CN115141193B - Optical chromophore compound, composite material containing same, thin film and photoelectric integrated device - Google Patents
Optical chromophore compound, composite material containing same, thin film and photoelectric integrated device Download PDFInfo
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- CN115141193B CN115141193B CN202110345549.4A CN202110345549A CN115141193B CN 115141193 B CN115141193 B CN 115141193B CN 202110345549 A CN202110345549 A CN 202110345549A CN 115141193 B CN115141193 B CN 115141193B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 132
- 230000003287 optical effect Effects 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000010409 thin film Substances 0.000 title abstract description 7
- 230000005693 optoelectronics Effects 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052736 halogen Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 230000008033 biological extinction Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- -1 aromatic Mirabilite compound Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009897 systematic effect Effects 0.000 description 3
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 2
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000000382 optic material Substances 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000003375 sulfoxide group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical group SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/08—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing alicyclic rings
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- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses an optical chromophore compound, a composite material containing the optical chromophore compound, a thin film and an optoelectronic integrated device. The optical chromophore compound takes Fisher alkali or Mi's alkali compound as pi-electron donor, tricyanofuran (TCF) and its derivative as pi-electron acceptor, and the donor and acceptor are connected by conjugated bridge with different side chain modification. The chromophore compound of the invention has a sequence parameter (phi) increased from almost zero to more than 0.1, and a hyperpolarizability (beta) and an electro-optic coefficient (r 33) increased by more than 3 times at most compared with an unmodified chromophore compound. At 1304nm, the high linear electro-optic coefficient (r 33) is shown, and at the concentration of 1.3X10- 20mL‑1, the electro-optic coefficient is 73.3pm/V for M2-SO2Ph, which is more than 30pm// V of the commercial inorganic electro-optic crystal lithium niobate.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to an optical chromophore compound, a composite material containing the optical chromophore compound, a thin film and a photoelectric integrated device.
Background
The organic polymer optical waveguide material has the advantages of simple manufacturing process, ultrafast response time, small dielectric constant and the like, and can be used for manufacturing complex photoelectric integrated devices through spin coating, film throwing, photoetching or imprinting and other processes, and can be produced in a large scale. However, the chromophore compound is often limited by lower electro-optic coefficient, and how to modify the chromophore compound simply and efficiently has great significance for the development of electro-optic materials.
Disclosure of Invention
To solve the above technical problems, a first object of the present invention is to provide an optical chromophore compound.
A second object of the present invention is to provide a composite material containing the above optical chromophore compound.
A third object of the present invention is to provide a thin film made of the above composite material, and an optoelectronic integrated device having the thin film.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aspect of the present invention provides an optical chromophore compound having a structural formula shown in formula 1:
R 1＝R2-R3 is formula 1;
in the formula 1, R 1 is pi-electron donor group, and is Fischer alkali, mirabilite or aromatic Mirabilite compound; the structure is shown as formula 2 or formula 3:
R 4 in the formula 2 and the formula 3 is selected from alkyl of C1-12;
R 2 is a conjugated bridge selected from cyclopentene and its derivatives or cyclohexene and its derivatives, and its structure is shown in formula 4 or formula 5:
R 5 in the formula 4 and the formula 5 is selected from alkyl of C1-12; r 6 is selected from a thioether or sulfoxide group;
r 3 is pi-electron acceptor group, tricyanofuran (TCF) and its derivative, its structure is shown in formula 6:
R 7、R8 in formula 6 is independently selected from C1-C6 alkyl or halogen substituted C1-C6 alkyl.
The optical chromophore compounds according to the invention preferably R 6 is selected from aromatic thioether or aromatic sulfoxide groups, more particularly R 6 is selected from the following substituents and derivatives thereof:
The derivative can be obtained by substitution derivatization on a benzene ring, and a specific derivatization method can be adopted by methods known in the art.
