CN115947727B - Preparation method and application of aza-olympic alkene dye molecule - Google Patents
Preparation method and application of aza-olympic alkene dye molecule Download PDFInfo
- Publication number
- CN115947727B CN115947727B CN202211072365.6A CN202211072365A CN115947727B CN 115947727 B CN115947727 B CN 115947727B CN 202211072365 A CN202211072365 A CN 202211072365A CN 115947727 B CN115947727 B CN 115947727B
- Authority
- CN
- China
- Prior art keywords
- olympic
- organic
- aza
- alkene
- dye molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 9
- 150000004056 anthraquinones Chemical class 0.000 claims description 9
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 7
- 238000000862 absorption spectrum Methods 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000000539 dimer Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical class CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- -1 perylene imides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical group C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to the field of organic optical, electric and magnetic functional materials, in particular to a preparation method and application of an aza-olympic alkene dye molecule, wherein X in the structural formula is hydrogen, fluorine, chlorine or bromine; the A and B units are ethylene or polycyclic aromatic hydrocarbon, which are the same or different, and the molecule of the invention has an asymmetric conjugated structure, so the dipole moment of the molecule is larger, good molecular accumulation such as pi-pi dimer is formed in a solid state, and simultaneously, the physical and chemical properties of the molecule such as HOMO and LUMO energy levels, absorption spectrum and the like can be further regulated and controlled by introducing halogen atoms on an anthraquinone structure or performing conjugated expansion on an Olympic structure, so that the material can be used in the fields of organic thin film transistors, organic spin devices, organic solar cells and the like.
Description
Technical Field
The invention relates to the field of organic optical, electric and magnetic functional materials, in particular to a preparation method and application of an aza-olympic alkene dye molecule.
Background
Organic semiconductor materials can be classified into p-type and n-type semiconductor materials according to the carrier transport type, and have hole and electron transport characteristics, respectively. Dye molecules having planar conjugated structures are a very important class of organic semiconductor materials, such as phthalocyanines, indigoids, isoindigoids, pyrrolopyrroldiketones, perylene imides, and imide-based materials, have been widely developed as high mobility semiconductor materials (Adv.Mater.2016, 28,3615,Adv.Mater.2020,32,1903882). However, at present, the types of dye-based organic semiconductor materials are limited, and particularly, the development of materials suitable for n-type semiconductors processed as solutions is relatively backward, so that new dye-based organic semiconductor materials still remain to be developed.
From the chemical structure point of view, organic semiconductor materials based on dye molecules are mostly composed of polycyclic aromatic hydrocarbons having planar conjugated structures and chromophoric groups, which are mostly azo, carbonyl, anthraquinone, imide, etc. (chem. Rev.2022,122, 565). The compound with imide group can regulate the energy level of the front track of the molecule through the electron-deficient action of carbonyl, and can introduce proper solubilizing substituent through nitrogen atom on the imide group. Meanwhile, the optimal performance of the organic dye molecules can be realized by introducing different types of solubilizing substituents and systematically regulating and controlling the stacking mode of the molecular solid state (New J.chem.2021,45,21001). For example, tetraazacoronene (J.Mater. Chem. C2018,6,1334) can be regarded as a flanking conjugated extended naphthalimide structure with 9, 10-dihydro-9, 10-bis (methine) anthracene as the nucleus to which four imide groups are attached, a red dye. However, the compound reported at present can only introduce substituent groups containing phenyl, and the monocrystal structure shows that the plane of the benzene ring is almost perpendicular to the conjugated plane of tetraazacoronene, so that the effective accumulation among molecules is influenced. Therefore, how to design new organic dye molecules and realize effective regulation and control of a molecular stacking mode by introducing proper substituents is a key for preparing novel dye organic semiconductor materials.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method and application of an aza-olympic alkene dye molecule.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: an aza-olympic alkene dye molecule of the invention comprises the following structural formula (I) or (II):
further, the invention is improved, wherein the A and B units are ethylene, benzene, naphthalene, phenanthrene, thiophene or thiaindene, and the A and B units are the same or different, and the specific structural formula is as follows:
further, the invention is improved by comprising any one of the following structures:
wherein R is a straight alkyl chain, a branched alkyl chain or a 4-alkylphenyl group, and the straight alkyl chain and the branched alkyl chain have the structural general formula: c (C) n H 2n+1 Wherein n is a natural integer from 1 to 20; the structural general formula of the 4-alkylphenyl is as follows: c (C) 6 H 4 C m H 2m+1 Wherein m is a natural integer of 1 to 20.
