprises the following steps:
p1, slowly dissolving metallic sodium in ethanol under the protection of argon, adding 2-mercaptoethanol under the ice bath condition, adding the compound (1) for reacting for 1 hour after fully mixing and stirring, adding the compound (2 b), refluxing at 65 ℃ overnight, extracting and concentrating with ethyl acetate after the reaction is finished, purifying by silica gel chromatography, and using ethyl acetate and petroleum ether as eluent to obtain the compound (3 b);
p2, slowly adding the mixture into an N, N-dimethylamide solution of the compound (3 b) in a flask filled with imidazole and tert-butyldimethyl chlorosilane, reacting for 3 hours at room temperature under the protection of argon, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (4 b);
p3, slowly adding diethyl cyanomethylphosphate into tetrahydrofuran solution of sodium hydride under the condition of ice bath in an argon protection environment, adding the compound (4 b), carrying out reflux reaction at 65 ℃ overnight, carrying out vacuum spin-drying on a solvent after the reaction is finished, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound (5 b);
p4, slowly adding a hexane solution of diisobutyl aluminum hydride into a dichloromethane solution of the compound (5 b), reacting for a period of time at the temperature of minus 78 ℃ under the protection of argon, adding a certain amount of dichloromethane and water for quenching at the temperature of 0 ℃, carrying out suction filtration after the reaction is finished, extracting filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (6 b);
p5, removing tert-butyl diphenyl chlorosilane protecting group of the compound (6 b) through alkali hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound (7 b);
p6, slowly adding the mixture into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 3, 5-di ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid, reacting for a period of time at 0 ℃ under a protective atmosphere, slowly adding the dichloromethane solution of the compound (7 b), heating and refluxing the mixture for reaction, extracting an organic phase by using dichloromethane, evaporating the solvent, purifying by using silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound (8 d);
p7, removing the (2-tetrahydropyran) protecting group of the compound (8 d) through acid hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (9);
p8, slowly adding the mixture into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 6,6' - ((ethane-1, 1-triacyltris (benzene-4, 1-diacyl)) tris (oxy)) tricarboxylic acid, reacting for a period of time at 0 ℃ under a protective atmosphere, slowly adding the dichloromethane solution of the compound (9), heating and refluxing the reaction, extracting an organic phase with dichloromethane, removing the solvent by spin drying, purifying by silica gel chromatography, and purifying by taking dichloromethane and ethyl acetate as eluent to obtain a compound (10);
p9, the compound (10) reacts with receptor molecules under the protection of argon, products are concentrated and purified through silica gel chromatography, and ethyl acetate and petroleum ether are used as eluent to obtain the chromophore H4; wherein the acceptor molecule is 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile.
In a third aspect, the present invention provides the use of said organic optical nonlinear chromophores H1, H2, H3 and H4 based on a single donor self-assembled structure, in particular as electro-optic materials and in electro-optic modems.
The application of preparing the chromophore into an electro-optical film is that the chromophore is dissolved in re-steamed 1, 2-trichloroethane, the dissolved chromophore solution is filtered by a PTFE filter with the thickness of 0.2mm, the filtered solution is coated on an ITO glass substrate in a rotating way, and the solvent is removed to obtain the electro-optical film.
The beneficial effects of the invention are as follows:
1. the invention provides a new self-assembled single donor structure. Four dendritic macromolecules H1, H2, H3 and HLD1 were synthesized by introducing aromatic dendrites (HD), trifluorobenzene dendrites (TFD), pentafluorophenyl dendrites (PFD) and Anthracyclines (AH) into the donor and bridge ends of push-pull tetraene chromophores. In addition, a tri-branched trifluorobenzene dendrimer containing multichromophore H4 is also synthesized. The self-assembly of supermolecules by pi-pi interactions of HD-PFD/PFD-AH/TFD-TFD minimizes dipole-dipole interactions of chromophores at high loading densities and maximizes the order of decentration of chromophores. Higher polarization efficiency and EO coefficient are obtained through a supermolecule self-assembly strategy of dendritic or multichromophoric structures and pi-pi stacking of fluoroaromatics and aromatic hydrocarbons.
2. The invention also provides a series of novel chromophore structures for intermolecular assembly, and pure films containing 1:1H1:H3, 1:2H3:HLD 1 and H4 respectively obtain larger r at 1310nm 33 (328, 317 and 279 pm/V). In addition, non-covalent crosslinks formed by pi-pi stacking between chromophores may beTo improve the long term alignment stability of the material. After 1000 hours of room temperature annealing, the initial electro-optic coefficient of the electrode self-assembled film can be maintained above 95%.
According to DFT theoretical calculation, the chromophore has higher hyperpolarizability, and besides the large first-order hyperpolarizability, the special structure of the functional self-assembly group isolated intermolecular interaction also has large space effect, so that the chromophore has higher polarization efficiency.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a structural general formula of chromophores H1-H3 prepared in example 1 of the present invention;
FIG. 2 is a specific structural formula of chromophores H1-H3 prepared in example 1 of the present invention;
FIG. 3 is a synthetic route for chromophores H1-H3 prepared in example 1 of the present invention;
FIG. 4 is a structural formula of chromophore H4 prepared in example 2 of the present invention;
FIG. 5 is a synthetic route for chromophore H4 prepared in example 2 of the present invention;
FIG. 6 is a thermogravimetric plot of chromophores H1-H4 prepared in examples 1 and 2 of the present invention;
FIG. 7 is a DSC plot of chromophores H1-H4 prepared in example 1 and example 2 of the present invention;
FIG. 8 is an ultraviolet-visible spectrum of chromophores H1-H4 prepared in example 1 and example 2 of the present invention in chloroform solvent;
FIG. 9 is a graph of the ultraviolet-visible spectrum of the chromophores H1-H4, H1-H3 mixture, H3-HLD1 mixture in an electro-optic film prepared in example 1 and example 2 of the present invention;
FIG. 10 is a graph of ultraviolet spectroscope of chromophores H1-H4 prepared in example 1 and example 2 of the present invention in different solvents;
FIG. 11 is the theoretical calculated energy level results for chromophores H1-H4 prepared in example 1 and example 2 of the present invention;
FIG. 12 is a graph of the electro-optic coefficient versus molecular density for chromophores H1-H4 prepared in example 1 and example 2 of the present invention;
FIG. 13 is a polarization efficiency curve (r) of chromophores H1-H4 prepared in examples 1 and 2 according to the present invention as a function of electric field 33 Values).
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
An organic optical nonlinear chromophore based on a single-donor self-assembled structure comprises H1-H3, the structure of which is shown in figure 4, and the chromophore H4 shows good solubility in common organic solvents, such as ethyl acetate, ethanol, acetone and the like.
