CN113072417A - Non-centrosymmetric nano graphene molecule based on triphenylene and preparation method thereof - Google Patents
Non-centrosymmetric nano graphene molecule based on triphenylene and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 125000005580 triphenylene group Chemical group 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 150000001993 dienes Chemical class 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 24
- 239000007983 Tris buffer Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001475 halogen functional group Chemical group 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 12
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000007363 ring formation reaction Methods 0.000 claims description 9
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- FQQOMPOPYZIROF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-one Chemical group O=C1C=CC=C1 FQQOMPOPYZIROF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002346 layers by function Substances 0.000 claims description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000002243 precursor Substances 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- OLRJMFKMKGWLEN-UHFFFAOYSA-N trifluoromethanesulfonic acid;triphenylene Chemical group OS(=O)(=O)C(F)(F)F.C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 OLRJMFKMKGWLEN-UHFFFAOYSA-N 0.000 description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 230000037230 mobility Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- -1 graphene compound Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
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Abstract
本发明公开了一种从可多边反应的苯并菲三芳炔前驱体出发，通过Diels‑Alder反应逐步反应制备出非中心对称的纳米石墨烯化合物，该发明有利于对于分子的边缘结构进行设计，可以较为有效的改善目标化合物的边缘和带隙，以达到调控化合物光电性能的目的，具有较好的电子传输性能。该合成路线简便、操作简单，且价格较低廉，是非常好的制备具有独特结构的非中心对称纳米石墨烯的方法。
The invention discloses a non-centrosymmetric nano-graphene compound prepared by step-by-step reaction through Diels-Alder reaction starting from a triphenylene triarylyne precursor which can react multilaterally. The invention is beneficial to the design of molecular edge structure. The edge and band gap of the target compound can be effectively improved, so as to achieve the purpose of regulating the optoelectronic properties of the compound, and have better electron transport properties. The synthetic route is simple, the operation is simple, and the price is relatively low, and it is a very good method for preparing non-centrosymmetric nano-graphene with a unique structure.
Description
Technical Field
The invention relates to the field of novel organic photoelectricity, and particularly relates to a method for preparing non-centrosymmetric nano graphene based on a triphenylene triarylalkyne type precursor 3,7, 10-tri (trimethylsilyl) -2,6, 11-tri (trifluoromethanesulfonate) triphenylene.
Background
Graphene has the advantages of high electron transmission efficiency, high electrical conductivity and strength, good thermal conductivity, excellent optical performance and the like, and is an ideal material for various photoelectric devices. In the aspect of photoelectric properties, the graphene nanosheet has very excellent controllable energy level and band gap characteristics, can be adjusted by controlling the extension degree, the molecular shape, the structural size and the edge topological structure of the pi conjugated structure, and has high designability.
In the field of the three-branch nano-graphene material, a common synthesis method is to design and synthesize a monomer, then use methods such as a palladium catalyst and the like to enable the monomer to generate cyclotrimerization [2+2+2] Diels-Alder reaction, and obtain the centrosymmetric three-branch nano-graphene material from branches and cores. The dendritic nano-graphene a (Angew. chem. int. Ed.2012, 51, 173-177) is prepared by trimerization of a designed monomer under the action of cesium fluoride and a palladium catalyst.
Recently, it has been reported that a precursor having polygonal reactivity reacts with other raw materials to synthesize a tridentate nanographene b "from a core and branches" (chem. Commun.2020, 56, 12853-12856).
However, the method of synthesizing the three-branch nano-graphene material by using the branch and core method needs to use a palladium catalyst, and the synthesis steps of synthesizing the monomers are complex, which is not favorable for further expansion of the system; the method of 'nucleus and branch' is adopted to synthesize the three-branch-shaped nano graphene material, although the synthesis steps are simplified, the synthesis route is shortened, and the synthesis efficiency of the reaction is integrally improved, the existing method has few synthesis examples, and the structure of the core precursor cannot be determined, so that the research in the direction is limited.
In addition, most of the existing three-branch-shaped nano graphene materials are of symmetrical structures, the research on the non-centrosymmetric nano graphene is not reported, and in the theoretical research level, compared with the centrosymmetric molecules, the non-centrosymmetric molecules have more variable energy levels and band gaps, and can be expected to be regulated and controlled by controlling the synthesis of the molecules, so that the more excellent photoelectric properties are embodied. Therefore, it is necessary to develop a non-centrosymmetric nanographene molecule and a preparation method thereof.