The preparation method of the aza-olympic alkene dye molecule comprises the following steps of raw materials, wherein the raw materials comprise any one of halogenated anthraquinone and halogenated olympic alkene ketone derivatives, the raw materials adopt a C-N coupling reaction to introduce two substituents, and the aza-olympic alkene dye molecule can be further prepared by Knoevenagel condensation reaction:
wherein Y is fluorine, chlorine or bromine:
carrying out C-N coupling reaction on halogenated anthraquinone and straight alkyl chain, branched alkyl chain or 4-alkylphenylamine, and then carrying out Knoevenagel condensation reaction on the halogenated anthraquinone and diethyl malonate;
the halogen olympic ketone derivative and straight alkyl chain, branched alkyl chain or 4-alkyl phenyl amine undergo C-N coupling reaction and then undergo Knoevenagel condensation reaction with diethyl malonate.
The application of the aza-olympic alkene dye molecule in the fields of organic thin film transistors, organic hot spots and organic solar cells comprises that any structure in the dye molecule acts on the fields of organic thin film transistors, organic thermoelectric and organic solar cells.
(III) beneficial effects
Compared with the prior art, the invention provides a preparation method and application of an aza-olympic alkene dye molecule, and the preparation method has the following beneficial effects:
the molecules of the invention have asymmetric conjugated structures, so that the dipole moment of the molecules is larger, good molecular accumulation such as pi-pi dimer forms can be formed in a solid state, and meanwhile, the physical and chemical properties of the molecules such as HOMO and LUMO energy levels, absorption spectrum and the like can be further regulated and controlled by introducing halogen atoms on an anthraquinone structure or performing conjugated expansion on an Olympic alkene structure, so that the material can be used in the fields of organic thin film transistors, organic spin devices, organic solar cells and the like.
Drawings
FIG. 1 is a schematic representation of a synthetic compound according to the invention, DAO-dp;
FIG. 2 is a schematic diagram of the synthetic compound ODI-do of the invention;
FIG. 3 is an absorption spectrum of the present invention;
FIG. 4 is a schematic diagram of electron transfer characteristics of a DAO-do device of the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-4, an aza-olympic alkene dye molecule of the present invention comprises the following structural formula (I) or (II):
in this embodiment, it is preferred that the units a and B are ethylene, benzene, naphthalene, phenanthrene, thiophene, or thiaindene, which are the same or different, and have the following specific structural formula:
in this embodiment, most preferably, the structure includes any one of the following structures:
wherein R is a straight alkyl chain, a branched alkyl chain or a 4-alkylphenyl group, and the straight alkyl chain and the branched alkyl chain have the structural general formula: c (C) n H 2n+1 Wherein n is a natural integer from 1 to 20; the structural general formula of the 4-alkylphenyl is as follows: c (C) 6 H 4 C m H 2m+1 Wherein m is a natural integer of 1 to 20.
According to the second technical scheme, the preparation method of the dye molecule based on the aza-olympic alkene is characterized in that halogenated anthraquinone or halogenated olympic ketone derivative is used as a raw material, two substituents are introduced through a C-N coupling reaction, and the dye molecule is prepared through Knoevenagel condensation reaction:
wherein Y is fluorine (F), chlorine (Cl) or bromine (Br);
carrying out C-N coupling reaction on halogenated anthraquinone and straight alkyl chain, branched alkyl chain or 4-alkylphenylamine, and then carrying out Knoevenagel condensation reaction on the halogenated anthraquinone and diethyl malonate;
the halogen olympic ketone derivative and the straight alkyl chain, branched alkyl chain or 4-alkyl phenyl amine undergo C-N coupling reaction, and then undergo Knoevenagel condensation reaction with diethyl malonate;
in a third technical scheme of the invention, the dye molecule based on the aza-olympic alkene is applied to the fields of organic thin film transistors, organic hot spots and organic solar cells.