The preparation process comprises the synthesis of chromophore H4, and comprises the following steps:
p1, under the condition of argon gas atmosphere and ice bath, adding metal sodium (88.23 mmol,2.0 g) into a double-neck flask, dissolving with proper amount of ethanol, adding 2-mercaptoethanol (88.23 mmol,6.89g,7.65 mL), adding compound 1 (132.35 mmol,20.68 g) after 20min, adding compound 2b (88.23 mmol,23.23 g) dissolved with proper amount of ethanol after 1h, refluxing at 65 ℃, standing overnight, extracting with EA, spinning through a chromatographic column, and obtaining compound 3b (30.30 g,65.9 mmol) with eluent ratio of 1:8-1:3 (EA: PE), wherein the yield is: 74.7% of a red oily liquid;
MS(MALDI)(M + ,C 26 H 37 NO 4 S):calcd:459.24；found:459.25. 1 H NMR(600MHz,CDCl 3 )δ7.92(d,J＝16.2Hz,1H,CH),7.46(d,J＝8.9Hz,2H,ArH),7.07(d,J＝16.1Hz,1H,CH),6.71(d,J＝8.9Hz,2H,ArH),4.58–4.56(m,1H,OCH),3.95–3.85(m,2H,NCH 2 ),3.67–3.57(m,6H,OCH 2 ),3.06(s,3H,NCH 3 ),2.83–2.80(m,2H,SCH 2 ),2.64(s,2H,CH 2 ),2.44(s,2H,CH 2 ),1.82–1.75(m,2H,CH 2 ),1.72–1.64(m,2H,CH 2 ),1.59–1.55(m,2H,CH 2 ),1.08(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ197.5,160.6,150.4,138.8,129.6,126.9,123.9,122.9,111.9,99.0,64.7,62.2,60.2,52.2,51.7,41.4,39.0,32.4,30.6,28.4,25.4,19.3.
p2, imidazole (79.08 mmol,5.38 g) was added to a two-necked flask under argon atmosphere, tert-butyldiphenylchlorosilane (79.08 mmol,21.73 g) and then compound 3b (65.9 mmol,30.30 g) dissolved in a proper amount of DMF was added to react for 3 hours at room temperature, after spinning dry, extracted with EA, spun dry through a chromatographic column, and the eluent ratio was 1:10-1:5 (EA: PE) to give compound 4b (31.32 g,44.87 mmol) in the following yield: 68.1% as a red oily liquid;
MS(MALDI)(M + ,C 42 H 55 NO 4 SSi):calcd:697.36；found:697.15. 1 H NMR(600MHz,CDCl 3 )δ7.92(d,J＝16.2Hz,1H,CH),7.67-7.64(m,4H,ArH),7.46–7.38(m,4H,ArH),7.37-7.33(m,4H,ArH),6.99(d,J＝16.2Hz,1H,CH),6.69(d,J＝8.9Hz,2H,ArH),4.62–4.60(m,1H,OCH),3.77(t,J＝6.8Hz,2H,NCH 2 ),3.97–3.79(m,2H,OCH 2 ),3.65-3.62(m,2H,OCH 2 ),3.62–3.47(m,2H,OCH 2 ),3.08(s,3H,NCH 3 ),2.97(t,J＝6.8Hz,2H,SCH 2 ),2.58(s,2H,CH 2 ),2.36(s,2H,CH 2 ),1.87–1.77(m,2H,CH 2 ),1.64–1.56(m,2H,CH 2 ),1.55–1.49(m,2H,CH 2 ),1.05(m,15H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ195.8,157.8,150.1,137.2,135.6,133.7,129.6,129.3,127.7,123.6,111.9,99.0,64.8,63.5,62.2,52.2,51.9,41.3,39.1,36.3,32.2,30.6,28.4,26.9,25.4,19.3.
p3, under argon atmosphere, sodium hydride (60%, 189.0mmol,7.17 g) was added to a two-necked flask, dissolved in an appropriate amount of THF, diethyl cyanomethylphosphonate (189.0 mmol,33.65 g) was added dropwise, and when the solution became clear, compound 4b (47.5 mmol,33.15 g) dissolved in THF was added, and after refluxing overnight at 68℃the solvent was dried, extracted with EA, purified by a column chromatography, eluent ratio 1:15-1:6 (EA: PE) to give Compound 5b (23.13 g,32.1 mmol) in the following yield: 67.5% of a red oily liquid;
MS(MALDI)(M + ,C 44 H 56 N 2 O 3 SSi):calcd:720.37；found:720.22. 1 H NMR(600MHz,CDCl 3 )δ7.84(d,J＝16.2Hz,1H,CH),7.67–7.63(m,4H,ArH),7.45–7.36(m,8H,ArH),6.84(d,J＝16.2Hz,1H,CH),6.69(d,J＝8.9Hz,2H,ArH),6.20(d,J＝14.8Hz,1H,CH),4.62–4.60(m,1H,OCH),3.96–3.80(m,2H,NCH 2 ),3.74(t,J＝6.8Hz,2H,OCH 2 ),3.66–3.50(m,4H,OCH 2 ),3.07(s,3H,NCH 3 ),2.73(t,J＝6.8Hz,2H,SCH 2 ),2.51(s,2H,CH 2 ),2.42(s,2H,CH 2 ),1.85–1.70(m,2H,CH 2 ),1.62–1.58(m,2H,CH 2 ),1.55–1.50(m,2H,CH 2 ),1.07(s,9H,CH 3 ),0.98(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ158.5,149.7,149.1,135.5,134.9,133.5,129.7,128.8,127.7,125.9,124.1,119.3,99.0,94.6,64.8,63.1,62.2,52.3,43.4,41.6,39.1,37.6,30.6,30.1,28.0,26.9,25.4,19.4,19.2.
p4, compound 5b (32.10 mmol,23.13 g) dissolved in DCM was added to a two-necked flask under argon atmosphere, diisobutylaluminum hydride (1.0M, 64.20mmol,64.20 mL) was added dropwise at-78℃and reacted at low temperature for 3 hours, 10mL of DCM and 10mL of water were slowly added at 0℃and quenched for 1 hour, extracted with DCM, purified by a chromatographic column after spinning the solvent, eluent ratio was 1:10-1:5 (EA: PE), and Compound 6b (18.91 g,26.12 mmol) was obtained in the following yield: 81.4% as dark red oily liquid;
MS(MALDI)(M + ,C 44 H 57 NO 4 SSi):calcd:723.38；found:723.40. 1 H NMR(600MHz,CDCl 3 )δ10.12(d,J＝8.0Hz,1H,CHO),7.95(d,J＝16.2Hz,1H,CH),7.63(d,J＝6.7Hz,4H,ArH),7.42–7.39(m,4H,ArH),7.35–7.33(m,4H,ArH,CH),6.97(d,J＝8.0Hz,1H,ArH),6.84(d,J＝16.2Hz,1H,CH),6.68(d,J＝8.9Hz,1H,CH),4.62–4.60(m,1H,OCH),3.96–3.80(m,2H,NCH 2 ),3.76(t,J＝7.0Hz,2H,OCH 2 ),3.65–3.50(m,4H,OCH 2 ),3.07(s,3H,NCH 3 ),2.74(t,J＝7.0Hz,2H,SCH 2 ),2.65(s,2H,CH 2 ),2.45(s,2H,CH 2 ),1.83–1.70(m,2H,CH 2 ),1.62–1.57(m,2H,CH 2 ),1.56–1.50(m,2H,CH 2 ),1.05(s,9H,CH 3 ),1.00(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.6,156.6,150.1,149.7,135.5,134.8,133.6,128.2,129.6,128.9,127.7,126.8,124.8,111.9,99.0,64.8,63.3,62.2,52.3,41.6,39.8,39.0,37.3,30.6,30.0,28.3,26.9,25.4,19.4,19.2.
p5, under argon, compound 6b (22.40 mmol,16.22 g) was added to a two-necked flask, dissolved in THF, added with tetraisobutylammonium fluoride (1.0M, 44.80mmol,44.8 mL), reacted at room temperature for 1h, extracted with EA after removal of the solvent under vacuum, purified by a chromatographic column with eluent ratio of 1:6-2:1 (EA: PE) to give dark red product compound 7b (9.79 g,20.16 mmol) in 90.0% yield;
MS(MALDI)(M + ,C 28 H 39 NO 4 S):calcd:485.26；found:485.21. 1 H NMR(600MHz,CDCl 3 )δ10.13(d,J＝8.1Hz,1H,CH),7.95(d,J＝16.2Hz,1H,CHO),7.43(d,J＝8.9Hz,2H,ArH),7.00(d,J＝8.1Hz,1H,ArH),6.90(d,J＝16.1Hz,1H,CH),6.71(d,J＝8.9Hz,2H,ArH,CH),4.59–4.57(m,1H,OCH),3.93–3.81(m,2H,NCH 2 ),3.65(t,J＝6.0Hz,2H,OCH 2 ),3.61–3.46(m,4H,OCH 2 ),3.05(s,3H,NCH 3 ),2.77(t,J＝6.1Hz,2H,SCH 2 ),2.75(s,2H,CH 2 ),2.52(s,2H,CH 2 ),1.59–1.48(m,6H,CH 2 ),1.04(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.6,135.5,128.9,127.3,126.7,124.7,124.3,112.0,99.0,64.8,62.2,61.22,52.2,41.73,39.9,39.0,38.2,30.6,30.1,28.3,25.4,19.4.