In the optical chromophore compound provided by the invention, pi-electron donor groups are conjugated and connected with pi-electron acceptor groups through conjugated bridges modified by different groups, and R 6 substituent groups modify cyclopentene or cyclohexene conjugated bridges. By structural modification, steric hindrance, bond length alternation and push-pull strength of the donor-acceptor are changed. The mercapto and sodium benzene sulfinate are easy to have substitution reaction with Cl atoms under the weak alkaline condition, and the reaction yield is high. The rigid structure of the conjugated bridge of cyclopentene and cyclohexene leads to the generated chromophore with large steric hindrance and chemical stability, and the R 6 substituent group with multiple electronegative atoms has stronger electron withdrawing capability compared with Cl atoms, so that the D-pi-A main chain electron cloud distribution is influenced.
According to the optical chromophore compound of the present invention, when the conjugated bridge R 2 is cyclohexene, the structure thereof is as shown in formula 4, preferably, R 5 in formula 4 is selected from C1-6 alkyl groups; for example, in a specific embodiment of the invention, R 5 may be tert-butyl. Chromophores need to be film-formed and then further applied to electro-optic waveguide processing. The main chain structure is an aromatic conjugated structure, the rigidity is high, the solubility is poor, alkyl groups such as tertiary butyl and the like can obviously improve the solubility of chromophores, and the solvent processing and the optical quality of film formation are easy to improve.
The pi-electron donor group of the optical chromophore compound according to the invention is a fischer base, a milbeine or an aromatic milbeine compound, preferably a fischer base or a milbeine compound; the structure of the catalyst is shown in a formula 2 or a formula 3, and preferably R 4 is selected from alkyl of C2-8; for example, R 4 can be ethyl, -CH 2CH(C2H5)C4H9, or the like. In particular embodiments of the invention, R 4 may be ethyl or-CH 2CH(C2H5)C4H9.
The optical chromophore compounds according to the invention have pi-electron acceptor groups that are Tricyanofuran (TCF) and derivatives thereof, the structure of which is shown in formula 6, preferably R 7、R8 are both methyl groups.
The optical chromophore compound according to the present invention preferably has a structural formula of one of the following formulae:
The optical chromophore compound provided by the invention is a nonlinear optical material and can be used for preparing optical composite materials, optical films, electro-optical devices and the like.
The invention also provides a synthetic route of the above optical chromophore compounds:
Wherein R 4、R5、R6、R7 and R 8 are as defined above.
The compounds F3 and M2 are reacted with the raw materials corresponding to R 6 to modify the conjugated bridge, so as to obtain the above optical chromophore compound.
Synthetic reference to Compound F3 Zhang,D.,Zou,J.,Wang,W.et al.Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics.Sci.China Chem.(2020).
Synthetic reference to Compound M2 Luo J,Lin F,Li M,et al.New push–pull polyene chromophores containing a Michler's base donor and a tricyanofuran acceptor:multicomponent condensation,allopolar isomerism and large optical nonlinearity[J].Journal of Materials Chemistry C,2017,5(9):2230-2234.
In a second aspect, the present invention provides a composite material comprising an optical chromophore compound as described above.
The composite material according to the invention preferably has a content of the optical chromophore compound of 10% to 90% by total weight of the composite material.
The composite material according to the invention preferably further comprises a polymer. The optical chromophore compound is mixed with polymer to prepare composite material, and the composite material has the advantages of great nonlinear coefficient, easy processing, etc. and may be prepared into film with excellent optical quality.
The composite material according to the present invention preferably, the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer and polycarbonate.
The composite material according to the invention preferably has an electro-optic coefficient r 33 in the range of 40pm/V to 80pm/V in the wavelength range 1000nm to 1600 nm; more preferably 46pm/V to 75pm/V.
The composite material according to the present invention preferably has a refractive index change value of 0.0005 to 0.005 under the action of an electric field of 10-40V/μm.
The composite material according to the invention preferably has a light absorption coefficient of 5000-30000/cm in the wavelength range of 400-1300 nm.
The electro-optic coefficient r 33 and the change value of the refractive index are obtained by making the composite material into a film and then testing.
In a third aspect the present invention provides a film made from the above composite material.
