CN100393725C

CN100393725C - Dithienyl trithiophene compound and its prepn and application

Info

Publication number: CN100393725C
Application number: CNB2004100463508A
Authority: CN
Inventors: 刘云圻; 孙艳明; 马永强; 肖恺; 于贵; 朱道本
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2004-06-04
Filing date: 2004-06-04
Publication date: 2008-06-11
Anticipated expiration: 2024-06-04
Also published as: CN1706848A

Abstract

The present invention relates to a dithienyl trithiophene compound having thiophene molecules with high mobility and excellent conjugation. The preparation method of the compound comprises the following steps: dissolving dithienyl trithiophene and 2-thienyl boric acid in tetrahydrofuran; adding tetra(triphenylphophine) palladium and Na2CO3 aqueous solution; carrying out reflux in a nitrogen atmosphere while heating; extracting the solution; removing organic solvent to obtain target products. Organic field effect transistor devices made by using the compound as an organic layer have maximum mobility of 0.102 sq cm/V. s and switch ratio larger than 10000.

Description

A kind of dithienyl three thiophthene compounds and preparation method and application

Technical field

The present invention relates to a kind of organic semiconductor material, relate in particular to a kind of dithienyl three thiophthene compounds.

The invention still further relates to the preparation method of above-mentioned materials.

The invention still further relates to the application of above-mentioned materials in organic field effect tube.

Background technology

From 1987 first organic field effect tube (OFET) be in the news since (Koezuka, H.; Tsumura, A.; Ando, T.Synth Met, 1987,18,699), OFET has obtained very big development.Because it has a lot of particular performances, thereby more and more is subject to people's attention.The advantage of organic field effect tube is: preparation technology is simple, cost is low, in light weight and snappiness good, can be used as smart card, electronic trademark, storer, transmitter and Active Matrix Display, is the key components of organic optoelectronic device and circuit.Especially in recent years, the research work of organic field effect tube had obtained significant progress especially, and being is all having bigger breakthrough on the material or on the device technology of preparing.Efficient organic light-emitting field effect transistor, single-crystal field effect transistor and to drive Organic Light Emitting Diode by OFET luminous, the logical circuit that is formed by OFET etc. is in the news in succession.At present report makes the OFET mobility with organic rubrene monocrystalline and can reach 15cm ²/ Vs (Sundar, V.C.; Zaumseil, J.; Podzorov, V.; Menard, E.; Willett, R.L.; Someya, T.; Gershenson, M.E.; Rogers, J.A.Science.2004,303,1644), the performance of approaching unformed silicon (a-Si:H) device.Under the size of the inorganic FET situation near the miniaturization natural limit, OFET has demonstrated great development and application prospect.

Organic semiconductor material can be divided into n N-type semiconductorN and p N-type semiconductorN by the difference of its current carrier.What play transmitting effect in the n N-type semiconductorN mainly is electronics, and the p N-type semiconductorN then mainly is the hole.With pentacene and thiophene series of studies in these two kinds of semiconductor materials is many.As everyone knows, pentacene be one by five phenyl ring and the molecule that gets up with good conjugated system, so its mobility is very high, and thiophene is because it has the focus that satisfactory stability and modifiability also become people's research.If both are combined, the thiophene molecule of the synthetic a kind of conjugated system of design may contributed aspect the field-effect material to some extent.

Summary of the invention

The object of the present invention is to provide a kind of dithienyl three thiophthene compounds.

Another purpose of the present invention is to provide the preparation method of above-mentioned materials.

Dithienyl three thiophthene compound structures provided by the invention are as follows:

Wherein, R can be H base, alkyl, aryl or thiophene.

Preparation method of the present invention, its key step is:

1. dibromo three thiophthenes and 2-thienyl boric acid are dissolved in the tetrahydrofuran (THF) in the 0.3-1mmol/ml ratio, the mol ratio of dibromo three thiophthenes and 2-thienyl boric acid is 1: 2-4 is mixed with mixing solutions a.

2. add tetrakis triphenylphosphine palladium in mixing solutions a, tetrakis triphenylphosphine palladium and dibromo three thiophthene mol ratios are 0.05-0.1: 1.

3. in the mixing solutions of step 2, add Na ₂CO ₃The aqueous solution (2mol/l), tetrahydrofuran (THF) and Na ₂CO ₃Aqueous solution volume ratio is 2: 1.Under nitrogen atmosphere, 80-100 ℃ reflux 48-72 hour; Cooling, reactant places cold water, and dichloromethane extraction separates drying, and organic solvent is removed in evaporation, crosses the target product of silicagel column.

The dithienyl three thiophthene compounds of the present invention's preparation can be made organic field effect tube as organic layer.

The invention has the advantages that:

1. synthetic route is simple, the compound purity height that obtains.

2. this compound has good conjugation performance, and is stronger than the conjugacy that singly connects thiophene.

3. have satisfactory stability and solubility, the solution that is made into is placed the not change of its ultraviolet absorption peak several weeks in air.Dissolve in chloroform, tetrahydrofuran (THF), toluene equal solvent.

4. good prospects for application is arranged in OFET, and its mobility and on-off ratio are all very high, and (μ is up to 0.102cm ²/ Vs, on-off ratio is greater than 10 ⁴).

Description of drawings

The ultra-violet absorption spectrum of Fig. 1 compound solution and fluorescence spectrum;

The ultra-violet absorption spectrum of Fig. 2 compound film and fluorescence spectrum;

The structural representation of Fig. 3 organic field effect tube (compound is an organic layer);

Fig. 4 is the curve of output of the field-effect transistor of compound;

Fig. 5 is the transition curve of the field-effect transistor of compound.