Based on the above scheme, the invention comprises the following embodiments:
example 1: synthesis of Compound DAO-dp
Under nitrogen protection, compound 1 (0.50 g,1.80 mmol), 4-tert-butylaniline (0.67 g,4.51 mmol), cs 2 CO 3 (2.35g,7.22mmol)、Pd 2 (bda) 3 (100 mg) and BINAP (200 mg) were added to mesitylene (10 mL), and after oxygen was removed by freeze-thaw cycle, the reaction solution was stirred at 180℃for 12 hours, the reaction solution was cooled, the solvent was removed, and the crude product was purified by silica gel column chromatography using ethyl acetate/dichloromethane (1:1) as eluent. The end product 2a was a dark purple solid (0.75 g, 83%), 1 H NMR(600MHz,CDCl 3 )δ(ppm)：11.24(s,2H)，7.66(d，J＝7.2Hz,2H),7.48(d，2H)，7.42(t，2H)，7.40(d，4H)，7.22(d,4H)，1.34(s，18H)； 13 C NMR(150MHz，CDCl 3 )δ(ppm)：188.89，184.04，149.20，147.95，137.07，314.37，133.96，126.41，123.88，120.25，117.15，115.30，34.50，31.42；MALDI-TOF-MS analysis：calcd for C 34 H 35 N 2 O 2 (M+H) + :503.262,found:503.485；
compound 2b (165 mg,0.33 mmol), diethyl malonate (530 mg,3.31 mmol) and potassium acetate (130 mg,1.32 mmol) were dissolved in DMF (3 ml) and reacted at 170℃for 1h under microwave-assisted conditions. After the solution was cooled to room temperature, it was settled in n-hexane and filtered to give a crude product. The product was purified by column chromatography on silica gel using methylene chloride/methanol (20:1) as eluent and further recrystallized from tetrahydrofuran solution, the final product DAO-dp was orange powder (34 mg),20％)， 1 H NMR(600MHz,CDCl 3 )δ(ppm):8.25(d,2H),7.66(t,J＝8.0Hz,2H),7.62(d,4H),7.25(d,4H),7.00(d,2H),1.40(s,36H). 13 C NMR(600MHz,CDCl 3 )δ(ppm):182.06,158.41,152.33,141.86,138.08,134.52,132.72,130.14,128.46,127.42,123.23,121.63,115.06,34.99,31.51.HR-MS analysis:calcd for C 37 H 32 N 2 NaO 3 (M+Na) + :575.2305,found:575.2287(error:3.1ppm)。
Example 2: synthesis of Compound DAO-dp
Under the protection of nitrogen, compound 1 (4.00 g,14.44 mmol), n-octylamine (4.66 g,36.09 mmol) and Cs 2 CO 3 (18.81g,57.74mmol)、Pd 2 (bda) 3 (400 mg) and BINAP (800 mg) were added to mesitylene (50 mL), and after oxygen was removed by freeze-thaw cycle, the reaction solution was stirred at 180℃for 12h, the reaction solution was cooled, the solvent was removed, and the crude product was purified by silica gel column chromatography using ethyl acetate/dichloromethane (1:1) as eluent, and the final product 2b was a dark purple solid (5.7 g, 85%). 1 H NMR(600MHz,CDCl 3 )δ(ppm):9.59(t,2H),7.51(d,J＝7.3Hz,2H),7.44(t,J＝7.9Hz,2H),7.00(d,J＝8.5Hz,2H),3.28(t,J＝12.3Hz,4H),1.76(m,4H),1.48(m,4H),1.32(m,16H),0.88(t,6H). 13 C NMR(150MHz,CDCl 3 )δ(ppm):189.02,184.78,151.23,134.38,134.05,117.66,114.74,114.33,43.12,31.83,29.25,27.25,22.67,14.11.MALDI-TOF-MS analysis:calcd for C 30 H 43 N 2 O 2 (M+H) + :463.325,found:463.542；
Compound 2b (153 mg,0.33 mmol), diethyl malonate (530 mg,3.31 mmol) and potassium acetate (130 mg,1.32 mmol) were dissolved in DMF (3 mL) and reacted at 170℃for 1h under microwave-assisted conditions. After the solution is cooled to room temperature, the solution is settled in normal hexane and filtered to obtain a crude product. The product was purified by column chromatography on silica gel using methylene chloride/methanol (20:1) as eluent and further recrystallized from toluene solution. The final product DAO-do was a bronze powder (70 mg, 38%). 1 H NMR(600MHz,CDCl 3 )δ(ppm):8.27(d,J＝7.2Hz,2H),7.88(t,J＝7.5Hz,2H),7.67(d,J＝8.3Hz,2H),4.40(t,4H),1.80(m,4H),1.50(m,4H),1.30(m,16H),0.88(t,6H). 13 C NMR(150MHz,CDCl 3 )δ(ppm):181.85,157.89,139.57,136.24,132.95,130.38,122.69,119.64,115.31,114.89,43.26,31.89,29.43,27.15,22.74,14.21.HR-MS analysis:calcd for C 33 H 40 N 2 NaO 3 (M+Na) + :535.2918,found:535.2931(error:2.4ppm)。