The invention also provides an optoelectronic integrated device, which is provided with the film. Preferably, the optoelectronic integrated device is an electro-optical device. The optical chromophore provided by the invention realizes a relatively large electro-optic effect.
Electro-optic or electro-absorption modulators are a type of device that modulates the intensity of a laser by a voltage. The electro-optical material has great significance for modulating the electrical signal. The existing electro-optic material has the problems of low electro-optic coefficient, poor solubility, low thermal stability, poor film forming quality and the like. The invention obviously improves the dissolubility, the processing property and the stability of the material and obviously increases the electro-optic coefficient by carrying out structural modification on the conjugated bridge of the chromophore compound. The method is simple and efficient, has high synthesis efficiency, and greatly simplifies synthesis time and cost. There is a broad potential for realizing large area preparation, assembly and application of modulators, and next generation information technology applications.
Drawings
FIG. 1 shows 1 H NMR results of compound F3-SNS of example 1.
FIG. 2 shows 13 C NMR results of compound F3-SNS of example 1.
FIG. 3 shows HRMS (ESI) m/z results for compound F3-SNS of example 1.
FIG. 4 shows 1 H NMR of compound F3-ONS of example 2.
FIG. 5 shows 13 C NMR results of compound F3-ONS of example 2.
FIG. 6 is the HRMS (ESI) m/z results for compound F3-ONS of example 2.
FIG. 7 shows 1 H NMR of compound F3-SO2Ph of example 3.
FIG. 8 shows 13 C NMR of compound F3-SO2Ph of example 3.
FIG. 9 is the HRMS (ESI) m/z results for compound F3-SO2Ph of example 3.
FIG. 10 shows 1 H NMR results of compound M2-SNS of example 4.
FIG. 11 shows 1 H NMR of compound M2-ONS of example 5.
FIG. 12 shows 13 C NMR results on compound M2-ONS of example 5.
FIG. 13 shows 1 H NMR of compound M2-SO2Ph of example 6.
FIG. 14 shows the results of 1 H NMR of compound M2-PhN4S of example 7.
FIG. 15 shows the results of 13 C NMR of compound M2-PhN4S of example 7.
FIG. 16 is a cyclic voltammogram of the compounds of examples 1-7 in tetra-n-butylammonium hexafluorophosphate/dichloromethane solution.
FIG. 17 is a graph showing the molar extinction coefficient spectrum of the compound F3-SNS of example 1 in solution.
FIG. 18 is a graph showing the molar extinction coefficient spectrum of the compound F3-ONS of example 2 in solution.
FIG. 19 is a graph showing the molar extinction coefficient spectrum of the compound F3-SO2Ph of example 3 in solution.
FIG. 20 is a graph showing the molar extinction coefficient spectrum of the compound M2-SNS of example 4 in solution.
FIG. 21 is a graph showing the molar extinction coefficient spectrum of the compound M2-ONS of example 5 in solution.
FIG. 22 is a graph showing the molar extinction coefficient spectra of the compound M2-SO2Ph of example 6 in solution.
FIG. 23 is a graph showing the molar extinction coefficient spectra of the compounds M2-PhN4S of example 7 in solution.
FIG. 24 is a graph showing the absorption coefficient spectra of pure films of the compounds of examples 1 to 7.
FIG. 25 is a graph showing the results of measuring the reflection intensity of TE and TM waves of unpolarized films, polarized films, when a film prepared by mixing the compound F3-SNS of example 1 with a polymer has a wavelength of 1304 nm.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about".
The synthetic routes for the optical chromophore compounds of examples 1-7 are as follows:
Wherein R 6 is
Example 1
This example prepared an optical chromophore compound (compound F3-SNS) having the structure shown below:
the optical chromophore compound is prepared by the steps of:
Step i, synthesizing F3:
Reference Zhang,D.,Zou,J.,Wang,W.et al.Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics.Sci.China Chem.(2020).https://doi.org/10.1007/s11426-020-9860-5.
