CN109516997B - Fluorenyl-like windmill-shaped nano grid and preparation method and application thereof - Google Patents
Fluorenyl-like windmill-shaped nano grid and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorenyl-like windmill sodiumA Mige, a preparation method and an application thereof belong to the fields of nanotechnology and organic electronics. The fluorenyl windmill-like nano grid is a closed-loop structure taking a fluorenyl-like micromolecule derivative as a monomer, and has the following structural general formula:
the fluorenyl-like windmill-shaped nano grid is prepared by Friedel-crafts reaction cyclization and has the characteristics of simple preparation, mild reaction conditions, high yield, high selectivity, simple and convenient post-treatment, greenness, no toxicity, regular structure, larger rigidity, good structure expansibility, good solubility and the like; because the ring framework of the organic solar cell contains a plurality of thiophene ring electron donors and the whole structure is non-planar, the organic solar cell has good application prospect in the field of organic solar cells after being grafted with acceptor groups.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to a soluble annular non-planar fluorenyl-like windmill grid and a synthesis method and application thereof.
Background
Organic photovoltaics are one of the most fundamental research directions in the field of Organic electronics, and research on Organic Solar Cells (OSCs) began in 1959, and has been progressing slowly for some time thereafter. By the early nineties, scientists discovered that with polymers as electron donors and fullerenes (C60) as electron acceptors, the resulting excitons could be efficiently ionized and transferred under light. Photovoltaic devices based on organic polymers and fullerene receptors have become a new research hotspot. However, due to the existence of defects of fullerene acceptor materials, such as: poor stability under illumination conditions; the synthesis is complex and the price is high; energy level adjustment is difficult; weak absorption in the visible range, etc. Therefore, some scientists wish to synthesize new efficient non-fullerene acceptor materials by rational design. Currently, non-fullerene acceptor material classes have been overlaid from small molecules to polymers. Non-fullerene small molecule acceptor materials have developed very rapidly in recent years, and PCE of organic solar cells based on small molecule non-fullerene acceptor materials has exceeded 12% at present, [ Zhao, j.; li, y.and Yan, H, Nature Energy 2016, 1; deng, d.; zhang, y.and Wei, z., Nature Communications 2016,7 ] surpasses solar cells with traditional fullerene materials as acceptors. Early non-fullerene small molecule acceptor materials mostly have 2D planar structures, such as V-BT, TFDPP and the like. The material is simple to synthesize, convenient to purify, rich in types of selectable construction units and easy to regulate and control energy level. However, through research, researchers find that the excellent performance of the fullerene material as a receptor material has a great relationship with the three-dimensional spherical structure of the fullerene material. The three-dimensional spherical structure not only can enable the fullerene material to realize isotropic electron transfer, but also can effectively accept and stabilize electrons and reduce the recombination of charges. Therefore, some researchers have tried to design molecules based on a 3D spatial structure that mimics fullerene materials to adjust the size of phase separation of the materials in the thin film while increasing charge dissociation transport efficiency. At present, the design idea is widely applied and a remarkable effect is achieved. However, most of the reported structures are non-fullerene small molecule materials with a non-planar structure designed by taking linear molecules such as spiro, indenothiophene dialkyl or diaryl derivatives and cyclopentadithiophene dialkyl or diaryl derivatives as nuclear access receptor groups, and non-fullerene small molecule materials with a non-planar structure taking a non-planar closed-loop structure as a core are not reported at present.
In 2014, professor of jiuhai proposed a novel structurally rigid nanoscale three-dimensional closed-loop structure, namely organic nanograms (l.wang, g. -w.zhang, c. -j.ou, l. -h.xie, j. -y.lin, y. -y.liu and w.huang, org.lett.,2014,16, 1748-. The nano-lattice has definite edges and vertexes, active sites and can be flexibly used for constructing one-dimensional, two-dimensional and three-dimensional network structures with complex structures. In addition, the closed-loop structure has good non-planar characteristics due to the fact that the ring skeleton of the closed-loop structure contains a plurality of sp3 carbons.