p6, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (25.0 mmol,4.8 g), 4-dimethylaminopyridine (2.5 mmol,0.31 g), 3, 5-bis ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid (7.5 mmol,3.32 g) were added to a two-necked flask under an argon atmosphere, an appropriate amount of DCM was added at 0℃for 45min, and after 2h, compound 7b (6.26 mmol,3.04 g) dissolved in an appropriate amount of DCM was added, and after 2h, the reaction was refluxed overnight at 40℃and extracted with DCM, the solvent was removed under vacuum and purified by a column chromatography to give compound 8d (5.61 g,6.1 mmol) in an eluent ratio of 1:8-1:5 (EA: PE) with the following yields: 97.8% as dark red oily liquid;
MS(MALDI)(M + ,C 49 H 49 F 6 NO 7 S):calcd:909.31；found:909.21. 1 H NMR(600MHz,CDCl 3 )δ10.07(d,J＝8.1Hz,1H,CHO),7.83(d,J＝16.2Hz,1H,CH),7.23(d,J＝8.8Hz,2H,ArH),7.16(d,J＝2.4Hz,2H,ArH),6.98–6.91(m,5H,ArH,CH),6.76(d,J＝16.1Hz,1H,CH),6.67–6.65(m,1H,ArH),6.48(d,J＝8.9Hz,2H,ArH),4.88(s,4H,OCH 2 ),4.49–4.47(m,1H,OCH),4.30(t,J＝6.2Hz,2H,NCH 2 ),3.82–3.68(m,2H,OCH 2 ),3.51–3.38(m,4H,OCH 2 ),2.92(s,3H,NCH 3 ),2.88(t,J＝6.2Hz,2H,SCH 2 ),2.66(s,2H,CH 2 ),2.38(s,2H,CH 2 ),1.64–1.58(m,2H,CH 2 ),1.51–1.40(m,4H,CH 2 ),0.95(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.5,165.6,159.1,156.3,152.1(dm, 1 J FC ～253Hz),151.0,150.5(dm, 1 J FC ～260Hz),149.7,140.1(dm, 1 J FC ～246Hz),138.5(dm, 1 J FC ～258Hz),135.3,132.3,128.9,126.9,124.6,124.3,111.8,111.2,108.6,107.6,99.1,68.5,64.7,63.7,62.2,52.1,41.7,39.8,38.9,33.4,30.9,30.6,30.1,28.3,25.4,19.4.
p7, compound 8d (6.17 mmol,5.61 g) dissolved in an appropriate amount of acetone is added into a single-neck flask, 1N HCl (1N, 12.34mmol,12.34 mL) is added for reaction for 2 hours at room temperature, sodium bicarbonate is added for neutralization, after spin drying, EA is used for extraction, the mixture is spun-dried and passes through a chromatographic column, the eluent ratio is 1:6-2:1 (EA: PE), and a dark red product compound 9 (3.91 g,4.73 mmol) is obtained, wherein the yield is: 76.4%;
MS(MALDI)(M + ,C 44 H 41 F 6 NO 6 S):calcd:825.26；found:825.15.1H NMR(600MHz,CDCl 3 )δ10.17(d,J＝8.1Hz,1H,CHO),7.93(d,J＝16.2Hz,1H,CH),7.32(d,J＝8.8Hz,2H,ArH),7.26(d,J＝2.4Hz,2H,ArH),7.09–7.01(m,5H,ArH,CH),6.85(d,J＝16.2Hz,1H,CH),6.77(t,J＝2.4Hz,1H,ArH),6.60(d,J＝8.7Hz,2H,ArH),4.99(s,4H,OCH 2 ),4.40(t,J＝6.2Hz,2H,NCH 2 ),3.82(t,J＝5.7Hz,2H,OCH 2 ),3.50(t,J＝5.7Hz,2H,OCH 2 ),3.00(s,3H,NCH 3 ),2.97(t,J＝6.2Hz,2H,SCH 2 ),2.76(s,2H,CH 2 ),2.48(s,2H,CH 2 ),1.05(s,4H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.6,165.6,159.1,156.2,152.2(dm, 1 J FC ～260Hz),150.9,150.5(dm, 1 J FC ～256Hz),140.2(dm, 1 J FC ～246Hz),138.5(dm, 1 J FC ～253Hz),135.1,132.7,132.3,128.8,128.4,127.0,124.8,112.3,111.2,108.6,107.7,68.5,63.6,60.2,54.7,41.7,39.8,38.8,33.5,30.1,28.3.
p8, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (12.02 mmol,2.31 g), 4-dimethylaminopyridine (1.20 mmol,0.15 g), 6' - ((ethane-1, 1-triacyltri (benzene-4, 1-diacyl)) tris (oxy) tricarboxylic acid (0.89 mmol,0.58 g) were added to a two-necked flask under argon atmosphere, a proper amount of DCM was added at 0℃for 45mins, compound 9 (4.01 mmol,3.31 g) dissolved in a proper amount of DCM was added, after 2h, the mixture was refluxed overnight at 40℃and extracted with DCM, the solvent was removed in vacuo and then purified by a chromatographic column at an eluent ratio of 1:50-1:10 (EA: DCM) to give compound 10 (2.44 g,0.79 mmol) in 88.2% yield as a dark red oily liquid;
MS(MALDI)(M + ,C 170 H 165 F 18 N 3 O 24 S 3 ):calcd:3070.07；found:3070.14. 1 H NMR(600MHz,CDCl 3 )δ10.16(d,J＝8.0Hz,3H,CHO),7.93(d,J＝16.2Hz,3H,CH),7.33(d,J＝8.8Hz,6H,ArH),7.25(d,J＝2.3Hz,6H,ArH),7.08–7.00(m,15H,ArH,CH),6.98(d,J＝8.8Hz,6H,ArH),6.84(d,J＝16.1Hz,3H,CH),6.78–6.75(m,9H,ArH),6.58(d,J＝8.9Hz,6H,ArH),4.97(s,12H,OCH 2 ),4.40(t,J＝6.2Hz,6H,NCH 2 ),4.25(t,J＝6.0Hz,6H,OCH 2 ),3.91(t,J＝6.3Hz,6H,OCH 2 ),3.60(t,J＝6.0Hz,6H,OCH 2 ),2.99(s,9H,NCH 3 ),2.97(t,J＝6.2Hz,6H,SCH 2 ),2.75(s,6H,CH 2 ),2.47(s,6H,CH 2 ),2.30(t,J＝7.5Hz,6H,CH 2 ),2.08(d,J＝20.0Hz,3H,CH 3 ),1.78–1.73(m,6H,CH 2 ),1.68–1.62(m,6H,CH 2 ),1.50–1.43(m,6H,CH 2 ),1.04(s,18H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.5,173.5,171.2,165.5,159.1,157.0,156.2,152.1(dm, 1 J FC ～255Hz),150.9(dm, 1 J FC ～257Hz),150.5,149.4,141.7,140.1(dm, 1 J FC ～258Hz),138.5(dm, 1 J FC ～247Hz),135.1,132.8,132.3,129.6,128.9,127.3,127.0,125.1,124.7,113.5,111.9,111.2,108.6,107.6,68.6,67.5,63.7,61.2,60.4,50.7,50.6,41.7,39.8,38.6,34.1,33.5,30.7,30.1,29.0,28.3,25.7,24.6,21.1,14.2.