Disclosure of Invention
The invention aims to develop and utilize a triphenylene triarylyne precursor 3,7, 10-tri (trimethylsilyl) -2,6, 11-tri (trifluoromethanesulfonate) triphenylene with a determined structure, and provides a non-centrosymmetric nano graphene molecule and a preparation method thereof based on further extension of the precursor to a 'core and branch' method.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of non-centrosymmetric nano graphene molecules is characterized in that 3,7, 10-tris (trimethylsilyl) -2,6, 11-tris (trifluoromethanesulfonate) triphenylene has a structure shown in a formula I, and the non-centrosymmetric nano graphene molecules are obtained through stepwise reaction with different dienes.
The 3,7, 10-tri (trimethylsilyl) -2,6, 11-tri (trifluoromethanesulfonate) triphenylene has three pairs of easily-leaving substituents, and can be removed under the action of a fluorine-containing reagent to form an intermediate containing three phenylalkyne groups:
the intermediate can perform Diels-Alder cyclization reactions with different dienes step by step under certain conditions, so that different non-centrosymmetric nano graphene molecules can be prepared.
As further preferable in the present technical solution: the diene is a cyclopentadienone derivative, and the structure of the diene is shown as formula II and formula III:
wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
The cyclopentadienone derivative, more preferably, has the following structure of formula II:
the cyclopentadienone derivative, more preferably, has the following structure of formula III:
the cyclopentadienone derivative, more preferably, comprises two equivalents of diene structure as follows:
as further preferable in the present technical solution: the diene is a thiophene derivative, and the structure of the diene is as shown in formula IV and formula V:
wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
Further, the thiophene derivative has the following structure:
as further preferable in the present technical solution: the diene is a furan derivative, and has a structure shown in formula VI and formula VII:
wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected fromSubstituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
Still further, the furan derivative has the following structure:
the preparation method of the non-centrosymmetric nano-graphene molecule comprises the following steps:
s1, carrying out Diels-Alder cyclization reaction on 3,7, 10-tris (trimethylsilyl) -2,6, 11-tris (trifluoromethanesulfonate) triphenylene and a diene to generate an intermediate I;
s2, carrying out Diels-Alder cyclization reaction on the intermediate I and a second diene to generate an intermediate II;
s3, carrying out Diels-Alder cyclization reaction on the intermediate II and a third diene to generate a compound I;
wherein: ar (Ar)1、Ar2、Ar3In a different structure of
Wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
The preparation method of the non-centrosymmetric nano-graphene molecule comprises the following steps:
A1. reacting 3,7, 10-tris (trimethylsilyl) -2,6, 11-tris (trifluoromethanesulfonate) triphenylene with a diene to generate an intermediate I or an intermediate III;
A2. carrying out Diels-Alder cyclization reaction on the intermediate I or the intermediate III and a second diene to generate a compound II or a compound III;
wherein: ar (Ar)1、Ar2In a different structure of
Wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
The invention also aims to provide a non-centrosymmetric nano-graphene molecule obtained by the preparation method of the non-centrosymmetric nano-graphene molecule, which has the following structure:
wherein: ar (Ar)1、Ar2、Ar3In a different structure of
Wherein: r1、R2、R3、R4Each independently selected from hydrogen, hydroxy, halo, alkyl, silyl, oxyalkyl, phenyl, aryl, heterocyclic aryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.
As further preferable in the present technical solution: the non-centrosymmetric nano graphene molecular structure is as follows:
the third purpose of the invention is to apply the non-centrosymmetric nano graphene molecule in the preparation of an organic electroluminescent device.
The non-centrosymmetric nano graphene molecules are used as an electron transport layer material of the organic electroluminescent device.
A fourth object of the present invention is to provide an organic electroluminescent device, which includes a substrate, an anode layer, a cathode layer, and at least one organic functional layer between the anode layer and the cathode layer, where the organic functional layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, and the electron transport layer of the electron transport layer contains non-centrosymmetric nanographene molecules.