Example 3: synthesis of Compounds ODI-do
Under nitrogen protection, compound 3 (640 mg,2.0 mmol), n-octylamine (0.65 g,5 mmol), cs 2 CO 3 (2.61g,8.0mmol)、Pd 2 (bda) 3 (120 mg) and BINAP (240 mg) were added to mesitylene (10 mL). After removal of oxygen by freeze-thaw cycle, the reaction solution was stirred at 180℃for 12h. The reaction solution was cooled to remove the solvent. The crude product was purified by column chromatography on silica gel using ethyl acetate/dichloromethane (1:1) as eluent. Pure product 4 was obtained as a dark purple solid (0.76 g, 75%). 1 H NMR(600MHz,CDCl 3 )δ(ppm):9.50(t,2H),8.42(d,J＝7.9Hz,2H),8.31(d,J＝8.4Hz,2H),8.06(d,J＝7.8Hz,2H),7.05(d,J＝8.4Hz,2H),3.30(t,J＝12.0Hz,4H),1.77(m,4H),1.48(m,4H),1.33(m,16H),0.88(t,6H). 13 C NMR(150MHz,CDCl 3 )δ(ppm):185.02,148.23,133.38,130.05,127.66,126.74,125.63,125.03,120.38,115.64,110.95,43.42,32.43,29.45,27.35,22.60,14.24.MALDI-TOF-MS analysis:calcd for C 35 H 44 N 2 O(M+H) + :509.353,found:509.497；
Compound 4 (508 mg,1.0 mmol), diethyl malonate (1.60 g,10.0 mmol) and potassium acetate (330 mg,4.0 mmol) were dissolved in DMF (10 mL) and reacted at 170℃for 1h under microwave-assisted conditions. After the solution was cooled to room temperature, it was settled in n-hexane and filtered to give a crude product. The product was purified by column chromatography on silica gel using methylene chloride/methanol (20:1) as eluent and further recrystallized from toluene solution. The final product ODI-do was a reddish brown powder (128 mg, 23%). 1 H NMR(600MHz,CDCl 3 )δ(ppm):8.54(d,J＝7.8Hz,2H),8.45(d,J＝8.3Hz,2H),8.21(d,J＝7.7Hz,2H),8.08(d,J＝8.3Hz,2H),4.34(t,4H),1.81(m,4H),1.49(m,4H),1.31(m,16H),0.88(t,6H). 13 C NMR(600MHz,CDCl 3 )δ(ppm):181.46,157.69,138.63,137.35,135.24,133.55,130.69，129.72，124.79,123.12,121.08,115.36,111.25,43.33,31.70,29.65,27.20,22.62,14.17.HR-MS analysis:calcd for C 38 H 42 N 2 NaO(M+Na) + :581.7425,found:581.7445(error:3.5ppm)。
Effect verification example:
(1) The absorption spectrum of the aza-olympic alkene dye molecules prepared in examples 1 and 2 was measured by using an ultraviolet-visible spectrophotometer and a fluorescence spectrophotometer, and the result is shown in fig. 3;
(2) Preparing a top gate bottom contact thin film transistor device: a heavily doped n-type silicon wafer is used as a substrate, gold (Au) with the thickness of about 50 nanometers is used as a source/drain electrode of a thin film transistor device, and DAO-do is used as a semiconductor transmission layer. A chloroform solution (6 mg/mL) was prepared at a rotation speed of 1000rpm for 60 seconds and a film thickness of 40 nm. Then carrying out thermal annealing treatment at 80 ℃; spin-coating PMMA as a dielectric layer with the thickness of 500nm; finally, gold (Au) with the thickness of about 50 nanometers is deposited to prepare the gate electrode of the device. The channel length width of the device prepared by the invention is 50 μm and 3000 μm, and the dielectric constant of the insulating layer is 4.6nF/cm 2 The devices were measured using a Keithley 4200 semiconductor tester under nitrogen atmosphere. FIG. 4 is an electron transfer characteristic of a DAO-do device from which the electron mobility of the device was calculated to be 2.3X10 -4 cm 2 V -1 s -1 。