synthesis of chromophore H4:
compound 10 (0.32 mmol,1.01 g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (1.15 mmol,0.36 g) was added to a two-necked flask under argon atmosphere, dissolved in 5-6mL ethanol, reacted at 65 ℃ for 3H, spin-dried over chromatography column, eluent ratio 1:7-1:1 (EA: PE), chromophore H4 (0.53 g,0.13 mmol) was obtained in the following yield: 41.8%;
HRMS(ESI)(M + ,C 218 H 183 F 27 N 12 O 24 S 3 ):calcd:3962.2277；found:3962.2223. 1 H NMR(600MHz,CDCl 3 )δ7.98(d,J＝15.9Hz,6H,CH),7.63–7.49(m,15H,ArH),7.42(d,J＝12.4Hz,3H,CH),7.35(d,J＝8.9Hz,6H,ArH),7.22(d,J＝2.3Hz,6H,ArH),7.05–7.02(m,12H,ArH),6.99–6.94(m,9H,ArH,CH),6.76(t,J＝6.1Hz,9H,ArH),6.57(d,J＝8.9Hz,6H,ArH),6.48(d,J＝14.6Hz,3H,CH),4.96(s,12H,OCH 2 ),4.37(t,J＝6.2Hz,6H,NCH 2 ),4.25(t,J＝6.0Hz,6H,OCH 2 ),3.90(t,J＝6.3Hz,6H,OCH 2 ),3.62(t,J＝6.0Hz,6H,OCH 2 ),3.02(s,9H,NCH 3 ),2.95(t,J＝6.3Hz,6H,SCH 2 ),2.54–2.45(m,6H,CH 2 ),2.35–2.20(m,12H,CH 2 ),1.79–1.72(m,6H,CH 2 ),1.68–1.61(m,9H,CH 3 ,CH 2 ),1.50–1.42(m,6H,CH 2 ),0.98(s,9H,CH 3 ),0.89(s,9H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ175.4,173.5,165.4,162.9,159.1,157.0,154.2,152.2(dm, 1 J FC ～255Hz),150.5(dm, 1 J FC ～259Hz),150.1,147.3,141.7,140.2(dm, 1 J FC ～249Hz),138.5(dm, 1 J FC ～258Hz),137.79,132.7,132.1,131.4,129.9,129.7,129.2,128.3,126.8,125.0,124.7,117.3,113.5,112.0,111.2,108.7,107.4,68.5,67.5,63.5,61.1,58.4,50.6,41.7,41.1,38.7,34.1,30.4,29.0,28.6,27.8,25.7,24.6.
example 2
An organic optical nonlinear chromophore based on a single-donor self-assembled structure comprises H1-H3, the structure of which is shown in figure 2, and the chromophores H1-H3 show good solubility in common organic solvents, such as ethyl acetate, ethanol, acetone and the like.
The preparation process comprises the synthesis of chromophores H1-H3, and comprises the following steps:
s1, adding metal sodium (32.03 mmol,0.74 g) into a double-neck flask under the condition of ice bath under the argon atmosphere, dissolving with proper amount of ethanol, adding 2-mercaptoethanol (32.03 mmol,2.26 mL), adding compound 1 (32.03 mmol,4.94 g) after 20min, adding compound 2a (32.03 mmol,9.4 g) dissolved with proper amount of ethanol after 1h, refluxing the reaction at 65 ℃ for overnight, extracting with EA after spinning, spinning through a chromatographic column, and obtaining compound 3a (6.7 g,13.6 mmol) with the eluent ratio of 1:10-1:5 (EA: PE), wherein the yield is: 42.5% of a red oily liquid;
MS(MALDI)(M + ,C 27 H 43 NO 3 SSi):calcd:489.79；found:489.81. 1 H NMR(300MHz,CDCl 3 )d 7.92(d,J＝16.1Hz,1H,CH),7.46(d,J＝8.6Hz,2H,ArH),7.04(d,J＝16.1Hz,1H,CH),6.68(d,J＝8.7Hz,2H,ArH),3.80–4.02(m,4H,NCH 2 ,OCH 2 ),3.48–3.60(m,4H,OCH 2 ,SCH 2 ),3.04(s,3H,NCH 3 ),2.59(m,2H,CH 2 ),2.45(m,2H,CH 2 ),1.07(s,6H,CH 3 ),0.87(s,9H,CH 3) ,0.01(s,6H,CH 3 ). 13 C{1H}NMR(126MHz,CDCl 3 )d 197.05,160.19,149.93,138.56,129.33,127.09,126.69,123.69,122.42,111.62,60.29,60.13,54.31,51.45,40.94,38.99,38.42,31.96,28.17,25.70,17.97,5.45.
s2, imidazole (14.4 mmol,0.98 g) and tert-butyl dimethyl chlorosilane (14.4 mmol,2.17 g) are added into a double-neck flask under argon atmosphere, then a compound 3a (2.93 g,6.0 mmol) dissolved by a proper amount of DMF is added, the mixture is reacted for 3 hours at room temperature, after spinning, the mixture is extracted by EA, spun-dried and passed through a chromatographic column, and the eluent proportion is 1:10-1:7 (EA: PE), thus obtaining a compound 4a (3.02 g,5.0 mmol) with the yield: 83.3% of a red oily liquid;
MS(MALDI)(M + ,C 33 H 57 NO 3 SSi 2 ):calcd:604.05；found:603.95. 1 H NMR(300MHz,CDCl 3 )d 7.89(d,J＝16.2Hz,1H,CH),7.44(d,J＝8.6Hz,2H,ArH),6.98(d,J＝16.2Hz,1H,CH),6.66(d,J＝8.7Hz,2H,ArH),3.82–3.67(m,6H,CH 2 ),3.51(m,2H,CH 2 ),2.96–2.78(m,3H,NCH 3 ),2.59(s,2H,CH 2 ),2.39(s,2H,CH 2 ),1.06(s,6H,CH 3 ),0.91–0.77(m,18H,CH 3 ),0.08–0.02(m,12H,CH 3 ). 13 C{1H}NMR(126MHz,CDCl 3 )d 195.67,157.70,150.03,137.20,129.20,128.01,123.97,123.37,111.84,62.79,60.12,54.46,51.87,41.18,39.13,36.53,32.14,30.62,28.26,25.77,18.14,5.45,5.63.
s3, adding sodium hydride (60%, 20mmol,0.80 g) into a double-neck flask under argon atmosphere, dissolving with a proper amount of THF, dropwise adding diethyl cyanomethylphosphonate (20.0 mmol,3.54 g), adding a compound 4a (5.0 mmol,3.02 g) dissolved with THF after the solution becomes clear, refluxing at 68 ℃ overnight, extracting with EA after spinning the solvent, purifying with a chromatographic column, and obtaining a compound 5a (2.3 g,3.7 mmol) with an eluent ratio of 1:15-1:8 (EA: PE), wherein the yield is: 74, as a red oily liquid;
(M + ,C 35 H 58 N 2 O 2 SSi 2 ):calcd:627.09；found:627.13. 1 H NMR(300MHz,CDCl 3 )d 7.84(d,J＝16.1Hz,1H,CH),7.38(d,J＝8.4Hz,2H,ArH),6.83(d,J＝16.1Hz,1H,CH),6.64(d,J＝8.4Hz,2H,ArH),6.23(s,1H,CH),3.82–3.61(m,4H,CH 2 ),3.48(m,2H,CH 2 ),2.99(m,3H,NCH 3 ),2.67(m,2H,CH 2 ),2.53(s,2H,CH 2 ),2.43(s,2H,CH 2 ),0.99(s,6H,CH 3 ),0.87(m,18H,CH 3 ),0.05–0.02(m,12H,CH 3 ). 13 C{1H}NMR(126MHz,CDCl 3 )d 158.13,149.59,148.68,134.79,128.63,125.94,124.50,123.94,118.84,111.66,94.47,62.11,60.34,54.37,38.86 30.57,29.8829.53,27.84,25.76,22.51,17.99,14.01,5.45,5.61.
