CN108238973A - A kind of liquid crystal semi-conducting material and its preparation method and application - Google Patents

A kind of liquid crystal semi-conducting material and its preparation method and application Download PDF

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CN108238973A
CN108238973A CN201611206500.6A CN201611206500A CN108238973A CN 108238973 A CN108238973 A CN 108238973A CN 201611206500 A CN201611206500 A CN 201611206500A CN 108238973 A CN108238973 A CN 108238973A
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liquid crystal
reaction
conducting material
desired intermediate
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孟鸿
陈彦彤
徐秀茹
贺耀武
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Peking University Shenzhen Graduate School
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    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/24—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing nitrogen-to-nitrogen bonds
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    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/13—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the technical field of thermotropic switches

Abstract

The present invention discloses a kind of liquid crystal semi-conducting material and its preparation method and application.The liquid crystal semi-conducting material includes organic semiconductor parent nucleus group, photochromic group and thermotropic liquid crystal mesogens, organic semiconductor parent nucleus is the core of entire molecule, photochromic group can carry out the property of ultraviolet light and visible ray sensitivity the transformation in conformation or structure, thermotropic liquid crystal mesogens assign the characteristic of molecular liquid crystal phase so as to make molecules align more orderly using its superior liquid crystal property, and then realize thermotropic semi-conducting material and improve mobility.Liquid crystal semi-conducting material of the present invention is prepared into Organic Thin Film Transistors using vapor deposition means, device performance is obviously improved after irradiating ultraviolet light, and the performance of device is even more promoted once again under ultraviolet light and annealing double action.The semi-conducting material of this kind of function type will realize their distinctive potential qualities, using such as intelligent device, sensor and functional switch etc. in the opto-electronic device.

Description

A kind of liquid crystal semi-conducting material and its preparation method and application
Technical field
The present invention relates to Organic Thin Film Transistors Material Field more particularly to liquid crystal type functional form Organic Thin Film Transistors materials Material and its preparation method and application.
Background technology
Based on Organic Thin Film Transistors (OTFT) in terms of integrated circuit, Active Matrix LCD At, Flexible Displays and sensor Extensive use, organic semiconductor attracted a large amount of concern over the last couple of decades.It (is based on inorganic thin-film transistors Si it) compares, organic film FET (OTFT) possesses many attracting advantages, such as simple, various and inexpensive Preparation method；Abundant and inexhaustible molecular structure alteration and the device performance for arbitrarily crimping and infinitely stretching.For The application of organic field effect tube is better achieved, we also need to further improve its device mobility, air-stable Property etc..Relative to traditional method for stepping up mobility, we are more likely to exploitation new type functional semi-conducting material and come Realize a kind of approach so as to fast lifting mobility.
Also there are some at present as the core material applied in organic field effect tube functional device for light control materials Problem：(1) organic semiconducting materials of the organic light-operated transistor of major part reported at present are both for different wave length visible ray Detection, it is also relatively fewer to the research of ultraviolet detector.And ultraviolet detection technology is in space safety communication, astronomical observation, combustion Burn the huge application prospects of various aspects such as engineering, purifying water process, flame monitoring and in ultraviolet detection technical foundation The technologies such as the ultraviolet guidance that grows up, ultraviolet early warning, ultraviolet communication therefore study Gao Ling in the immense value of national defence Quick, fast-response, low noise, small size, low-power consumption and integrate ultraviolet light detection, modulation, switching function ultraviolet organic light Control transistor is of great significance.(2) mobility of organic light-operated transistor need to be improved；(3) it is used to prepare organic light-operated Soluble, the printable organic semiconducting materials of transistor more lack；(4) the stability side of organic light-operated transistor device Face is to be improved.In conclusion the high performance ultraviolet light response organic semiconducting materials of solution processable type are one important Research direction.
In numerous semi-conducting materials, due to and benzene material powerful π-pi-conjugated system shows it is outstanding Device performance.In recent years, many studies have reported azobenzene chromophore based on its outstanding reversible photoisomerization characteristic and Has the application prospect in reversible phase transfer catalysis (PTC), detector and intelligence sensor etc..In addition, some researches show that, The liquid crystalline phase of high-sequential can promote molecule organic semiconductor preferably to be carried in particular directions into rearrangement so as to improve device Flow the transport capacity of son.