Disclosure of Invention
The invention aims to provide a fluorenyl-like windmill-shaped nano grid, a preparation method and application thereof, and provides a preparation method of a soluble cyclic fluorenyl-like windmill grid with regular structure and excellent performance. In addition, the invention also indicates the application of the organic semiconductor material in the field of organic solar cells.
In order to achieve the purpose, the invention adopts the technical scheme that:
a fluorenyl-like windmill nanogrid based on cyclopentadithiophene or indenothiophene and having a rigid non-planar geometry having the structure of formula I:
in the formula: n is a natural number of 1-10;
R1is alkyl chain, alkoxy chain or aromatic hydrocarbon with alkyl chain or alkyl chain introduced at the 4-position of benzene ring, R2Is a halogen atom or a photoelectric active group.
Said R1The aromatic hydrocarbon is an alkyl chain, an alkoxy chain or aromatic hydrocarbon with the alkyl chain or the alkyl chain introduced to the 4 th position of a benzene ring, wherein the alkyl chain and the alkoxy chain comprise a linear type and a branched type, and the specific structure is as follows:
wherein n and m are natural numbers between 0 and 20.
Said R2Is one or more of fluorine, chlorine, phenyl, fluorene, carbazole, diphenylamine, 9-phenylfluorene, pyrrolopyrroledione and derivatives thereof, indolone derivatives, rhodanine and derivatives thereof, perylene imide and derivatives thereof, and the likeThe specific structural formula is as follows:
wherein R is3-R8Is a straight chain type or branched chain type alkyl chain, and X is a hydrogen atom, a fluorine atom or a chlorine atom.
A preparation method of a fluorenyl-like windmill-shaped nano grid comprises the following steps: at room temperature, acid is used as a catalyst, and in a dry organic solvent, the fluorenyl-like tertiary alcohol derivative is subjected to self-cyclization to obtain the fluorenyl-like windmill nano grid, wherein the reaction route is shown as a formula II:
in the formula: n is a natural number of 1 to 10.
The acid is one or a mixture of Lewis acid or protonic acid, preferably, the acid is: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid, titanium tetrachloride or hydrofluoric acid-antimony pentafluoride.
Preferably, the dry organic solvent is: dichlorobenzene, chlorobenzene, dichloromethane, trichloromethane, 1, 2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran or 1, 4-dioxane.
The fluorene-like windmill-shaped nanograms can be applied to organic solar cells.
Has the advantages that: in order to conveniently apply efficient green Friedel-crafts reaction to carry out ring-closing reaction, in addition, two types of fluorene structures, namely Cyclopentadithiophene (CPDT) and Indenothiophene (IDT), containing thiophene rings are selected as cores by combining the molecular design thought of A-D-A, and the non-planar non-fullerene fluorenyl windmill grid organic small molecule receptor material is obtained in one step through Friedel-crafts reaction of tertiary alcohol derivatives of the fluorene structures. The design and synthesis of the non-planar fluorenyl-like windmill grid can provide a new idea for the design and synthesis of novel non-planar organic small molecule receptor materials.
Hydrogen and carbon spectra by nuclear magnetic resonance (1H NMR、13C NMR), time-of-flight mass spectrometry (MALDI-TOF MS) and the like, and the like; the thermal stability of the material was tested by thermogravimetric analysis and differential thermal analysis; their electrochemical properties were characterized by cyclic voltammetry; the spectral stability of the material is tested in a high-temperature annealing mode of the film; selecting a proper wide-bandgap donor material through energy level matching, selecting a proper polymer donor material through energy level matching, mixing the two materials, spin-coating the materials to form a film, annealing the film, and characterizing the appearance of the film through AFM; the bulk heterojunction photovoltaic device is prepared by mixing the two materials in a blending mode and the photoelectric conversion efficiency of the bulk heterojunction photovoltaic device is tested.