s4, under argon atmosphere, adding a compound 5a (3.7 mmol,2.3 g) dissolved in DCM into a double-neck flask, dropwise adding diisobutylaluminum hydride (1M, 7.4mmol,7.4 mL) at-78 ℃ for reaction for 3 hours, slowly adding 10mL of DCM and 10mL of water at 0 ℃ for quenching for 1 hour, extracting with DCM, spin-drying the solvent, purifying with a chromatographic column, and eluting with the eluent with the ratio of 1:10-1:7 (EA: PE) to obtain a compound 6a (1.54 g,2.44 mmol) with the yield of: 66, as a dark red oily liquid;
MS(MALDI)(M + ,C 35 H 59 NO 3 SSi 2 ):calcd:630.09；found:630.15. 1 H NMR(300MHz,CDCl 3 )d 10.12(d,J＝6.4Hz,1H,CHO),7.94(d,J＝16.1Hz,1H,CH),7.40(d,J＝6.8Hz,2H,ArH),6.98(d,J＝6.6Hz,1H,CH),6.85(d,J＝16.1Hz,1H,CH),6.65(d,J＝6.8Hz,2H,ArH),3.72(m,4H,CH 2 ),3.49(m,2H,CH 2 ),3.01(s,3H,NCH 3 ),2.70(s,2H,CH 2 ),2.47(s,2H,CH 2 ),2.11(s,2H,CH 2 ),1.01(s,6H,CH 3 ),0.86(m,18H,CH 3 ),0.02(s,12H,CH 3 ). 13 C{1H}NMR(126MHz,CDCl 3 )d 190.77,156.09,149.77,149.50,134.66,128.57,127.97,126.58,124.35,111.44,62.08,60.25,54.48,41.36,39.62,38.82,37.39,30.42,29.66,28.04,25.51,17.94,5.49,5.63.
s5, adding a proper amount of acetone-soluble compound 6 (12.2 mmol,7.7 g) into a single-neck flask, adding 1N HCl (1N, 48.9 mmol), reacting for 3 hours at room temperature, then neutralizing with sodium bicarbonate, performing spin-drying, extracting with EA, performing spin-drying through a chromatographic column, and obtaining a dark red product compound 7a (3.4 g,8.8 mmol) with the eluent ratio of 1:5-2:1 (EA: PE), wherein the yield is: 72.0%;
MS(MALDI)(M + ,C 23 H 31 NO 3 S):calcd:401.56；found:401.78. 1 H NMR(300MHz,CDCl 3 )d 10.08(d,J＝8.1Hz,1H,CHO),7.94(d,J＝16.2Hz,1H,CH),7.42(d,J＝8.8Hz,2H,ArH),6.97(d,J＝8.1Hz,1H,CH),6.86(d,J＝16.2Hz,1H,CH),6.72(d,J＝8.8Hz,2H,ArH),3.81(m,2H,OH),3.62(m,2H,NCH 2 ),3.52(m,2H,OCH 2 ),3.02(s,3H,NCH 3 ),2.76(m,4H,SCH 2 ,OCH 2 ),2.49(m,2H,CH2),2.31(m,2H,CH 2 ),1.02(s,6H,CH 3 ). 13 C{1H}NMR(126MHz,CDCl 3 )d 191.79 157.37,150.83,150.17,135.29,128.85 127.50,126.49,124.92,124.52,112.12,61.06,59.86,54.54,41.95,39.78,38.74,38.02,29.97,28.17.
s6, adding 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (3.28 mmol,0.63 g), 4-dimethylaminopyridine (0.33 mmol,0.040 g) and 3, 4-bis (benzyloxy) benzoic acid (1.63 mmol,0.55 g) into a two-neck flask under argon atmosphere, adding a proper amount of DCM at 0 ℃ for 45min, adding a compound 7a (0.82 mmol,0.33 g) dissolved by the proper amount of DCM after 2h, refluxing overnight at 40 ℃, extracting by the DCM, spinning through a chromatographic column, and obtaining a compound 8a (0.70 mmol,0.72 g) by eluent with the ratio of 1:8-1:5 (EA: PE) with the yield: 85% as dark red oily liquid;
MS(MALDI)(M + ,C 65 H 63 NO 9 S):calcd:1033.42；found:1033.36. 1 H NMR(600MHz,CDCl 3 )δ10.18(d,J＝8.0Hz,1H,CHO),7.94(d,J＝16.2Hz,1H,CH),7.44–7.31(m,24H,ArH,CH),7.24(d,J＝2.3Hz,2H,ArH),7.03(d,J＝8.0Hz,1H,ArH),6.81(t,J＝2.4Hz,3H,ArH),6.62(d,J＝8.9Hz,2H,ArH),5.02(d,J＝5.2Hz,8H,OCH 2 ),4.45(t,J＝5.9Hz,2H,NCH 2 ),4.37(t,J＝6.3Hz,2H,OCH 2 ),3.70(t,J＝5.8Hz,2H,OCH 2 ),3.00(s,3H,NCH 3 ),2.95(t,J＝6.3Hz,2H,SCH 2 ),2.76(s,2H,CH 2 ),2.44(s,2H,CH 2 ),1.05(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.6,166.2,165.9,159.8,156.1,151.1,149.4,136.5,135.1,131.9,131.7,128.9,128.6,128.1,127.6,127.2,126.9,125.2,124.8,111.9,108.4,107.5,107.3,70.3,63.6,62.3,50.7,41.6,39.9,38.6,33.3,30.1,28.4,26.9.
s7, adding 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (2.76 mmol,0.53 g), 4-dimethylaminopyridine (0.28 mmol,0.034 g), 3, 5-bis ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid (1.4 mmol,0.61 g) into a two-necked flask under argon atmosphere, adding a proper amount of DCM at 0 ℃, after 45mins, adding a proper amount of DCM-dissolved compound 7a (0.69 mmol,0.28 g), after 2h, refluxing the reaction at 40 ℃, extracting with DCM, removing the solvent under vacuum, purifying with a chromatographic column, wherein the eluent ratio is 1:8-1:5 (EA: PE), and obtaining a compound 8b (0.58 g,0.48 mmol) with the following yield: 69.6% as dark red oily liquid;
MS(MALDI)(M + ,C 65 H 51 F 12 NO 9 S):calcd:1250.31；found:1250.32. 1 H NMR(600MHz,CDCl 3 )δ10.18(d,J＝8.0Hz,1H,CHO),7.90(d,J＝16.2Hz,1H,CH),7.34(d,J＝8.8Hz,2H,ArH),7.25(d,J＝2.4Hz,2H,ArH),7.17(d,J＝2.4Hz,2H,ArH),7.06–7.01(m,9H,ArH,CH),6.79(d,J＝16.2Hz,1H,CH),6.76(t,J＝2.4Hz,1H,ArH),6.72(t,J＝2.3Hz,1H,ArH),6.66(d,J＝8.9Hz,1H,ArH),4.97(s,4H,OCH 2 ),4.93(s,4H,OCH 2 ),4.49(t,J＝5.8Hz,2H,NCH 2 ),4.39(t,J＝6.2Hz,2H,OCH 2 ),3.74(t,J＝5.8Hz,2H,OCH 2 ),3.05(s,3H,NCH 3 ),2.96(t,J＝6.2Hz,2H,SCH 2 ),2.76(s,2H,CH 2 ),2.43(s,2H,CH 2 ),1.05(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.5,165.8,165.5,159.1,156.1,152.2(dm, 1 J FC ～260Hz),150.5(dm, 1 J FC ～246Hz),149.5,140.2(dm, 1 J FC ～258Hz),138.5(dm, 1 J FC ～257Hz),134.7,132.6,132.1,128.9,128.4,127.6,127.1,125.2,124.9,111.9,111.2,108.6,107.5,68.5,63.6,62.4,50.6,41.6,39.8,38.3,33.5,30.0,28.3.