Invention content
It is put forward for the first time organic half for one end of photochromic group being introduced, there is high mobility, be conjugated greatly in the present invention Conductor parent nucleus group, and there is soluble, height to obtain by introducing thermotropic liquid crystal mesogens in the other end of photochromic group The organic semiconducting materials of mobility, outstanding ultraviolet light response characteristic, and investigate its ultraviolet light-operated transistor performance.It will improve Existing organic semiconducting materials become new type functional semi-conducting material and push its hair in fields such as transistor sensors Exhibition.Several liquid crystal semi-conducting materials, molecular structural formula are as follows：
Wherein, substituent R be it is following in any one：
The value of m and n is 1~15.
Specifically, the MOLECULE DESIGN of liquid crystal semi-conducting material that the present invention designs meets claimed below:
(1) the good semiconductor parent nucleus that higher carrier transport function can be provided of device performance there are one tool, half Conductor parent nucleus is the core of entire molecule；
(2) introducing one has the azobenzene chromophore of photochromic property or has the functional groups of similarity, should Class group is sensitive to ultraviolet light and visible ray, can carry out the transformation in conformation or structure so as to the functional load as entire molecule When；
(3) 1-2 long alkyl chain or branch are added to put forward high molecular solubility, and assigns the characteristic of molecular liquid crystal phase So as to make molecules align more orderly using its superior liquid crystal property, and then realize thermotropic semi-conducting material and improve migration Rate.
The molecule for having requirements above equally possesses good air stability, electrochemical stability, p-type semiconductor Performance, photic and thermotropic modulating properties etc. is established to apply in transistor device, transistor sensor and other intelligent devices Fabulous basis and prospect are determined.
Description of the drawings
The high resolution mass spectrum of desired end product in Fig. 1 embodiments 1；
The ultra-violet absorption spectrum of desired end product in Fig. 2 embodiments 1.
Specific embodiment
The present invention provides liquid crystal semi-conducting material and its preparation method and application, to make the purpose of the present invention, technical solution And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein Example is only used to explain the present invention, is not intended to limit the present invention.
Specifically, liquid crystal semi-conducting material of the invention, molecular structural formula are as follows：
Embodiment 1
Specifically,
With
For illustrate, when parent nucleus knot Structure is anthracene, and photochromic function structure is azobenzene, and thermotropic liquid crystal part is the straight alkoxy chain of length of carbon atom number 10, the molecule The three parts group of photochromic, thermotropic liquid crystal and semiconductor property is had been assigned, by a series of characterization method, such as TGA, POM, DSC, UV-vis ultraviolet spectra, AFM and STM show that the molecule has good air stability, various calorifics Matter liquid crystal texture, outstanding photo-isomerisable phenomenon etc..Organic Thin Film Transistors is prepared after irradiating ultraviolet light using vapor deposition means Device performance is obviously improved, and the performance of device is even more promoted once again under ultraviolet light and annealing double action.This kind of function The semi-conducting material of type will realize their distinctive potential qualities, using such as intelligent device in the opto-electronic device, sensor and function Property switch etc..
Specifically, the synthetic route of the liquid crystal semiconductor molecule is as follows：
A, 4- nitrophenols are added to K2CO3Anhydrous dimethyl formamide suspension in, heat the mixture to 80 DEG C, bromo-decane is then added in into system and reacts 6h.Solvent is removed after reaction, and crude product is dissolved in chloroform and spent Ionized water is cleaned multiple times.Merge organic layer MgSO4It is dry, then filter out MgSO4, it is loaded into proper silica gel and crosses column acquisition target Intermediate product.
B, by the SnCl of gained desired intermediate and 5 times of equivalents in a2It is added in two mouth flask and then adds in ethyl alcohol simultaneously It is heated to reflux.When system starts reflux, add in concentrated hydrochloric acid and maintain reaction 5h.Mixed system is acidified after reaction, There are a large amount of Precipitations then to filter and repeatedly rinse to dissolve until there is no products with dichloromethane.Mother liquor is washed with water simultaneously It is repeatedly extracted with dichloromethane, the desired intermediate for being finally spin-dried for organic solution.
C, at 5 DEG C hereinafter, NaNO by 2.5M2Solution is slowly added into the hydrochloric acid mixed solution of desired intermediate in b In.The system temperature is maintained to be then slowly added in the NaOH solution of phenol at 5 DEG C or so.It is thick to produce with the addition of NaCl Object is precipitated out from system, and pure desired intermediate is obtained after being recrystallized with n-hexane.