Compared with the prior art, the invention has the beneficial effects that:
(1) by optimizing the synthesis method, the invention designs the preparation of the non-centrosymmetric nano graphene compound by gradually reacting from a precursor capable of multilateral reaction. The method synthesizes the non-centrosymmetric nano-graphene molecules for the first time, and has pioneering significance.
(2) The method has the advantages of simple synthetic route, simple operation and low price, and is a very good method for preparing the non-centrosymmetric nano graphene with a unique structure.
(3) According to the synthesis method, tripartite Diels-Alder reaction is carried out by utilizing the triphenylene triarylyne precursor, the edge structure of the molecule is designed by a stepwise synthesis method, the edge and band gap of a target compound can be effectively improved, the purpose of regulating and controlling the photoelectric property of the compound is achieved, and the compound has better electron transport property.
Drawings
FIG. 1 is a synthetic route for synthesizing non-centrosymmetric nano-graphene according to the present invention;
FIGS. 2 to 7 are mass spectrograms of Compound 4, Compound 5, Compound of interest TM-1, Compound of interest TM-2, Compound 6, Compound of interest TM-3, respectively;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 Synthesis of non-centrosymmetric Compounds route 1 Synthesis of TM-1
(1) Synthetic route to Compound 4
Precursor I (100mg, 0.112mmol), compound 1(65mg, 0.169mmol) and cesium fluoride (25mg, 0.164 mmol) were placed in a 35mL screw-top bottle, 9mL acetonitrile and 3mL dichloromethane were added, bubbled for 30min, sealed and heated to 90 ℃ under reflux, reacted for 12 h. The product was filtered, washed with a large amount of acetonitrile and subjected to column chromatography to give 48mg of compound 4 as a pale yellow solid powder with a yield of 42%.
MS: calculate [ M]+: 1022.20, test [ M/z ═ M]+: 1022.2, see fig. 2.
(2) Synthetic route to Compound 5
The obtained compound 4(110mg, 0.108mmol), compound 2(83.5mg, 0.161mmol) and cesium fluoride (20.4mg, 0.134mmol) were put into a 75mL screw-top bottle, 6mL of methylene chloride and 15mL of acetonitrile were added, bubbling was carried out for 30min, the bottle mouth was closed, and the reaction was carried out at 90 ℃ for 12 hours. The product was filtered, washed with a large amount of acetonitrile, and column-chromatographed to give 20mg of compound 5 as a pale green solid powder with a yield of 14.40%.
MS: calculate [ M]+: 1290.47, test [ M/z ═ M]+: 1290.5, see fig. 3.
(3) Synthetic route for compound TM-1
The prepared Compound 5(50 mg)0.039mmol), compound 3(35mg, 0.092mmol) and cesium fluoride (15mg, 0.099mmol) were put in a 56mL screw bottle, 5mL of methylene chloride and 12mL of acetonitrile were added, bubbling was carried out for 30min, the bottle mouth was closed, and the reaction was carried out at 90 ℃ for 12 hours. The product was filtered, washed with a large amount of acetonitrile, and subjected to column chromatography to give 40mg of compound TM-1 as a pale green solid powder with a yield of 72.6%. H NMR (400MHz, CDCl)3)δ8.67(s，1H)，8.63(s，1H)，8.59(s，1H),8.56(s，1H),8.49(s，1H)，8.48(s，1H)，8.24(s，1H)，8.22(s，1H)，8.03(s，1H)，7.98(s，1H)，7.82-7.81(d，4H)，7.46(m，10H)，7.41-7.37(m，12H),7.15-7.12(m，12H)，6.85(m，12H)，1.09-1.08(d，18H)ppm。
MS: calculate [ M]+: 1422.61, test [ M/z ═ M]+: 1422.6, see fig. 4.
The synthesis method of the stepwise synthesis successfully synthesizes the non-centrosymmetric nano-graphene molecule TM-1, is suitable for various diene bodies, is simple, and is beneficial to performing edge modification on the molecule so as to better improve the photoelectric effect of the molecule.