s8, adding 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (2.92 mmol,0.56 g), 4-dimethylaminopyridine (0.30 mmol,0.036 g) and 3, 5-bis ((perfluorophenyl) methoxy) benzoic acid (1.5 mmol,0.75 g) into a two-neck flask under argon atmosphere, adding a proper amount of DCM at 0 ℃, after 45min, adding a proper amount of DCM-dissolved compound 7a (0.73 mmol,0.29 g), after 2h, refluxing overnight at 40 ℃, extracting with DCM, spin-drying a chromatographic column, eluent ratio of 1:8-1:5 (EA: PE), and obtaining a compound 8c (0.55 g,0.40 mmol) with the yield: 54.8% as dark red oily liquid;
MS(MALDI)(M + ,C 65 H 43 F 20 NO 9 S):calcd:1393.23；found:1393.33. 1 H NMR(600MHz,CDCl 3 )δ10.18(d,J＝8.0Hz,1H,CHO),7.88(d,J＝16.1Hz,1H,CH),7.34–7.29(m,4H,ArH),7.27–7.23(m,2H,ArH),7.01(d,J＝8.0Hz,1H,ArH),6.81–6.72(m,3H,ArH,CH),6.64(d,J＝8.8Hz,2H,ArH),5.09(s,4H,OCH 2 ),5.02(s,4H,OCH 2 ),4.50(t,J＝5.8Hz,2H,NCH 2 ),4.38(t,J＝6.3Hz,2H,OCH 2 ),3.78(t,J＝5.8Hz,2H,OCH 2 ),3.07(s,3H,NCH 3 ),2.96(t,J＝6.3Hz,2H,SCH 2 ),2.76(s,2H,CH 2 ),2.44(s,2H,CH 2 ),1.05(s,6H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ191.6,165.9,165.5,159.2,159.0,156.2,156.0,149.5,146.7(dm, 1 J FC ～253Hz),145.1(dm, 1 J FC ～260Hz),141.6(dm, 1 J FC ～257Hz),139.8(dm, 1 J FC ～245Hz),139.2,134.9,132.2,132.0,128.8,127.3,126.9,125.1,124.6,111.8,108.6,107.6,63.7,62.3,62.1,57.9,50.4,41.5,39.8,38.3,33.2,30.9,30.0,28.3.
synthesis of chromophore H1:
in a two-necked flask, compound 8a (0.34 mmol,0.35 g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.41 mmol,0.13 g) was added under argon atmosphere, dissolved in 5-6mL ethanol, reacted at 65℃for 3H, dried by spin through chromatography column with eluent ratio of 1:10-1:3 (EA: PE) to give chromophore H1 (0F) (0.26 g,0.20 mmol) in the following yield: 58.8%;
HRMS(ESI)(M + ,C 81 H 69 F 3 N 4 O 9 S):calcd:1331.4816；found:1331.4815. 1 H NMR(600MHz,CDCl 3 )δ7.95(d,J＝16.0Hz,1H,CH),7.55–7.48(m,5H,ArH),7.44–7.33(m,22H,ArH),7.32–7.28(m,2H,ArH),7.22(d,J＝2.3Hz,2H,ArH),7.20(d,J＝2.3Hz,2H,ArH),6.89(d,J＝16.0Hz,1H,CH),6.82–6.75(m,2H,CH),6.60(d,J＝9.0Hz,2H,ArH),6.47(d,J＝14.6Hz,1H,CH),4.99(s,8H,OCH 2 ),4.43(t,J＝5.8Hz,2H,NCH 2 ),4.32(t,J＝6.2Hz,2H,OCH 2 ),3.69(t,J＝5.8Hz,2H,OCH 2 ),3.00(s,3H,NCH 3 ),2.91(t,J＝6.3Hz,2H,SCH 2 ),2.44(s,2H,CH 2 ),2.34–2.21(m,2H,CH 2 ),0.96(s,3H,CH 3 ),0.88(s,3H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ175.6,166.2,165.9,162.8,159.8,157.2,154.5,150.1,147.3,137.9,136.4,131.7,131.4,129.9,129.7,129.2,128.7,128.2,127.6,126.8,125.1,124.7,117.2,112.0,110.7,108.6,108.4,107.5,107.1,70.3,63.4,62.2,58.2,50.6,41.7,41.1,38.7,34.2,30.4,29.7,29.3,28.6,27.9.
synthesis of chromophore H2:
in a two-necked flask, compound 8b (0.52 mmol,0.65 g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.62 mmol,0.20 g) was added under argon atmosphere, dissolved in 5-6mL ethanol, reacted at 65℃for 3H, dried by spin through chromatography column with eluent ratio 1:10-1:3 (EA: PE) to give chromophore H2 (3F) (0.43 g,0.28 mmol) in the following yield: 53.8%;
HRMS(ESI)(M + ,C 81 H 57 F 15 N 4 O 9 S):calcd:1547.3685；found:1547.3687. 1 H NMR(600MHz,CDCl 3 )δ7.95(d,J＝16.0Hz,2H,CH),7.60–7.50(m,5H,ArH),7.42(d,J＝12.3Hz,1H,CH),7.36(d,J＝8.9Hz,2H,ArH),7.22(d,J＝2.3Hz,2H,ArH),7.16(d,J＝2.4Hz,2H,ArH),7.05–6.99(m,8H,ArH),6.91(d,J＝16.0Hz,1H,CH),6.76(t,J＝2.3Hz,1H,ArH),6.72(t,J＝2.3Hz,1H,ArH),6.65(d,J＝9.0Hz,2H,ArH),6.50(d,J＝14.7Hz,1H,CH),4.95(s,4H,OCH 2 ),4.94(s,4H,OCH 2 ),4.49(t,J＝5.8Hz,2H,NCH 2 ),4.36(t,J＝6.2Hz,2H,OCH 2 ),3.76(t,J＝5.8Hz,2H,OCH 2 ),3.07(s,3H,NCH 3 ),2.94(t,J＝6.3Hz,2H,SCH 2 ),2.45(s,2H,CH 2 ),2.31(s,2H,CH 2 ),0.99(s,3H,CH 3 ),0.89(s,3H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ175.4,165.8,165.4,163.0,159.1,156.8,153.8,152.2(dm, 1 J FC ～257Hz),150.5(dm, 1 J FC ～245Hz),150.1,147.3,140.2(dm, 1 J FC ～260Hz),138.5(dm, 1 J FC ～253Hz),137.3,132.6,132.1,132.0,131.4,129.9,129.7,129.6,129.3,128.3,126.8,125.1,124.8,117.5,112.0,111.2,110.6,108.7,108.6,107.5,107.3,68.5,63.5,62.3,58.5,50.6,41.7,41.0,38.5,34.1,31.9,30.3,29.7,29.3,28.6,27.7,27.2,22.7,14.1.