D, by gained desired intermediate in c in N2In the lower addition round-bottomed flask of protection, dry dichloromethane and three Ethamine is slowly added into syringe and is cooled to -20 DEG C.Trifluoromethanesulfonic anhydride is slowly dropped to followed in turn by syringe In system and maintain 20 DEG C of thermotonus 1.5h.Q. s. methylene chloride is added in after reaction and with water and saturated common salt moisture Qing Xi not be 3 times, obtained organic layer Na2SO4Suitable silica gel is added in after dry filter and crosses column, desired intermediate.
E, desired intermediate, 2- borates anthracene and Pd (PPh will be obtained in d3)4It is added in pressure bottle and is persistently filled with N2Maintain 15min.Then, in order in N2The lower K for adding in ethyl alcohol, toluene and 2M of protection2CO3Aqueous solution, 90 DEG C of heating were reacted Night.It treats after reaction, mixed system to be filtered and carefully cleans filter cake with water, ethyl alcohol and acetone successively, crude product is done Sublimation purification obtains pure desired end product and is named as APDPD after dry.Elemental analysis result is as follows：C36H38N2The result of calculation of O： C,84.01；H,7.44；N, 5.44. test result：C,84.12；H,7.41；N,5.34.
Above-mentioned steps e can also be substituted using following steps
A, by gained intermediate objective product, potassium acetate, Pd (dppf) Cl in d2It is added to and is equipped with connection boric acid pinacol ester 120 DEG C of reaction 3h are heated in the pressure bottle of 1,4- dioxane solvents；It is more that system is filtered to take into filter cake water after reaction Filter cake dissolving is added in suitable silica gel and crosses column, obtains desired intermediate by secondary cleaning in methylene chloride；
B, by gained target product, 2- bromines anthracene, Pd (PPh in A3)4It is added in pressure bottle and continues with Aliquat 336 It is filled with N215min is maintained, semiconductor parent nucleus is carried out unilateral；Then, in order in N2Protection is lower to add in toluene and the Na of 2M2CO3 Aqueous solution heats 90 DEG C of reactions overnight；It treats after reaction, mixed system to be filtered and careful with water, ethyl alcohol and acetone successively Ground cleans filter cake, and sublimation purification obtains pure desired end product after crude product is dried.
The liquid crystal semiconductor molecule APDPD of obtained azo-based anthracene, high resolution mass spectrum is as shown in Figure 1, result is shown Show in gained final powders in addition to desired end product APDPD does not contain other compositions.Its ultraviolet absorption curve as shown in Fig. 2, As seen from the figure, which can issue the variation of raw molecular configuration in the irradiation respectively of ultraviolet-visible light well So as to influence UV absorption.
Embodiment 2
WithFor
Its synthetic route is as follows：
A, 4- nitrophenols are added to K2CO3Anhydrous dimethyl formamide suspension in, heat the mixture to 80 DEG C, bromo-decane is then added in into system and reacts 6h.Solvent is removed after reaction, and crude product is dissolved in chloroform and spent Ionized water is cleaned multiple times.Merge organic layer MgSO4It is dry, then filter out MgSO4, it is loaded into proper silica gel and crosses column acquisition target Intermediate product.
B, by the SnCl of gained desired intermediate and 5 times of equivalents in a2It is added in two mouth flask and then adds in ethyl alcohol simultaneously It is heated to reflux.When system starts reflux, add in concentrated hydrochloric acid and maintain reaction 5h.Mixed system is acidified after reaction, There are a large amount of Precipitations then to filter and repeatedly rinse to dissolve until there is no products with dichloromethane.Mother liquor is washed with water simultaneously It is repeatedly extracted with dichloromethane, the desired intermediate for being finally spin-dried for organic solution.
C, at 5 DEG C hereinafter, NaNO by 2.5M2Solution is slowly added into the hydrochloric acid mixed solution of desired intermediate in b In.The system temperature is maintained to be then slowly added in the NaOH solution of phenol at 5 DEG C or so.It is thick to produce with the addition of NaCl Object is precipitated out from system, and pure desired intermediate is obtained after being recrystallized with n-hexane.
D, by gained desired intermediate in c in N2In the lower addition round-bottomed flask of protection, dry dichloromethane and three Ethamine is slowly added into syringe and is cooled to -20 DEG C.Trifluoromethanesulfonic anhydride is slowly dropped to followed in turn by syringe In system and maintain 20 DEG C of thermotonus 1.5h.Q. s. methylene chloride is added in after reaction and with water and saturated common salt moisture Qing Xi not be 3 times, obtained organic layer Na2SO4Suitable silica gel is added in after dry filter and crosses column, desired intermediate.
E, desired intermediate, 2,6- diborates anthracene and Pd (PPh will be obtained in d3)4It is added in pressure bottle and continues It is filled with N2Maintain 15min.Then, in order in N2The lower K for adding in ethyl alcohol, toluene and 2M of protection2CO3Aqueous solution heats 90 DEG C instead It should stay overnight.It treats after reaction, mixed system to be filtered and carefully cleans filter cake with water, ethyl alcohol and acetone successively, will slightly be produced Sublimation purification obtains pure desired end product after object drying.
Above-mentioned steps e can also be substituted using following steps
A, by gained intermediate objective product, potassium acetate, Pd (dppf) Cl in d2It is added to and is equipped with connection boric acid pinacol ester 120 DEG C of reaction 3h are heated in the pressure bottle of 1,4- dioxane solvents；It is more that system is filtered to take into filter cake water after reaction Filter cake dissolving is added in suitable silica gel and crosses column, obtains desired intermediate by secondary cleaning in methylene chloride；
B, by gained target product, 2,6- dibromoanthracenes, Pd (PPh in A3)4It is added in pressure bottle simultaneously with Aliquat 336 Persistently it is filled with N215min is maintained, unilateral or bilateral substitution is carried out to semiconductor parent nucleus；Then, in order in N2Protection is lower to add in first The Na of benzene and 2M2CO3Aqueous solution heats 90 DEG C of reactions overnight；It treats after reaction, mixed system to be filtered and successively with water, second Alcohol and acetone carefully clean filter cake, and sublimation purification obtains pure desired end product after crude product is dried.
Embodiment 3
With
For, synthesis Route is as follows：
A, the n-BuLi of 4.3ml is added in into the 50ml THF solutions equipped with 2- methyl -3 bromo thiophene (5.70mmol) Hexane solution (1.6M, 6.88mmol), in N215min is stirred under protection at a temperature of -60 DEG C.Then in -60 DEG C of temperature The lower octafluoro cyclopentene for adding in 0.35ml of degree, the mixed system continue to be stirred to react 3h.Dilute hydrochloric acid quenching is added in after reaction, Using extracted by ether product and it is washed with water.Merge organic layer MgSO4It is dry, filtering, add in suitable silica gel cross column obtain it is pure Intermediate product.
B, gained intermediate product (10mmol) in a is added in 100ml glacial acetic acid, then added at room temperature into the system Enter NBS (25mmol), reaction 5h is stirred continuously at 55 DEG C.After reaction, mixed solution is added in excessive ice water And extracted with dichloromethane, and with saturated sodium carbonate solution and water washing it is multiple after use MgSO4Dry, filtering adds in suitable Silica gel crosses column and obtains pure intermediate product.
C, gained intermediate product (1mmol) and -6 borate BTBT (2.5mmol) of 2- decyloxies in b are added to 30ml's In THF, Pd (PPh are then added at room temperature3)4(0.25mmol) and anhydrous Na2CO3(2N,15ml).System is heated to 75 DEG C in N236h is stirred at reflux under protection.It is extracted with ethyl acetate after reaction, and with a large amount of saturated salt solution and deionization Water washing is multiple, uses MgSO4Dry, filtering adds in suitable silica gel and crosses column and obtains pure final product.
In conclusion present invention introduces photochromic, thermotropic liquid crystal and the three parts group of semiconductor property, simultaneously also The air stability for increasing molecule and the solubility in conventional organic solvent make such molecule have outstanding device performance. Azobenzene compound refers to connect the molecule of two benzene ring structures containing azo double bond (- N=N-) in molecular structure.Azobenzene Class compound there are two kinds of isomers, respectively rodlike trans- (trans) isomers and cis- (cis) isomers for turning shape, The present invention is by introducing azobenzene chromophore or having the functional groups of similarity to make it have photochromic property.Liquid crystal is A kind of new states of matter between solid state and liquid state is a kind of flexible material with self-assembling function, is being divided Son and microscopic scale, have order and mobility.