EXAMPLE 2 Synthesis of non-centrosymmetric Compounds route 2 Synthesis of TM-2 and TM-3
(1) Synthetic route for compound TM-2
Prepared compound 4(90mg, 0.088mmol), compound 2(183mg, 0.477mmol) and cesium fluoride (70mg, 0.460mmol) were put into a 75mL screw bottle, 6mL of dichloromethane and 15mL of acetonitrile were added, bubbling was carried out for 30min, the bottle mouth was closed, and the reaction was carried out for 12 hours by heating to 90 ℃. The product was filtered, washed with a large amount of acetonitrile and separated by column chromatography to give 20mg of compound TM-2 as a pale green solid powder with a yield of 14.60%. H NMR (400MHz, CDCl)3)δ8.58(s，2H)，8.51(s，2H)，8.47(s，2H)，7.99-7.97(d，4H)，7.83-7.81(d，8H),7.48-7.46(d，8H),7.38(s，8H)，7.15(s，12H),6.87-6.80(m，12H),1.09-1.08(d，36H)ppm。
MS: calculate [ M]+: 1558.74, test [ M/z ═ M]+: 1558.7 as shown in fig. 5.
(2) Synthetic route to Compound 6
Precursor I (100mg, 0.112mmol), compound 1(173mg, 0.450mmol) and cesium fluoride (34mg, 0.225mol) were placed in a 56mL screw-top bottle, 9mL acetonitrile and 3mL dichloromethane were added, bubbled for 30min, sealed and heated to 90 ℃ under reflux, reacted for 12 hours. The product was filtered, washed with a large amount of acetonitrile and subjected to column chromatography to give 92mg of compound 6 as a pale yellow solid powder with a yield of 71%. H NMR (500MHz, CDCl)3)δ8.71(s，1H),8.62-8.59(m，3H)，8.25(s，1H)，7.94(s，1H)，7.34-7.28(m，10H)，7.21-7.18(m，2H),7.13-7.12(d，8H),6.91-6.82(m，20H)，0.32(s，9H)ppm。
MS: calculate [ M]+: 1156.36, test [ M/z ═ M]+: 1156.4, as shown in fig. 6.
(3) Synthetic route for compound TM-3
Compound 6(30mg, 0.026mmol), Compound 2(16mg, 0.042mmol) and cesium fluoride (14mg, 0.092mmol) were placed in a 56mL screw-top flask, 3mL dichloromethane and 9mL acetonitrile were added, bubbled for 30min, the flask was closed, heated to 90 ℃ and reacted for 12 hours. The product was filtered and washed with copious amounts of acetonitrile. A yellowish green solid powder was obtained, which was separated by column chromatography to finally obtain 14mg of the compound TM-3 as a pale green solid powder with a yield of 37.84%. H NMR (400MHz, CDCl3) Δ 8.76-8.74(d, 4H), 8.47(s, 2H), 7.98-7.97(d, 2H), 7.84(s, 4H),7.50-7.45(m, 10H), 7.37-7.29(m, 4H),7.18(s, 4H), 7.08-6.95(m, 12H),6.85-6.69(m, 22H), 1.21(s, 18H) ppm.
MS: calculate [ M ] +: 1424.63, test [ M ] +: 1424.6, as shown in fig. 7.
The synthesis of the compounds TM-2 and TM-3 illustrates the great effect of compound proportioning equivalent in the stepwise design reaction, and the method has very good controllability, and the synthesis of the compounds can be controlled to a great extent through the reactant proportioning so as to be better applied to the practice.
Example 3
Synthesizing non-centrosymmetric nano-graphene molecules according to the method of example 1 or example 2, wherein dienes required by the synthesis of the non-centrosymmetric nano-graphene molecules are shown in the following table:
example 4
Preparing a device:
1. substrate treatment: water, sulfuric acid: hydrogen peroxide is 3: 7 the substrate is cleaned by plasma cleaning of the mixed solution, isopropanol, oxygen and dried for one and a half hours at 90 ℃. After cooling to room temperature, a drop of octadecyltrichlorosilane was deposited on the substrate by vapor deposition, and the system was heated to 120 ℃ and held under vacuum for 2 hours.
2. Samples were spin coated onto substrates to a thickness of 20-40 μ nm.
3. Based on a field effect transistor with bottom gate top contact, a doped n-type silicon wafer is used as a gate electrode, and a drain electrode and a source electrode with the thickness of 30nm are deposited on the device by a method of sublimating a gold film.
4. After the device is prepared, the material mobility can be obtained.
Using the test conditions described above, the synthetic material mobilities described above were all 1.5cm2V-1s-1A rank.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in 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 (10)
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