synthesis of chromophore H3:
in a two-necked flask, compound 8c (0.38 mmol,0.53 g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.38 mmol,0.13 g) was added under argon atmosphere, dissolved in 5-6mL ethanol, reacted at 65℃for 3H, dried by spin through chromatography column with eluent ratio of 1:10-1:3 (EA: PE) to give chromophore H3 (5F) (0.33 g,0.20 mmol) in the following yield: 52.6%;
HRMS(ESI)(M + ,C 81 H 49 F 23 N 4 O 9 S):calcd:1691.2931；found:1691.2937. 1 H NMR(600MHz,CDCl 3 )δ7.93(d,J＝16.0Hz,1H,CH),7.59–7.49(m,5H,ArH),7.44(d,J＝12.3Hz,1H,CH),7.33(d,J＝9.0Hz,3H,ArH),7.28-7.22(m,4H,ArH),6.89(d,J＝15.9Hz,1H,CH),6.82–6.70(m,2H,ArH,CH),6.65(d,J＝8.8Hz,2H,ArH),6.51(d,J＝14.6Hz,1H,CH),5.07(s,4H,OCH 2 ),5.02(s,4H,OCH 2 ),4.51(t,J＝5.7Hz,2H,NCH 2 ),4.36(t,J＝6.2Hz,2H,OCH 2 ),3.80(t,J＝5.8Hz,2H,OCH 2 ),3.09(s,3H,NCH 3 ),2.94(t,J＝5.6Hz,2H,SCH 2 ),2.46(s,2H,CH 2 ),2.33(s,2H,CH 2 ),0.99(s,3H,CH 3 ),0.90(s,3H,CH 3 ). 13 C NMR(151MHz,CDCl 3 )δ175.5,165.8,165.5,162.9,159.2,159.0,150.2,147.3,146.7(dm, 1 J FC ～260Hz),145.1(dm, 1 J FC ～258Hz),141.6(dm, 1 J FC ～246Hz),139.9(dm, 1 J FC ～254Hz),139.6,137.48,132.0,131.4,129.8,129.4,129.2,128.3,126.8,125.0,124.6,117.28,111.9,111.1,110.7,108.9,108.6,107.5,107.3,63.5,62.1,60.4,58.3,57.9,50.4,41.6,41.1,38.4,34.0,30.3,29.3,28.5,27.8,21.1,14.2.
in order to more clearly illustrate the invention, the invention also performs the following demonstration experiments on chromophores H1-H4 prepared in the examples:
(1) Spectral absorption characteristics and thermal stability
(1) The thermal stability of chromophores H1-H4 is characterized by a thermogravimetric curve, see FIG. 6;
(2) the UV-visible spectrum of chromophores H1-H4 in chloroform solution is shown in FIG. 8;
(3) the UV-visible spectrum of chromophores H1-H4 in the film is shown in FIG. 9;
wherein, the main parameters in the spectral absorption characteristics and the thermal stability of the four chromophore molecules are shown in table 1;
TABLE 1 spectral absorption and thermal stability parameters for four chromophore molecules
Wherein lambda is max a 、λ max b 、λ max d Is the measurement result of the chromophore molecules in chloroform, 1, 4-dioxane and electro-optical film respectively, delta lambda c Is lambda max a 、λ max b A difference between them;
the chromophores H1-H4 have similar color development offset behaviors, and color development offset occurs between 52nm and 57 nm. The maximum absorption wavelengths of the chromophores in chloroform were 749nm, 728nm, 742nm and 739nm, respectively, in different solvents. From the near maximum absorption wavelength data of chromophores H1-H4 in chloroform, it can be seen that the addition of different self-assembled spacer groups does not hinder the charge transfer of the effective molecules in the conjugated structure. Their absorption wavelengths are above 725nm, which generally means that they have a large primary hyperpolarizability.
The maximum absorption wavelength (lambda) of chromophores H1-H4 in the film max ) 773nm, 759nm and 755nm, respectively, unlike in solution. This phenomenon suggests that there may be different interactions between chromophores composed of different separating groups and polymers.
(2) Energy level calculation
The charge transfer interactions within the chromophore can be calculated by the energy gap difference between the HOMO-LUMO molecular orbitals. To further analyze the composition of HOMO-LUMO and the deep information of the leading-edge orbits, the inventors run a multiswn program using Ros-Schuis (SCPA) partitioning and DFT computation;
chromophores are divided into three parts: donor, pi-bridge and acceptor, and calculate the percentage contribution: for the four chromophores H1-H4, HOMO is predominantly stabilised by the contributions of the donor (42.90% -45.38%) and pi-bridge (32.15-33.73%), while LUMO is predominantly stabilised by the contributions of the acceptor (42.48% -44.02%) and pi-bridge (40.65% -40.95%).
DFT calculations were used to calculate the HOMO-LUMO energy gap (ΔE), see FIG. 11, for the ΔE of chromophores H1-H4 of 1.958eV,1.981eV,1.977eV and 1.938eV, respectively. These four chromophores have similar spacer groups attached to the electron bridge and donor, respectively. These chromophores all have similar conjugated structures, and it can be seen from the uv absorbance data that the substituted steric hindrance groups do not affect the conjugated structure.
(3) Electro-optic coefficient
The invention compares the conversion of microscopic hyperpolarizability of four chromophores with different isolated functional groups to macroscopic r 33 Efficiency of the values. First, chromophores are prepared into electro-optic films: the above chromophores were dissolved in re-evaporated 1, 2-trichloroethane, the dissolved chromophores solution was filtered through a 0.2mm PTFE filter, the filtered solution was spin-coated on an ITO glass substrate, and after removing the solvent, the synthetic film of the chromophores composite was heated overnight in vacuum at 50 ℃ to ensure removal of residual solvent. The contact polarization process is at the glass transition temperature of the electro-optic material(T g ) The above is carried out at a temperature of 5-10deg.C. The electro-optic coefficient r of the polarized film at 1310nm wavelength is calculated by adopting a Teng-Man simple reflection method 33 The method uses a thin ITO electrode with low reflectivity and good transparency to minimize multiple reflections. As previously mentioned, controlling the geometry and delocalization of molecules by introducing sterically isolating groups in the chromophore may be an effective method of minimizing interactions between chromophores, and therefore these methods may have significant advantages, and may best convert the β value to r 33 Values, thereby increasing macroscopic electro-optic activity.
(4) Assembled device performance
Measuring each performance index of the four small molecular chromophores assembled into a device, and the results are shown in Table 2;
TABLE 2 Performance index for several small molecule chromophore assembled devices
Average polarization efficiency (r 33 Polarization field or r 33 /E p ) 1.63.+ -. 0.07, 2.26.+ -. 0.08, 1.36.+ -. 0.07 and 2.76.+ -. 0.08nm, respectively 2 /V 2 Higher than the host guest polymeric material as shown in fig. 13. In the case of similar primary hyperpolarizabilities, the difference in polarization efficiency between H1 and H3 is mainly due to the number of chromophores per unit volume, although the concentration of chromophores in the electro-optic film H2 is low, its polarization efficiency is high. H3 is subjected to pi-pi superposition through an electrostatic mechanism, and a high polarization induction sequence is obtained. Due to the multichromophore structure, the polarization efficiency of H4 is further improved to 2.76+/-0.08 nm 2 /V 2 : the three chromophore molecules are connected to the middle core in a covalent bond mode, so that the chromophore molecules can be ensured to freely rotate under the action of an electric field, the chromophores can be effectively separated, and the electrostatic interaction between the molecules is weakened. Of course, increasing the polarization efficiency of chromophore H4 also benefits from pi-pi stacking of trifluorobenzene, resulting in a highly polarization-induced order.
To evaluate the effect of the self-assembly effects of HD-PFD and PFD-AH on EO performance, basic devices of 1:1h1:h3 and 1:2h3:hld 1 were fabricated, wherein chromophore HLD1 was synthesized in known literature. And performing polarization treatment to calculate polarization efficiency.