Step ii, synthesizing a compound F3-SNS:
In a flask, compound F3 (0.18 g,0.27 mmol), 2-mercaptobenzothiazole (89.7 mg,0.54 mmol), triethylamine (54.3 mg,0.54 mmol), acetonitrile 10mL, chloroform 5mL, and reflux for 2 days was added. After the reaction was completed, silica gel was added, the solvent was evaporated, and DCM was used: EA (volume ratio 50:1) column (0.16 g, 74%).
The 1 H NMR detection result of the compound F3-SNS is as follows, and a specific spectrogram is shown in FIG. 1:
1H NMR(300MHz,Chloroform-d)δ8.69(d,J＝13.0Hz,1H),8.39(d,J＝15.6Hz,1H),8.08(d,J＝7.4Hz,1H),7.95–7.88(m,1H),7.81(d,J＝8.1Hz,1H),7.74–7.60(m,2H),7.49–7.39(m,2H),7.39–7.30(m,2H),6.77(d,J＝7.1Hz,1H),6.68(d,J＝15.6Hz,1H),6.29(d,J＝13.0Hz,1H),3.86(d,J＝7.2Hz,2H),3.14(d,J＝14.8Hz,1H),2.94(d,J＝16.4Hz,1H),2.28(dt,J＝28.3,13.6Hz,2H),1.96(d,J＝5.7Hz,1H),1.68(d,J＝4.6Hz,7H),1.52–1.28(m,8H),1.13(s,9H),1.00(td,J＝7.3,5.7Hz,3H),0.91(td,J＝7.1,3.0Hz,3H).
The result of 13 C NMR detection of the compound F3-SNS is as follows, and a specific spectrum is shown in FIG. 2:
13C NMR(101MHz,CDCl3)δ175.69,173.33,166.84,153.35,148.49,144.88,143.42,143.39,139.05,135.78,134.92,134.85,130.94,130.52,129.32,128.93,127.71,126.56,126.23,125.03,124.25,122.14,121.09,118.59,113.78,112.73,112.02,110.97,104.07,103.33,97.03,96.72,54.91,47.55,42.34,42.30,39.25,39.17,32.53,31.36,31.03,29.22,29.07,28.40,27.83,27.39,26.98,26.94,24.53,24.36,23.13,23.07,14.08,11.20.
The HRMS (ESI) m/z calculated for this compound F3-SNS (C 50H52N5OS2 +(M+H)+) was 802.36078 and found to be 802.36041. The specific results are shown in FIG. 3.
Example 2
This example prepares an optical chromophore compound (compound F3-ONS) having the structure shown below:
the procedure is as in example 1, substituting 2-mercaptobenzothiazole as starting material with 2-mercaptobenzoxazole.
In a flask, compound F3 (0.18 g,0.27 mmol), 2-mercaptobenzoxazole (81.1 mg,0.54 mmol), triethylamine (54.3 mg,0.54 mmol), acetonitrile 10mL, chloroform 5mL, and reflux overnight. After the reaction was completed, silica gel was added, the solvent was evaporated, and DCM was used: EA (volume ratio 50:1) column (0.14 g, 68%).
The 1 H NMR detection result of the compound F3-ONS is as follows, and a specific spectrogram is shown in FIG. 4:
1H NMR(300MHz,Chloroform-d)δ8.61(d,J＝12.9Hz,1H),8.42(d,J＝15.6Hz,1H),8.14(d,J＝7.4Hz,1H),7.82(d,J＝8.1Hz,1H),7.71–7.57(m,2H),7.49–7.33(m,3H),7.30(s,1H),7.27(s,1H),6.77(d,J＝7.1Hz,1H),6.65(d,J＝15.5Hz,1H),6.28(d,J＝13.0Hz,1H),3.85(d,J＝7.3Hz,2H),3.12(d,J＝14.8Hz,1H),2.93(d,J＝16.0Hz,1H),2.30(dt,J＝27.6,13.4Hz,2H),1.96(d,J＝5.5Hz,1H),1.73(d,J＝3.9Hz,7H),1.40(dp,J＝23.6,8.1,6.5Hz,8H),1.11(s,9H),1.00(q,J＝7.2Hz,3H),0.91(td,J＝7.1,3.2Hz,3H).