The main advantages of the invention are:
(1) the fluorenyl-like windmill-shaped nano grid is prepared by Friedel-crafts reaction cyclization, and has the advantages of simple preparation, mild reaction conditions, high yield, high selectivity, simple and convenient post-treatment, greenness and no toxicity;
(2) the structure of the fluorenyl-like windmill-shaped nano grid is regular, has higher rigidity, good structure expansibility and good solubility;
(3) the ring framework of the flourenyl-like windmill-shaped nano grid contains a plurality of electron donor thiophene rings, and the whole structure is non-planar, so the flourenyl-like windmill-shaped nano grid has a good application prospect in the field of organic solar cells after being connected with an acceptor group.
Drawings
FIG. 1a is a nuclear magnetic hydrogen spectrum of cyclopentadithiophene-based aerovane I prepared in example 1;
FIG. 1b is a nuclear magnetic carbon spectrum of cyclopentadithiophene-based Piperger I prepared in example 1;
FIG. 1c is a time-of-flight mass spectrum of cyclopentadithiophene windmill grid I prepared in example 1;
FIG. 2a is a nuclear magnetic hydrogen spectrum of cyclopentadithiophene-based aerogels II prepared in example 2;
FIG. 2b is a time-of-flight mass spectrum of cyclopentadithiophene-based aerobergel II prepared in example 2;
FIG. 2c is a cyclic voltammogram of cyclopentadithiophene windmill III prepared in example 2.
Detailed Description
The invention is further explained below with reference to the drawings.
The invention relates to a fluorenyl-like windmill nano grid, which is based on Cyclopentadithiophene (CPDT) or Indenothiophene (IDT) and has a rigid non-planar geometric structure as shown in formula I:
in the formula: n is a natural number of 1-10;
R1is alkyl chain, alkoxy chain or aromatic hydrocarbon with alkyl chain or alkyl chain introduced at the 4-position of benzene ring, R2Is a halogen atom or a photoelectric active group.
As a preferred embodiment, R1The aromatic hydrocarbon is an alkyl chain, an alkoxy chain or aromatic hydrocarbon with the alkyl chain or the alkyl chain introduced to the 4 th position of a benzene ring, wherein the alkyl chain and the alkoxy chain comprise a linear type and a branched type, and the specific structure is as follows:
wherein n and m are natural numbers between 0 and 20.
As a preferred embodiment, R2The compound is one or more of fluorine, chlorine, phenyl, fluorene, carbazole, diphenylamine, 9-phenylfluorene, pyrrolopyrrole dione and derivatives thereof, indolone derivatives, rhodanine and derivatives thereof, perylene imide and derivatives thereof, and has the following specific structural formula:
wherein R is3-R8Is a straight chain type or branched chain type alkyl chain, and X is a hydrogen atom, a fluorine atom or a chlorine atom.
The synthesis method of the fluorenyl-like windmill-shaped nanogel comprises the following steps: at room temperature, acid is used as a catalyst, and in a dry organic solvent, the fluorenyl-like tertiary alcohol derivative is subjected to self-cyclization to obtain the fluorenyl-like windmill grid, wherein the reaction route is shown as a formula II:
wherein the acid comprises Lewis acid and protonic acid, and the addition amount of the acid catalyst is 2 to 20 times of that of the fluorenyl-like tertiary alcohol derivative calculated by molar weight according to the reaction activities of different substrates; the reaction concentration of the fluorenyl-like tertiary alcohol derivative is between 0.1 and 10 millimoles per liter according to the reactivity of different substrates.
The lewis acids and protonic acids are specifically: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid, titanium tetrachloride, or hydrofluoric acid-antimony pentafluoride in combination of 1 or more.
The dried organic solvents were: dichlorobenzene, chlorobenzene, dichloromethane, trichloromethane, 1, 2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran or 1, 4-dioxane.