Average polarization efficiencies of chromophore mixing ratios 1:1h1:h3 and 1:2h3:hld 1 were 3.26±0.10 and 3.17±0.09nm, respectively 2 /V 2 Significantly higher than the chromophores H1 and HLD1. Intermolecular interactions between the electronegative aromatic benzene ring groups and the electropositive pentafluorophenyl groups or pi-pi stacking of trifluorobenzene contribute to achieving a high polarization-induced order. When the temperature rises to the glass transition temperature of the electro-optic film, the molecular arrangement formed by the intermolecular hydrogen bonds will be dissociated by the electric field polarization. Then, under the action of an electric field, the electro-optical film is gradually cooled to room temperature, and polarization orientation under the action of the electric field is fixed through a non-covalent cross-linking network, so that the order of eccentric chromophores is enhanced and stabilized. Optimal r for 1:1H1:H3 and 1:2H3:HLD 1 33 The values were 328 and 317pm/V, respectively, much higher than the chromophore of the previously reported diethylphenyl donor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The self-assembled organic optical nonlinear chromophore is characterized in that the chromophore molecule is H4, and the structural formula is shown as follows:
2. a method of synthesizing a self-assembled organic optical nonlinear chromophore according to claim 1, wherein said method of synthesizing chromophore H4 comprises the steps of:
p1, 4- (methyl (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethyl) amino) benzaldehyde and a compound 1 are subjected to Knoevenagel condensation reaction under the conditions of sodium ethoxide and 2-mercaptoethanol to obtain a compound 3b;
p2, connecting a tert-butyl diphenyl silicon-based protecting group to the alcoholic hydroxyl of the compound 3b to obtain a compound 4b;
p3, the compound 4b and diethyl cyanomethylphosphate react through a Wittig-Hornor reaction to obtain a compound 5b;
p4, reducing cyano groups in the compound 5b through diisobutylaluminum hydride to obtain aldehyde compound 6b;
p5, removing the protecting group of the compound 6b through alkaline hydrolysis to obtain a compound 7b;
p6, connecting a self-assembled isolating group on the alcoholic hydroxyl group of the compound 7b through Steglich esterification to obtain a compound 8d;
p7, the compound 8d is subjected to acid hydrolysis to obtain a compound 9;
p8, connecting a tri-furcation isolation group on the alcoholic hydroxyl group of the compound 9 through Steglich esterification to obtain a compound 10;
p9, condensing the compound 10 with an acceptor molecule to prepare the chromophore H4;
3. the method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the steps P1 and P2 are specifically:
p1, slowly dissolving metallic sodium in ethanol under the protection of argon, adding 2-mercaptoethanol under the ice bath condition, adding the compound 1 for reaction for 1 hour after fully mixing and stirring, adding the compound 2b, refluxing at 65 ℃ for overnight, extracting and concentrating with ethyl acetate after the reaction is finished, purifying by silica gel chromatography, and using ethyl acetate and petroleum ether as eluent to obtain a compound 3b;
p2, slowly adding the mixture into an N, N-dimethylamide solution of the compound 3b in a flask filled with imidazole and tert-butyldimethyl chlorosilane, reacting for 3 hours at room temperature under the protection of argon, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 4b.
4. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P3 specifically comprises:
and P3, slowly adding diethyl cyanomethylphosphate into tetrahydrofuran solution of sodium hydride under the condition of argon protection and ice bath, adding the compound 4b, carrying out reflux reaction at 65 ℃ overnight, carrying out vacuum spin-drying on the solvent after the reaction is finished, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 5b.
5. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P4 specifically comprises:
p4, slowly adding a hexane solution of diisobutyl aluminum hydride into a dichloromethane solution of the compound 5b, reacting for a period of time at the temperature of minus 78 ℃ under the protection of argon, adding a certain amount of dichloromethane and water for quenching at the temperature of 0 ℃, carrying out suction filtration after the reaction is finished, extracting filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 6b.
6. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P5 specifically comprises:
and P5, removing the tertiary butyl diphenyl chlorosilane protecting group of the compound 6b through alkaline hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 7b.
7. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the P6 and P7 steps are specifically:
p6, slowly adding the mixture into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 3, 5-di ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid, reacting for a period of time at 0 ℃ under a protective atmosphere, slowly adding the dichloromethane solution of the compound 7b, heating and refluxing the mixture for reaction, extracting an organic phase with dichloromethane, removing a solvent by spin drying, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound 8d;
and (3) removing the (2-tetrahydropyran) protecting group of the compound 8d through acid hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain the compound 9.
8. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P8 is specifically:
p8, slowly adding into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 6,6' - ((ethane-1, 1-triacyltris (benzene-4, 1-diacyl)) tris (oxy)) tricarboxylic acid, reacting for a period of time under the protection of argon at 0 ℃, slowly adding into the dichloromethane solution of the compound 9, heating and refluxing to react, extracting an organic phase with dichloromethane, removing the solvent by spin drying, purifying by silica gel chromatography, and purifying by using dichloromethane and ethyl acetate as eluent to obtain the compound 10.
9. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P9 specifically comprises:
p9, reacting the compound 10 with an acceptor molecule under the protection of argon, concentrating a product, purifying by silica gel chromatography, and eluting with ethyl acetate and petroleum ether to obtain the chromophore H4; wherein the acceptor molecule is 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile.
10. Use of a self-assembled organic optical nonlinear chromophore according to claim 1 as electro-optic material and in an electro-optic modem.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore with D-pi-A structure modified by dendritic group, and synthetic method and application thereof |
| CN107216320A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore with double-donor structure and synthesis method and application thereof |
| CN109293643A (en) * | 2017-07-24 | 2019-02-01 | 中国科学院理化技术研究所 | Flexible spacer group modified organic second-order nonlinear optical chromophore, and preparation method and application thereof |
| WO2021003296A1 (en) * | 2019-07-02 | 2021-01-07 | University Of Washington | Crosslinkable nonlinear-optical chromophore system |
-
2022
- 2022-04-01 CN CN202210338231.8A patent/CN114656432B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore with D-pi-A structure modified by dendritic group, and synthetic method and application thereof |
| CN107216320A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore with double-donor structure and synthesis method and application thereof |
| CN109293643A (en) * | 2017-07-24 | 2019-02-01 | 中国科学院理化技术研究所 | Flexible spacer group modified organic second-order nonlinear optical chromophore, and preparation method and application thereof |
| WO2021003296A1 (en) * | 2019-07-02 | 2021-01-07 | University Of Washington | Crosslinkable nonlinear-optical chromophore system |
Non-Patent Citations (10)
| Title |
|---|
| Design and synthesis of organic optical nonlinear multichromophore dendrimers based on double-donor structures;Fenggang Liu et al.;《 Mater. Chem. Front.》;第5卷;第8341-8351页 * |
| Enhancement of electro-optic properties of nonlinear optical chromophores by introducing pentafluorobenzene group into the donor and π-bridge;Jinlong Lei et al.;《Dyes and Pigments》;第170卷;第1-8页 * |
| Influence of Monomer Optical Purity on the Conformation and Properties of Chiral, Donor-Embedded Polybinaphthalenes for Nonlinear Optical Purposes;Guy Koeckelberghs et al.;《Chem. Mater.》;第17卷;第118-121页 * |
| Molecular Engineering of Structurally Diverse Dendrimers with Large Electro-Optic Activities;Huajun Xu et al.;《ACS Appl. Mater. Interfaces》;第11卷;第21058-21068页 * |
| Self-assembled binary chromophores with enhanced electro-optic activity and alignment stability;Fenggang Liu et al.;《Materials Letters》;第263卷;第1-3页 * |
| Supramolecular self-assembled nonlinear optical molecular glasses with enhanced electro-optic activity and alignment stability;Caiqin Gu et al.;《Dyes and Pigments》;第202卷;第1-11页 * |
| Ultra-efficient and stable electro-optic dendrimers containing supramolecular homodimers of semifluorinated dipolar aromatics;Jieyun Wu et al.;《Mater. Chem. Front.》;第2卷;第901-909页 * |
| Ultrahigh Electro-Optic Coefficients, High Index of Refraction, and Long-Term Stability from Diels − Alder Cross-Linkable Binary Molecular Glasses;Huajun Xu et al.;《Chem. Mater.》;第32卷;第1408-1421页 * |
| Ultralarge and Thermally Stable Electro-Optic Activities from Supramolecular Self-Assembled Molecular Glasses;Tae-Dong Kim et al.;《J. AM. CHEM. SOC. 》;第129卷;第488-489页 * |
| 基于分子间π-π堆积有机电光材料的研究;黄泽铃;《中国优秀硕士学位论文全文数据库 工程科技I辑》;全文 * |
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