The result of 13 C NMR detection of the compound F3-ONS is as follows, and a specific spectrum is shown in FIG. 5:
13C NMR(101MHz,CDCl3)δ175.73,173.28,161.11,151.88,148.17,145.10,143.53,143.50,141.72,140.53,139.29,135.41,134.84,131.03,130.58,129.21,128.93,127.55,126.32,125.04,124.80,124.04,119.39,118.37,113.72,112.70,111.95,110.98,110.25,103.79,103.36,96.99,96.66,55.03,47.55,42.23,39.22,39.14,32.53,31.37,31.03,29.21,29.07,28.49,27.88,27.37,26.92,26.90,24.53,24.34,23.12,23.05,14.05,11.20,11.17.
The HRMS (ESI) m/z calculated for this compound F3-ONS (C 50H52N5O2S+(M+H)+) was 786.38362 and found to be 786.38330. The specific results are shown in FIG. 6.
Example 3
This example provides an optical chromophore compound (compound F3-SO2 Ph) having the structure shown below:
The procedure is as in example 1, substituting sodium benzene sulfinate for the starting 2-mercaptobenzothiazole.
The 1 H NMR detection result of the compound F3-SO2Ph is as follows, and a specific spectrogram is shown in FIG. 7:
1H NMR(400MHz,Chloroform-d)δ9.00(d,J＝15.7Hz,1H),8.66(d,J＝12.7Hz,1H),8.18(d,J＝7.4Hz,1H),7.90–7.81(m,3H),7.69(t,J＝7.7Hz,1H),7.60–7.53(m,1H),7.49(dd,J＝8.4,6.7Hz,2H),7.43(dd,J＝8.3,7.2Hz,1H),7.36(d,J＝8.3Hz,1H),6.83(d,J＝15.7Hz,1H),6.75(d,J＝7.2Hz,1H),6.10(d,J＝12.7Hz,1H),3.80(d,J＝7.4Hz,2H),2.95(td,J＝15.2,4.9Hz,2H),2.31–2.16(m,1H),2.05(td,J＝13.7,7.7Hz,1H),1.98–1.88(m,1H),1.83(s,3H),1.75(s,3H),1.55–1.23(m,9H),1.05(s,9H),0.97(q,J＝7.2Hz,3H),0.89(td,J＝7.2,3.6Hz,3H).
the result of 13 C NMR detection of the compound F3-SO2Ph is as follows, and a specific spectrum is shown in FIG. 8:
13C NMR(101MHz,CDCl3)δ175.35,173.89,148.30,145.30,143.55,143.34,141.79,138.70,138.65,133.80,133.25,130.94,130.58,129.49,129.45,129.31,128.94,127.57,126.30,125.54,123.86,118.37,116.20,112.35,111.67,110.48,103.70,102.69,99.33,97.79,56.12,47.53,42.45,42.42,39.09,39.02,32.44,31.24,30.99,29.61,29.07,29.02,28.54,28.50,27.20,26.67,26.62,24.48,24.27,23.09,23.04,14.05,11.20,11.15.
the calculated HRMS (ESI) m/z of this compound F3-SO2Ph (C 49H53N4O3S+(M+H)+) was 777.38329 and found to be 777.38287. The specific results are shown in FIG. 9.
Example 4
This example prepared an optical chromophore compound (compound M2-SNS) having the structure shown below:
the optical chromophore compound is prepared by the steps of:
step i, synthesizing M2:
reference Luo J,Lin F,Li M,et al.New push–pull polyene chromophores containing a Michler's base donor and a tricyanofuran acceptor:multicomponent condensation,allopolar isomerism and large optical nonlinearity[J].Journal of Materials Chemistry C,2017,5(9):2230-2234..
Step ii, synthesizing a compound M2-SNS:
The same preparation method as that of the compound F3-SNS of example 1 was carried out, wherein the substituted compound F3 was the compound M2.