Embodiment:

Synthetic route is shown below.

Wherein, R can be H base, alkyl, aryl or thiophene.

Embodiment 1

A. synthetic two bromos, three thiophthenes (being called for short compound 3)

The synthetic employing known technology of three thiophthenes (compound 1) and compound 3, but concrete reference (Allared, F.; Hellberg, J.; Remonen, T.Tetra.Lett.2002,43,1553.Pedulli, G.F.; Tiecco, M.; Guerra, M.; Martelli, G.; Zanirato, P.J.C.S.Perkin II.1978,212.)

B. synthetic dithienyl three thiophthenes (being called for short compound 4)

In the 250ml there-necked flask, add 0.392g (1.1mmol) two bromos three thiophthenes (compound 3), 0.294g (2.2mmol) 2-thienyl boric acid (compound 2), 30mg Pd (PPh ₃) ₄, add 20mlTHF solution and 10ml Na then ₂CO ₃(2M), mixed solution reflux 2 days.Use CH behind the cool to room temperature ₂Cl ₂Extraction, organic phase MgSO ₄Drying is rotated evaporate to dryness then.Thick product hi-sil method purifying, sherwood oil is as leacheate.Obtain lurid dithienyl three thiophthenes (0.21g, 53.0%) at last.

The dithienyl three thiophthene compounds of the present invention's preparation are a kind of thiophene molecules with high mobility, good conjugacy, below with ultimate analysis, nucleus magnetic resonance, mass spectral characteristi the chemical structure of this compound, studied the photophysical property of compound with ultra-violet absorption spectrum and fluorescence spectrum.With it is that organic semiconductor layer has been made transistor, and good device performance shows that compound is a kind of semiconductor material of excellence.

Mass spectrum [MS (EI)] m/z:360 (M ⁺).

Ultimate analysis (Anal.Calcd for C ₁₆H ₈S ₅): C, 53.30; H, 2.24. test: C, 52.50; H, 2.70.

Nucleus magnetic hydrogen spectrum [ ¹H NMR (400 MHz, CDCl ₃)], δ _H(7.05 2H, dd, J=3.6,5.2), 7.23 (2H, dd, J=1.2,3.6), 7.27 (2H, dd, J=1.2,3.6), 7.36 (2H, s).

Adopt identical synthetic route and synthetic method, the 2-thienyl boric acid with in the alternate embodiments 2 such as 5-alkylthrophene boric acid, 5-aryl thiophene boric acid, 5-thienyl thienyl boric acid can obtain corresponding dithienyl three thiophthene derivatives.

The above-claimed cpd luminosity:

Fig. 1 has provided the ultra-violet absorption spectrum and the fluorescence spectrum of compound solution, and its ultraviolet maximum absorption peak position is 387nm, and fluorescence emission maximum peak position is about 432nm.Fig. 2 has provided the ultra-violet absorption spectrum and the fluorescence spectrum of compound film, and its ultraviolet maximum absorption peak position is 356nm, and no matter fluorescence emission maximum peak position is in solution or the film about 398nm, and this compound all can send blue fluorescence.Just the ultraviolet of film and fluorescence are with respect to the equal blue shift slightly of the ultraviolet of solution and fluorescence, and this may be that the H-gathering has taken place organic molecule under filminess.

The field-effect transistor character of above-claimed cpd:

Fig. 3 has provided the structural representation of organic field effect tube, as shown in the figure, adopts highly doped silicon chip as substrate, and the thick silicon-dioxide of 470nm is as insulation layer, and source-drain electrode all uses gold as electrode.The thick organic layer of 40nm in vacuum tightness near 10 ^-4Evaporation is to silicon-dioxide under the Pa.At room temperature use Hewlett-Packard (HP) 4140B semi-conductor test instrument to measure its electrical property.

Fig. 4 and Fig. 5 be the curve of output and the transition curve of field-effect transistor respectively.With the synthetic new compound is that organic layer has been made a lot of organic field effect tube devices, and in these devices, wherein the highest mobility can reach 0.102cm ²/ Vs, on-off ratio is greater than 10 ⁴

All experimental results show that this compound is a kind of organic field effect tube material of excellence.

Claims

1. dithienyl three thiophthene compounds, its structure as shown in the formula:

In the formula: R is the H base.

2. one kind prepares the preparation method of compound according to claim 1, and its key step is:

A) dibromo three thiophthenes and 2-thienyl boric acid are dissolved in respectively in the tetrahydrofuran (THF) in the 0.3-1mmol/ml ratio, be 1 by dibromo three thiophthenes and 2-thienyl boric acid mol ratio again: 2-4 is mixed with mixing solutions;

B) add tetrakis triphenylphosphine palladium in the mixing solutions of step 1 preparation, tetrakis triphenylphosphine palladium and dibromo three thiophthene mol ratios are 0.05-0.1: 1;

C) adding concentration in the mixing solutions of step 2 preparation is the Na of 2mol/l ₂CO ₃The aqueous solution, tetrahydrofuran (THF) and Na ₂CO ₃Aqueous solution volume ratio is 2: 1; Under nitrogen atmosphere, 80-100 ℃ reflux 48-72 hour; Cooling, reactant places cold water, and dichloromethane extraction is removed organic solvent and is got target product.

3. preparation method as claimed in claim 2 is characterized in that, the hi-sil method purifying of the target product described in the step c.

4. dithienyl three application of thiophthene compound in field-effect transistor as claimed in claim 1.