The concrete synthesis steps of the fluorenyl-like windmill-shaped nano grid are as follows: adding the dried organic solvent into a reaction bottle, fully dissolving the fluorenyl-like tertiary alcohol derivative in a constant-pressure dropping funnel filled with the dried organic solvent, measuring acid by using an injector and injecting the acid into the reaction bottle, opening a valve of the constant-pressure dropping funnel and dropwise adding the constant-pressure dropping funnel into the reaction bottle, stirring for reaction for 2-4h until a reaction substrate completely reacts, and adding water to quench and neutralize the reaction. Extracting with dichloromethane, combining dichloromethane extraction liquid of organic phases, drying with anhydrous magnesium sulfate, filtering out a drying agent, removing the solvent by reduced pressure distillation, and separating the crude product by silica gel chromatography column chromatography to obtain the corresponding target product fluorenyl-like windmill grid.
The electrochemical property of the fluorenyl-like windmill-shaped nano grid is represented by cyclic voltammetry, and the fluorenyl-like windmill-shaped nano grid can be applied to organic solar cells.
The technical solutions of the present invention are further described below with reference to examples, but the examples do not limit the embodiments of the present invention. The invention is capable of many different embodiments and is not limited to only those described in this specification. Those skilled in the art should implement the invention within the scope of the present invention without departing from the spirit of the invention of the present application.
Example 1: cyclopentadithiophene-based windmill grid I
220ml of dried dichloromethane is added into a reaction bottle, cyclopentadithiophene tertiary alcohol-1 (0.2g, 0.42mM) is fully dissolved in a constant pressure dropping funnel containing 200ml of dried dichloromethane, boron trifluoride ethyl ether (0.1ml) is measured by a syringe and injected into the reaction bottle, a valve of the constant pressure dropping funnel is opened, dropwise adding is carried out into the reaction bottle, the reaction is stirred for 4 hours until the reaction substrate is completely reacted, and water is added to quench and neutralize the reaction. Extracting with dichloromethane, combining dichloromethane extracts of organic phases, drying with anhydrous magnesium sulfate, filtering to remove a drying agent, distilling under reduced pressure to remove the solvent, and separating and purifying a crude product by passing through a silica gel chromatographic column to obtain the cyclopentadithiophene windmill grid I (0.0729g, 38%) as a light yellow powder solid.
1H NMR(400MHz,CD3Cl)δ7.58-7.56(d,J＝7.2Hz,8H),7.37(s,4H),7.37-7.33(t,J＝8.8Hz,4H),7.28-7.22(m,6H),6.84(s,4H),6.81-6.79(d,J＝8.8Hz),3.95-3.86(m,8H),1.77-1.70(m,8H),1.45-1.39(m,8H),1.29-1.25(m,32H),0.88-0.84(t,J＝6.8,12H).13C NMR(100MHz,CDCl3)δ158.6,155.5,154.7,150.6,145.3,137.5,136.6,134.8,134.3,128.9,128.6,127.4,125.4,121.5,119.1,114.4,68.0,58.8,31.8,31.4,30.2,29.7,29.3,29.3,29.2,26.1,22.6,14.1.MALDI-TOF-MS(m/z):calcd for C116H112O4S8:1825.64；found:1824.20.
Example 2: cyclopentadithiophene-based windmill grid II
Adding 250ml of dried dichloromethane into a reaction bottle, fully dissolving cyclopentadithiophene tertiary alcohol-2 (0.8g and 2.3mM) in a constant pressure dropping funnel containing 200ml of dried dichloromethane, measuring boron trifluoride diethyl etherate (0.2ml) by using a syringe, dropwise adding the boron trifluoride diethyl etherate into the reaction bottle by opening a valve of the constant pressure dropping funnel, stirring for reacting for 4 hours until a reaction substrate is completely reacted, and adding water to quench and neutralize the reaction. Extracting with dichloromethane, combining dichloromethane extracts of organic phases, drying with anhydrous magnesium sulfate, filtering to remove a drying agent, distilling under reduced pressure to remove the solvent, and separating and purifying a crude product by a silica gel chromatographic column to obtain the cyclopentadithiophene windmill grid II (0.272g, 36%) as a light yellow powder solid.