The semi-conducting material of the present invention is prepared into Organic Thin Film Transistors using vapor deposition means, the device after irradiating ultraviolet light Part performance is obviously improved, and the performance of device is even more promoted once again under ultraviolet light and annealing double action.This kind of function type Semi-conducting material will realize their distinctive potential qualities, using such as intelligent device in the opto-electronic device, sensor and functionality Switch etc..
It should be understood that the application of the present invention is not limited to the above, it for those of ordinary skills, can To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect range.

Claims (9)

1. a kind of liquid crystal semi-conducting material, which is characterized in that its molecular structural formula be it is following in any one：
Wherein, substituent R be it is following in any one：
The value of m and n is 1~15.
2. liquid crystal semi-conducting material according to claim 1, which is characterized in that the liquid crystal semi-conducting material includes organic Semiconductor parent nucleus group, photochromic group and thermotropic liquid crystal mesogens, the organic semiconductor parent nucleus group and thermotropic liquid crystal base Group is located at the both ends of the photochromic group respectively.
3. liquid crystal semi-conducting material according to claim 2, which is characterized in that the photochromic group for azobenzene or There are the functional groups of similarity；The thermotropic liquid crystal mesogens are substituent R.
4. the liquid crystal semi-conducting material according to Claims 2 or 3, which is characterized in that the organic semiconductor parent nucleus group Unilateral or bilateral be connected with the photochromic group.
5. a kind of preparation method of liquid crystal semi-conducting material, which is characterized in that including step：
A, 4- nitrophenols are added to K2CO3Anhydrous dimethyl formamide suspension in, heat the mixture to 80 DEG C, Then corresponding halogenated hydrocarbons is added in into system and reacts 6h；Solvent is removed after reaction, and crude product is dissolved in chloroform simultaneously It is cleaned multiple times with deionized water；Merge organic layer MgSO4It is dry, then filter out MgSO4, it is loaded into proper silica gel and crosses column acquisition Desired intermediate one；
B, by the SnCl of gained desired intermediate one and 5 times of equivalents in a2It is added in two mouth flask and then adds in ethyl alcohol and add Heat reflux；When system starts reflux, add in concentrated hydrochloric acid and maintain reaction 5h；Mixed system is acidified after reaction, is had A large amount of Precipitations then filter and repeatedly rinse to dissolve until there is no products with dichloromethane；Mother liquor is washed with water Dichloromethane repeatedly extracts, and organic solution is finally spin-dried for obtaining desired intermediate two；
C, at 5 DEG C hereinafter, NaNO by 2.5M2Solution is slowly added into b in the hydrochloric acid mixed solution of desired intermediate two； The system temperature is maintained to be then slowly added in the NaOH solution of phenol at 5 DEG C or so；With the addition of NaCl, crude product from It is precipitated out in system, pure desired intermediate three is obtained after being recrystallized with n-hexane；
D, by gained desired intermediate three in c in N2In the lower addition round-bottomed flask of protection, dry dichloromethane and triethylamine It is slowly added into syringe and is cooled to -20 DEG C；Trifluoromethanesulfonic anhydride is slowly dropped to system followed in turn by syringe In and maintain 20 DEG C of thermotonus 1.5h；Q. s. methylene chloride is added in after reaction and is distinguished with water and saturated salt solution clear It washes 3 times, obtained organic layer Na2SO4Suitable silica gel is added in after dry filter and crosses column, obtains desired intermediate four；
E, desired intermediate four, corresponding semiconductor parent nucleus borate and Pd (PPh will be obtained in d3)4It is added in pressure bottle And persistently it is filled with N215min is maintained, unilateral or bilateral substitution is carried out to semiconductor parent nucleus；Then, in order in N2Protection is lower to be added in The K of ethyl alcohol, toluene and 2M2CO3Aqueous solution heats 90 DEG C of reactions overnight；It treats after reaction, by mixed system filtering and successively Filter cake is carefully cleaned with water, ethyl alcohol and acetone, sublimation purification obtains pure desired end product after crude product is dried.