The result of 1 H NMR detection of the compound M2-SNS is as follows, and a specific spectrum is shown in FIG. 10:
1H NMR(300MHz,Chloroform-d)δ7.93(d,J＝8.1Hz,1H),7.86–7.70(m,2H),7.55–7.43(m,1H),7.43–7.34(m,1H),7.23(dd,J＝15.2,10.5Hz,3H),6.93(d,J＝8.5Hz,2H),6.72–6.51(m,4H),6.24(d,J＝8.6Hz,2H),3.42(q,J＝7.0Hz,4H),3.30(q,J＝7.1Hz,4H),3.12(d,J＝7.4Hz,2H),3.03(d,J＝7.7Hz,2H),1.66(s,6H),1.18(dt,J＝17.5,7.0Hz,12H).
Example 5
This example prepares an optical chromophore compound (compound M2-ONS) with the structure shown below:
the same procedure was followed as for the preparation of compound F3-ONS of example 2, substituting compound F3 with compound M2.
The 1 H NMR detection result of the compound M2-ONS is as follows, and the specific spectrogram is shown in FIG. 11:
1H NMR(300MHz,Chloroform-d)δ7.79(d,J＝15.6Hz,1H),7.73–7.66(m,1H),7.57–7.47(m,1H),7.44–7.32(m,2H),7.28–7.20(m,2H),7.10(d,J＝12.4Hz,1H),6.95–6.86(m,2H),6.63(dd,J＝10.6,6.3Hz,3H),6.53(d,J＝15.6Hz,1H),6.20–6.08(m,2H),3.42(q,J＝7.0Hz,4H),3.28(q,J＝7.0Hz,4H),3.09(dd,J＝31.7,5.6Hz,4H),1.69(s,6H),1.21(t,J＝7.0Hz,6H),1.14(t,J＝7.0Hz,6H).
the result of 13 C NMR detection of the compound M2-ONS is as follows, and a specific spectrum is shown in FIG. 12:
13C NMR(101MHz,CDCl3)δ175.49,172.39,160.53,152.03,151.88,149.01,148.46,148.15,145.52,142.61,141.90,137.93,132.86,131.50,130.88,129.49,125.56,124.82,124.76,120.99,119.14,115.75,112.45,111.68,110.96,110.80,110.22,110.17,97.67,96.95,55.76,44.48,44.20,29.30,27.16,26.85,12.70.
Example 6
This example prepares an optical chromophore compound (compound M2-SO2 Ph) having the structure shown below:
the same preparation method as that of the compound F3-SO2Ph of the example 3 is adopted, wherein the compound F3 is replaced by a compound M2.
The 1 H NMR detection result of the compound M2-SO2Ph is as follows, and a specific spectrum is shown in FIG. 13:
1H NMR(300MHz,Chloroform-d)δ8.77(d,J＝15.9Hz,1H),7.70–7.53(m,3H),7.43(t,J＝7.7Hz,2H),7.31(d,J＝2.5Hz,1H),7.26(d,J＝8.6Hz,2H),7.10(d,J＝8.5Hz,2H),6.79(d,J＝8.5Hz,2H),6.74–6.49(m,4H),3.51(q,J＝7.0Hz,4H),3.41(q,J＝7.0Hz,4H),3.06–2.81(m,4H),1.87(s,6H),1.29(t,J＝6.9Hz,6H),1.20(t,J＝7.0Hz,6H).
Example 7
This example prepares an optical chromophore compound (compound M2-PhN S) with the following structure:
The same procedures used in example 1 were repeated except that compound F3-SNS was used instead of compound M2 and 2-mercaptobenzothiazole was substituted with 5-mercapto1-phenyl-tetrazole.
The 1 H NMR detection result of the compound M2-PhN S is as follows, and a specific spectrum is shown in FIG. 14:
1H NMR(400MHz,Chloroform-d)δ7.95(d,J＝15.5Hz,1H),7.59–7.50(m,1H),7.47(dd,J＝8.6,6.7Hz,2H),7.34–7.18(m,4H),6.90(d,J＝8.6Hz,2H),6.76–6.51(m,6H),6.37(d,J＝15.5Hz,1H),3.42(q,J＝7.0Hz,4H),3.33(q,J＝7.0Hz,4H),3.06–2.96(m,2H),2.96–2.85(m,2H),1.71(s,6H),1.19(dt,J＝16.5,7.0Hz,12H).
the 13 C NMR detection result of the compound M2-PhN S is as follows, and a specific spectrum is shown in FIG. 15:
13C NMR(101MHz,CDCl3)δ175.66,172.16,152.48,151.38,149.41,148.54,148.20,144.39,141.94,138.01,133.09,132.65,131.18,130.78,130.65,129.71,129.09,125.73,124.99,120.57,115.63,112.42,111.61,111.13,110.99,110.45,97.06,96.95,55.95,44.51,44.13,29.22,26.89,26.66,12.70.
Test example 1
The compounds of examples 1-7 were subjected to cyclic voltammetry using 0.1M tetra-n-butylhexafluoroammonium phosphate/dichloromethane as electrolyte, platinum wire electrode as working electrode, platinum sheet electrode as counter electrode, ag/AgCl as reference electrode, and calibrated with ferrocene. FIG. 16 is a cyclic voltammogram of a chromophore compound. As can be seen from fig. 16, the material has reversible redox peaks, showing a reversible redox process.
Test example 2
The compounds of examples 1-7 were subjected to absorption spectroscopy, and the compounds of examples 1-7 were diluted to a 1X 10 -5 M solution in dioxane (1, 4-dioxane), chloroform (chloroform), dichloromethane (dichloromethane), acetone (acetone), acetonitrile (acetonic), methanol (methanol), dimethyl sulfoxide (DMSO), respectively, using UV-vis-NIR absorption spectroscopy; the test was performed at room temperature using a 1cm quartz cuvette. Wherein the extinction coefficient (ε) of the material is defined by the formula: a=epsilon cb, a being the absorbance of the maximum absorption peak; c is the mass concentration of the material; b is the thickness of the cuvette used. FIGS. 17-23 are graphs of extinction coefficient (Extinction Coefficient) results. The compound was dissolved in chloroform and spin-coated onto glass to form a thin film, called a pure film. The thickness of the film was measured by a step meter, and the absorption coefficient was calculated by measuring the absorbance of the maximum absorption peak. The absorption coefficient is according to the formula: a= lgT = Kbc, a is absorbance of the maximum absorption peak, T is light transmittance, K is absorption coefficient, b is thickness, and c is concentration. FIG. 24 is a graph showing the normalized absorption coefficient results for pure films. As can be seen from FIGS. 17-23, the material shows Strong near infrared absorption and a thermochromic effect (Strong vis-NIR Absorption and Solvatochromism).
Test example 3
The prism-coupled waveguide refractive index test was performed on the compound F3-SNS of example 1, in which the incident wavelength was 1304nm.
Test method reference Wang,W.;Wu,J.;Chen,K.;Huang,Q.;Luo,J.;Chiang,K.S.,Graphene electrodes for electric poling of electro-optic polymer films.Optics Letters,2020,45,2383-2386.Kuzyk,M.G.and C.W.Dirk,Characterization Techniques and Tabulations for Organic Nonlinear Optical Materials.1998:Marcel Dekker.
The chromophore compound and the polymer methyl methacrylate-styrene copolymer are mixed according to a certain proportion (the chromophore compound accounts for 10-20wt%) and added with dibromomethane to be fully dissolved and uniformly mixed, and spin-coated on ITO glass. And processing and testing after vacuum drying. The film thickness was measured using a step gauge. Gold plating was used as the positive electrode, ITO was used as the negative electrode, and an electric field (100V/. Mu.m) was applied. After the temperature is increased and the glass transition temperature is increased to 108-113 ℃, the leakage current is obviously increased, which indicates that the polarization is successful, and the temperature is reduced and cooled. The prism coupling used was a commercial prism coupling tester, model 2010/M, manufacturer Metricon, U.S.A.
The test results are shown in fig. 25, table 1 and table 2. FIG. 25 is a graph showing the results of measuring the reflection intensity of TE and TM waves on unpolarized film and polarized film, respectively, at 1304nm laser wavelength, with a chromophore-containing ratio of 15.75% in the F3-SNS polarized film, which corresponds to a number density N of 1.30X10 20cm-1 in the polymer. As can be seen from fig. 25: after polarization, the TE and TM refractive indexes of the polarized film are changed, and the TM after polarization is obviously larger than TE. Table 1 shows the refractive index test results of the prism-coupled waveguide at 1304nm for the compound F3-SNS polarizing film. Under the application of a certain voltage, the refractive index of the compound changed significantly, which indicates that the compound F3-SNS of example 1 had a good electro-optic effect. The compounds of examples 2-7 exhibited similar electro-optic effects as shown in table 2 below.
TABLE 1 results of refractive index testing of prism-coupled waveguides at 1304nm for compound F3-SNS polarizing films
TABLE 2 maximum absorption wavelength λ max (film blended with Polymer) for different chromophore compounds at a number density N of 1.30X10 20cm-1, electro-optic coefficient (r 33), order parameter (Φ) and hyperpolarizability (β μ)
The electro-optical coefficients of the compound F3 and the compound M2 which are not modified by the conjugated bridge are described in the literature Zhang,D.,Zou,J.,Wang,W.et al.Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics.Sci.China Chem.2021,64,263-273.
The chromophore compound provided by the invention has the sequence parameter (phi) increased from almost zero to more than 0.1, and the hyperpolarizability (beta) and the electro-optic coefficient (r 33) increased by more than 3 times at most compared with the unmodified chromophore compound. At 1304nm, the high linear electro-optic coefficient (r 33) is shown, and at the concentration of 1.3X10- 20mL-1, the electro-optic coefficient is 73.3pm/V for M2-SO2Ph, which is more than 30pm// V of the commercial inorganic electro-optic crystal lithium niobate.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (15)
1. An optical chromophore compound, wherein the structural general formula of the optical chromophore compound is shown as formula 1:
R 1＝R2-R3 is formula 1;
In formula 1, the structure of R 1 is shown as formula 2 or formula 3:
R 4 in the formula 2 and the formula 3 is selected from alkyl of C1-12;
The structure of R 2 is shown as formula 5 or formula 6:
R 5 in the formula 4 and the formula 5 is selected from alkyl of C1-12; r 6 is selected from the following substituents:
The structure of R 3 is shown in formula 6:
R 7、R8 in formula 6 is independently selected from C1-C6 alkyl or halogen substituted C1-C6 alkyl.
2. The optical chromophore compound of claim 1, wherein R 4 is ethyl or-CH 2CH(C2H5)C4H9.
3. The optical chromophore compound of claim 1, wherein R 5 is tert-butyl.
4. The optical chromophore compound of claim 1, wherein R 7、R8 are each methyl.
5. The optical chromophore compound of claim 1, wherein the optical chromophore compound has a structural formula of one of the following:
6. a composite material comprising the optical chromophore compound of any of claims 1-5.
7. The composite of claim 6, wherein the optical chromophore compound is present in an amount of 10% -90% by total weight of the composite.
8. The composite of claim 6, wherein the composite further comprises a polymer.
9. The composite of claim 8, wherein the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer, and polycarbonate.
10. The composite of claim 9, wherein the composite has an electro-optic coefficient r 33 in the range of 40pm/V to 80pm/V over a wavelength range of 1000nm-1600 nm.
11. The composite of claim 9, wherein the refractive index of the composite changes by a value of 0.0005 to 0.005 under an electric field of 10 "40V/μm.
12. The composite of claim 9, wherein the composite has a light absorption coefficient of 5000 to 30000/cm in the wavelength range of 400nm-1300 nm.
13. A film made from the composite material of any one of claims 6-12.
14. An optoelectronic integrated device having the film of claim 13.
15. The optoelectronic integrated device of claim 14, wherein the optoelectronic integrated device is an electro-optic device.
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