1H NMR(400MHz,CD3Cl)δ7.59-7.57(d,J＝7.6,8H),7.40(s,4H),7.38-7.30(m,24H),7.10-7.07(dd,J＝8.4,8H),6.98(s,4H).MALDI-TOF-MS(m/z):calcd for C84H48S8:1313.15；found:1312.67.
Example 3
Measuring the electronic energy level of cyclopentadithiophene-based aerogels II by electrochemical cyclic voltammetry, wherein Ag/AgNO3As reference electrode, Fc/Fc+For internal reference. According to the initial oxidation potential (E)ox) And initial reduction potential (E)red) Lowest Unoccupied Molecular Orbital (LUMO) energy level (E)LUMO) And Highest Occupied Molecular Orbital (HOMO) energy level (E)HOMO) Can be represented by equation ELUMO/HOMO＝-e(Ered/ox+4.682) (eV). (in our measurement System, the redox potential of Fc/Fc + vs. Ag/AgNO3At 0.118V, we compared the truth of Fc/Fc +The empty level was set to 4.8 eV. ) The LUMO and HOMO energy levels of the cyclopentadithiophene windmill lattice II are-3.54 eV and-5.85 eV respectively.
Therefore, the fluorenyl-like windmill-shaped nano grid has good application prospect in the field of organic solar cells.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. A preparation method of a fluorene-like windmill-shaped nano grid is characterized by comprising the following steps: the method comprises the following steps:
adding 220ml of dried dichloromethane into a reaction bottle, fully dissolving 0.2g of cyclopentadithiophene tertiary alcohol-1 in a constant-pressure dropping funnel containing 200ml of dried dichloromethane, measuring 0.1ml of boron trifluoride diethyl etherate by using an injector, injecting into the reaction bottle, opening a valve of the constant-pressure dropping funnel, dropwise adding into the reaction bottle, stirring for reacting for 4 hours until a reaction substrate is completely reacted, adding water, and quenching for neutralization reaction; extracting with dichloromethane, combining dichloromethane extract liquid of organic phases, drying with anhydrous magnesium sulfate, filtering out a drying agent, removing the solvent by reduced pressure distillation, and separating and purifying a crude product by passing through a silica gel chromatographic column to obtain 0.0729g of light yellow powdery solid cyclopentadithiophene windmill grid I with the yield of 38%;
the structural formula of the cyclopentadithiophene tertiary alcohol-1 is as follows:
the structural formula of the cyclopentadithiophene windmill grid I is as follows:
or adding 250ml of dried dichloromethane into a reaction bottle, fully dissolving 0.8g of cyclopentadithiophene tertiary alcohol-2 into a constant-pressure dropping funnel containing 200ml of dried dichloromethane, measuring 0.2ml of boron trifluoride diethyl etherate by using an injector, injecting into the reaction bottle, opening a valve of the constant-pressure dropping funnel, dropwise adding into the reaction bottle, stirring for reacting for 4 hours until a reaction substrate is completely reacted, and adding water to quench and neutralize the reaction; extracting with dichloromethane, combining dichloromethane extract liquid of organic phases, drying with anhydrous magnesium sulfate, filtering out a drying agent, removing the solvent by reduced pressure distillation, and separating and purifying a crude product by passing through a silica gel chromatographic column and a column to obtain 0.272g of cyclopentadithiophene-based aerogei II as a light yellow powdery solid with the yield of 36%;
the structural formula of the cyclopentadithiophene tertiary alcohol-2 is as follows:
the structural formula of the cyclopentadithiophene windmill lattice II is as follows:
2. the application of a fluorenyl-like windmill grid in an organic solar cell is characterized in that the fluorenyl-like windmill grid is cyclopentadithiophene-based windmill grid II;
the structural formula of the cyclopentadithiophene windmill lattice II is as follows:
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