6. a kind of preparation method of liquid crystal semi-conducting material, which is characterized in that including step：
A, 4- nitrophenols are added to K2CO3Anhydrous dimethyl formamide suspension in, heat the mixture to 80 DEG C, Then corresponding halogenated hydrocarbons is added in into system and reacts 6h；Solvent is removed after reaction, and crude product is dissolved in chloroform simultaneously It is cleaned multiple times with deionized water；Merge organic layer MgSO4It is dry, then filter out MgSO4, it is loaded into proper silica gel and crosses column acquisition Desired intermediate one；
B, by the SnCl of gained desired intermediate one and 5 times of equivalents in a2It is added in two mouth flask and then adds in ethyl alcohol and add Heat reflux；When system starts reflux, add in concentrated hydrochloric acid and maintain reaction 5h；Mixed system is acidified after reaction, is had A large amount of Precipitations then filter and repeatedly rinse to dissolve until there is no products with dichloromethane；Mother liquor is washed with water Dichloromethane repeatedly extracts, and organic solution is finally spin-dried for obtaining desired intermediate two；
C, at 5 DEG C hereinafter, NaNO by 2.5M2Solution is slowly added into b in the hydrochloric acid mixed solution of desired intermediate two； The system temperature is maintained to be then slowly added in the NaOH solution of phenol at 5 DEG C or so；With the addition of NaCl, crude product from It is precipitated out in system, pure desired intermediate three is obtained after being recrystallized with n-hexane；
D, by gained desired intermediate three in c in N2In the lower addition round-bottomed flask of protection, dry dichloromethane and triethylamine It is slowly added into syringe and is cooled to -20 DEG C；Trifluoromethanesulfonic anhydride is slowly dropped to system followed in turn by syringe In and maintain 20 DEG C of thermotonus 1.5h；Q. s. methylene chloride is added in after reaction and is distinguished with water and saturated salt solution clear It washes 3 times, obtained organic layer Na2SO4Suitable silica gel is added in after dry filter and crosses column, obtains desired intermediate four；
E, by gained intermediate objective product four, potassium acetate, Pd (dppf) Cl in d2It is added to connection boric acid pinacol ester equipped with 1,4- 120 DEG C of reaction 3h are heated in the pressure bottle of dioxane solvent；It is repeatedly clear that system is filtered to take into filter cake water after reaction It washes, filter cake dissolving is added in suitable silica gel in methylene chloride crosses column, obtains desired intermediate five；
F, by gained target product five, corresponding bromo semiconductor parent nucleus, Pd (PPh in e3)4Pressure resistance is added to Aliquat336 It is filled in bottle and persistently N215min is maintained, unilateral or bilateral substitution is carried out to semiconductor parent nucleus；Then, in order in N2Under protection Add in toluene and the Na of 2M2CO3Aqueous solution heats 90 DEG C of reactions overnight；It treats after reaction, by mixed system filtering and successively Filter cake is carefully cleaned with water, ethyl alcohol and acetone, sublimation purification obtains pure desired end product after crude product is dried.
7. a kind of preparation method of liquid crystal semi-conducting material, which is characterized in that including step：
A, n-BuLi hexane solution is added in into the THF solution equipped with 2- methyl -3 bromo thiophene, in N2In -60 DEG C under protection At a temperature of stir 15min；The octafluoro cyclopentene of 0.35ml is then added at a temperature of -60 DEG C, which continues to stir Mix reaction 3h；Dilute hydrochloric acid quenching is added in after reaction, using extracted by ether product and is washed with water；Merge organic layer to use MgSO4Dry, filtering adds in suitable silica gel and crosses column and obtains pure intermediate product one；
B, gained intermediate product one in a is added in glacial acetic acid, then NBS is added in into the system at room temperature, at 55 DEG C It is stirred continuously reaction 5h；After reaction, mixed solution is added in excessive ice water and is extracted with dichloromethane, and with full With sodium carbonate liquor and water washing it is multiple after use MgSO4Dry, filtering adds in suitable silica gel and crosses column and obtains pure intermediate product Two；
C, gained intermediate product two and semiconductor parent nucleus borate in b are added in THF, then add in Pd at room temperature (PPh3)4And anhydrous Na2CO3；System is heated to 75 DEG C in N236h is stirred at reflux under protection；Ethyl acetate is used after reaction Extraction, and washed repeatedly with a large amount of saturated salt solution and deionized water, use MgSO4Dry, filtering adds in suitable silica gel mistake Column obtains pure final product.
8. the liquid crystal semi-conducting material in claim 1-4 is prepared into Organic Thin Film Transistors, application in the opto-electronic device.
9. application according to claim 8, which is characterized in that the photoelectric device includes intelligent device, sensor and work( It can property switch.
CN201611206500.6A 2016-12-23 2016-12-23 A kind of liquid crystal semi-conducting material and its preparation method and application Pending CN108238973A (en)

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