The aza-olympic alkene molecules adopted by the invention are plane conjugated skeleton structural units with two electron-deficient imide structures, and because the molecules have the characteristics of the electron-deficient imide units and the up-down separation structure of anthraquinone or olympic alkene structures, a certain degree of charge transfer exists in the molecules, and because of the existence of the imide structures, the molecules have lower HOMO energy levels and LUMO energy levels, and in addition, a solubilizing group can be introduced through the imide structural units, so that the solubility of the molecules is ensured.
The molecules of the invention have asymmetric conjugated structures, so that the dipole moment of the molecules is larger, good molecular accumulation such as pi-pi dimer forms can be formed in a solid state, and meanwhile, the physical and chemical properties of the molecules such as HOMO and LUMO energy levels, absorption spectrum and the like can be further regulated and controlled by introducing halogen atoms on an anthraquinone structure or performing conjugated expansion on an Olympic alkene structure, so that the material can be used in the fields of organic thin film transistors, organic spin devices, organic solar cells and the like.
Although embodiments of the present invention have been described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. An aza-olympic alkene dye molecule characterized by the following structural formula (I):
2. the method for preparing the aza-olympic alkene dye molecule according to claim 1, which is characterized by comprising the steps of raw materials, wherein the raw materials are halogenated anthraquinone, and the raw materials adopt a C-N coupling reaction to introduce two substituents, and can be further prepared through Knoevenagel condensation reaction;
3. use of an aza-olympic ene dye molecule according to claim 1 in the field of organic thin film transistors, organic hotspots and organic solar cells, characterized in that the dye molecule according to claim 1 is used in the field of organic thin film transistors, organic thermoelectric and organic solar cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211072365.6A CN115947727B (en) | 2022-09-02 | 2022-09-02 | Preparation method and application of aza-olympic alkene dye molecule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211072365.6A CN115947727B (en) | 2022-09-02 | 2022-09-02 | Preparation method and application of aza-olympic alkene dye molecule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115947727A CN115947727A (en) | 2023-04-11 |
| CN115947727B true CN115947727B (en) | 2024-03-19 |
Family
ID=87281349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211072365.6A Active CN115947727B (en) | 2022-09-02 | 2022-09-02 | Preparation method and application of aza-olympic alkene dye molecule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115947727B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768369A (en) * | 2008-12-31 | 2010-07-07 | 大连理工大学 | Weather-resistance perylene imide dye and preparation method and application thereof |
-
2022
- 2022-09-02 CN CN202211072365.6A patent/CN115947727B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768369A (en) * | 2008-12-31 | 2010-07-07 | 大连理工大学 | Weather-resistance perylene imide dye and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| 6H-Anthra[1,9,8-c,d,e,f]-2,7-naphthyridine derivatives. II. Nitration of anthranaphthyridine-1,6,11-triones;Reznichenko, S. V.等;Khimiya Geterotsiklicheskikh Soedinenii(第12期);1645-1648 * |
| 6H-Anthra[1,9,8-cdef]-2,7-naphthiridine;Reznickenko, S. V.等;Khimiya Geterotsiklicheskikh Soedinenii(第5期);679-681 * |
| Color-tunable arylaminoanthraquinone dyes through hydrogen-bond-assisted charge transfer interaction;Takashi Takeda等;RSC Adv.;第11卷;24217–24231 * |
| From anthraquinone to heterocoronene as stable red chromophore;Ruomeng Duan等;J. Mater. Chem. C;第6卷;1334-1337 * |
| Reznichenko, S. V.等.6H-Anthra[1,9,8-c,d,e,f]-2,7-naphthyridine derivatives. II. Nitration of anthranaphthyridine-1,6,11-triones.Khimiya Geterotsiklicheskikh Soedinenii.1976,(第12期),1645-1648. * |
| Ruomeng Duan等.From anthraquinone to heterocoronene as stable red chromophore.J. Mater. Chem. C.2018,第6卷1334-1337. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947727A (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xin et al. | Azulene–pyridine-fused heteroaromatics | |
| Rohr et al. | Liquid crystalline coronene derivatives | |
| US8022214B2 (en) | Organic semiconductor materials and precursors thereof | |
| TWI415317B (en) | Organic semiconductors, their manufacture and semiconductor devices comprising them | |
| Reghu et al. | Air stable electron-transporting and ambipolar bay substituted perylene bisimides | |
| JP2008513544A (en) | Carbonyl-functionalized thiophene compounds and related device structures | |
| US20100006830A1 (en) | Organic semiconductor compound based on 2,7-bis-(vinyl)[1]benzothieno[3,2-b]benzothiophene, organic semiconductor thin film and transistor using the same and methods of forming the same | |
| WO2020058203A1 (en) | Novel fluorescent pyrene derivatives, methods for preparing the same, and uses thereof | |
| WO2011047624A1 (en) | Sulfur containing heterocycle-fused naphthalene tetracarboxylic acid diimide derivatives, preparation method and use thereof | |
| Fan et al. | Discotic mesogens based on triphenylene-fused benzimidazole or perimidine: facile synthesis, mesomorphism, optical properties and self-assembly | |
| Shibuya et al. | Linear Biazulene Isomers: Effects of Molecular and Packing Structure on Optoelectronic and Charge-Transport Properties | |
| Wu et al. | Synthesis of largely π-extended naphthalenediimides via C–H activation towards highly soluble and narrow band-gap organic optoelectronic materials | |
| Duan et al. | Organic field-effect transistors based on two phenylene–thiophene oligomer derivatives with a biphenyl or fluorene core | |
| Wanwong et al. | BODIPY dyads and triads: synthesis, optical, electrochemical and transistor properties | |
| CN115947727B (en) | Preparation method and application of aza-olympic alkene dye molecule | |
| CN107814813B (en) | N-type quinoid dithiophene field effect semiconductor material and preparation method and application thereof | |
| US9315671B2 (en) | Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors | |
| CN114195698B (en) | Imide fluoranthene molecular building block, preparation and application thereof | |
| KR20100006294A (en) | Organic nanofiber structure based on self-assembled organogel and organic nanofiber transistors using thereof, and the manufacturing method of them | |
| CN114933609B (en) | N-type organic semiconductor material based on isoindigo fluorine boron hybridization, preparation method thereof and organic field effect transistor | |
| Hoang et al. | New π-extended triphenylene-based organic semiconductors in field-effect transistors | |
| JP7162129B2 (en) | Indaceno derivatives as organic semiconductors | |
| CN109942585B (en) | Organic semiconductor material, preparation method, field effect transistor device and manufacturing method thereof | |
| KR101390666B1 (en) | Diketopyrrolopyrrole- and tellurophene-based polymers derivative, organic semiconductor thin film and organic thin film transistor comprising the same | |
| CN111518121B (en) | Aminobenzofuran diketone-based oligomer, preparation method and application thereof, and organic field effect transistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |