CN101402852B

CN101402852B - Carbazolyl-containing unsymmetrical photochromicsm di-fragrant alkene monomer or polymer and electrochemical polymerization preparation method thereof

Info

Publication number: CN101402852B
Application number: CN 200810107380
Authority: CN
Inventors: 蒲守智; 范丛斌; 刘卫军; 缪文娟
Original assignee: Jiangxi Technology Normal College
Current assignee: Jiangxi Technology Normal College; Jiangxi Science and Technology Normal University
Priority date: 2008-11-12
Filing date: 2008-11-12
Publication date: 2012-03-14
Anticipated expiration: 2028-11-12
Also published as: CN101402852A

Abstract

The invention discloses a dissymmetrical photochromic diaryl monomer or polymer comprising a carbazolyl and an electrochemical polymerization preparation method thereof. The monomer can maintain excellent photochromic performances both in a liquid or in a film; moreover, both opened ring state (colorless state) and closed ring state (assuming in a color state) have the characteristics of excellent chemical and thermal stability, remarkable fatigue resistivity and higher sensitivity and the like. Moreover, the monomer has pointed absorption wavelength, changes different substitutional groups and can control the range of the absorption wavelength thereof better, thereby being matched with the lasers with different wavelengths and used for researching multi-wavelength optical information storage medium.

Description

The asymmetric photochromic diaryl alkene monomer of carbazolyl-containing or polymkeric substance and electrochemical polymerization preparation method thereof

Technical field

The present invention relates to a kind of asymmetric photochromic diaryl alkene monomer or polymkeric substance and electrochemical polymerization preparation method thereof of carbazolyl-containing.

Background technology

IT industry is the leading industry of the national economic development, and information storage then is the mainstay of information industry, is the assurance that realization information is effectively used.Optical storage is the important information memory technology that after magnetic storage, develops rapidly, and as far as optical memory material, commonly used have rare earth-transition metal alloy, oxide compound magneto-optic memory technique, organic dye and a photochromic material etc.The CD that great majority are produced with this technology is a read-only optical disc, will certainly cause the inconvenience of use and the waste of resource like this.In recent years the organic photochromic molecule has caused people's extensive concern; It is found that and to utilize photochromic molecular switch characteristic to come the storage of control information; This quasi-molecule has the Bistable quantized system; Under extraneous light action, several different methods can take place these two kinds of steady states can detected reversible tautomerization.Photochromic organic dye such as azo, spiro-pyrans and two fragrant alkene etc. are to study more general organic molecule photoswitch material.In these photochromic compounds, two fragrant alkene have Heat stability is good, sensitivity of light is strong and fatigue resistence is high characteristics, are to get a good chance of one of material that is applied to by molecular switch therefore.

In recent years; Research group's design by the M.Irie leader is synthetic; Developed the substituted diaryl ethylene photochromic compound of heterocycle base, this compounds generally shows advantages such as good thermostability, resistance to fatigue, high cyclisation quantum yield and sensitivity.Carbazole unit during two fragrant alkene are photochromic is to have good environmental stability, photoconductivity, hole transmission and the effective material cell of electroluminescent, in industry, has purposes widely.Though there is the number of chemical method can the polymkeric substance carbazole, those methods always have many places of not complying with one's wishes, and are loaded down with trivial details such as polymerization method, productive rate low and expensive.

Summary of the invention

The object of the invention just provides a kind of asymmetric photochromic diaryl alkene monomer or polymkeric substance and electrochemical polymerization preparation method thereof of carbazolyl-containing.

The asymmetric photochromic diaryl alkene monomer of carbazolyl-containing of the present invention or the general formula of molecular structure of polymkeric substance are following:

Wherein R is the verivate substituting group of hydrogen, methyl, phenyl ring and benzene, and for example R can be the substituting group of following type:

The asymmetric photochromic diaryl alkene monomer of carbazolyl-containing of the present invention or the electrochemical polymerization preparation method of polymkeric substance are: with 2-substituting group thiophene is raw material; Bromination under condition of ice bath at first; Under the n-Butyl Lithium effect; Remove the bromine on five, product generates single the replacement or disubstituted Perfluorocyclopentene with the Perfluorocyclopentene reaction again; Again under the n-Butyl Lithium effect, bromo normal hexane carbazole and the substituted Perfluorocyclopentene reaction of thiophene are obtained target small molecules product at last, last small molecules product obtains title product in the electrochemical workstation polymerization.

The asymmetric photochromic diaryl alkene monomer of carbazolyl-containing of the present invention or the main application of polymkeric substance have: directly with the practical VHD of such Composite Preparation, the VHD that organic photon type can be wiped rewriting, supper-fast optical information technical field of memory; Be used to prepare electrogen switch, molecular wire element; Be used to prepare photochromic luminescent device etc.

Advantage of the present invention mainly contains the following aspects:

1, the asymmetric photochromic diaryl alkene monomer of carbazolyl-containing all can keep the good photochromic performance in solution or film, and open loop attitude (colourless attitude) and equal tool good chemical of closed loop attitude (colour generation attitude) and characteristics such as thermostability, significant fatigue resistence and higher sensitivity;

2, the asymmetric photochromic diaryl alkene polymer monomer of carbazolyl-containing has specified absorbing wavelength; Can find out from accompanying drawing; The absorption spectrum of colour generation attitude is positioned at 450～600nm; Be that the laser apparatus of 532nm is complementary just in time, can be used for the development of shorter wavelength organic photochromic photon type recording medium with wavelength.Write fashionablely, at first use wavelength to be λ ₁Rayed, storage media is converted to the closed loop attitude by state open loop attitude, use wavelength to be λ then ₂Light change compound into the open loop attitude from the closed loop attitude.The conversion characteristic of primary binary " 0 " and " 1 " is come canned data in the storage, according to the variation of transsmissivity, can record information recorded then.

Description of drawings

Fig. 1 is the asymmetric photochromic diaryl alkene monomer of carbazolyl-containing of the present invention or the general formula of molecular structure of polymkeric substance;

Fig. 2 is the photochromic reactions principle schematic of polymer monomer of the present invention;

Fig. 3 is The compounds of this invention 1a monomer abosrption spectrogram before and after hexane solution medium ultraviolet rayed;

Fig. 4 is compound 1a monomer anodic polarization curves figure of the present invention;

Fig. 5 is the cyclic voltammogram of The compounds of this invention 1a monomer in BFEE and acetonitrile solution;

Fig. 6 is compound 1a resulting polymers diaphragm figure of the present invention;

Fig. 7 is compound 1a polymer membrane of the present invention and the infrared map of monomer;

Fig. 8 is compound 1a polymer membrane of the present invention and monomer nucleus magnetic hydrogen spectrum map.

Embodiment

Embodiment 1: [compound 1a]:

In general formula, when R is hydrogen, promptly constitute photochromic compound 1a, its name is called: gather [1-(2-thiotolene-3-yl), 2-[2-methyl-5-(N-n-hexyl carbazole) thiene-3-yl-)] Perfluorocyclopentene (1a), structural formula is following:

Its synthetic schemes is shown in Scheme 1:

Concrete synthesis step is described below:

1,3,5-two bromo-2-thiotolenes (1)

Under condition of ice bath, (25.617g 261.4mmol) is dissolved in the acetate, drips the acetate that contains the liquid bromine down in whipped state, behind the continuation ice bath reaction 8hr., adds moisture liquid, and water is used Na with 5-thiotolene (4) ₂

After the neutralization, use extracted with diethyl ether again, merge organic phase, use saturated Na ₂

Figure 2008101073803100002G2008101073803D0004184217QIETU

Wash anhydrous MgSO successively with the aqueous solution ₄Drying filters, and revolves to boil off solvent, and 52 ℃ of cuts are collected in underpressure distillation, obtain light yellow liquid 55.69g.

Productive rate: 83.25%.

Structure is identified: IR (cm ^-1) 780.4,810.1,949.8,1010.5,1138.8,1301.7,1450.9,1535.8,2785.8,3080.9.

2,2-methyl-3 bromo thiophene (2)

Under nitrogen and-78 ℃ of conditions, (5.12g 20mmol) is dissolved in the anhydrous diethyl ether with 1; Stir, slowly inject n-BuLi (20mmol), low-temp reaction is after half a hour; Naturally after 1.5hr. is reacted in the continuation that heats up; Add the entry stopped reaction, separatory is abandoned water, uses sherwood oil to cross silicagel column as eluent and gets product 3.27g.

Productive rate: 92.0%.

Structure is identified: ¹HNMR (400MHz, CDCl ₃, TMS) δ 2.40 (s, 3H ,-CH ₃), 6.89,6.90 (d, 1H, thiophene-H), 7.06,7.07 (d, 1H, thiophene-H).

3, [1,2-(2-thiotolene-3-yl)] Perfluorocyclopentene (3)

Reach under-78 ℃ of conditions at nitrogen, (3.27g 18.5mmol) is dissolved among the refining THF, stirs the hexane solution that adds n-BuLi (18.5mmol) and keeps low temperature stirred solution 30min with 2-methyl-3 bromo thiophene; (1.26mL 9.25mmol) joins in the reaction flask, and continuation rises to room temperature after reaction mixture is stirred 2hr. at low temperatures naturally, adds the suitable quantity of water termination reaction with the perfluoro cyclopentenes.Separatory is also used extracted with diethyl ether.Merge organic phase, distillation is desolvated, vacuum-drying.Resistates obtains combining red solid 2.47g with the separation of sherwood oil silica gel column chromatography.

Productive rate: 72.5%.

Structure is identified: ¹HNMR (400MHz, CDCl ₃, TMS) δ 2.41 (s, 6H ,-CH ₃), 6.69 (s, 2H, thiophene-H), 6.93 (s, 2H, thiophene-H).

4, N-(6-bromine n-hexyl) carbazole (4)

With carbazole (3.34g, 20.0mmol) be dissolved in DMSO (DMSO 99.8MIN., 30mL) in; Enriching NaOH solution adds (TBAB) Tetrabutyl amonium bromide (0.4g) and 1,6-dibromo-hexane (4.88g behind the stirring 20min; 20.0mmol), stirring at room 4h adds the water stopped reaction; Extracted with diethyl ether, the separation of petrol ether/ethyl acetate 2:1 silica gel column chromatography obtains white solid 4.95g.

Productive rate: 75.1%

Structure is identified: ¹HNMR (400MHz, CDCl ₃, TMS) δ 1.38-1.55 (m, 4H ,-CH ₂), 1.78-1.92 (m, 4H ,-CH ₂), 3.36 (t, 2H ,-CH ₂), 4.32 (t, 2H, ,-CH ₂), 7.23 (t, 2H, phenyl-H), 7.39,7.41 (d, 2H, phenyl-H), δ 7.46 (t, 2H, phenyl-H), δ 8.10,8.12 (d, 2H, phenyl-H).

5, [1-(2-thiotolene-3-yl), and 2-[2-methyl-5-(N-n-hexyl carbazole) thiene-3-yl-)] Perfluorocyclopentene (5)

Reach under-78 ℃ of conditions at nitrogen, (1.84g 10.0mmol) is dissolved among the refining THF, stirs the hexane solution that adds n-BuLi (10.0mmol) and keeps low temperature stirred solution 30min with [1,2-(2-thiotolene-3-yl)] Perfluorocyclopentene; (3.30g 10.0mmol) joins in the reaction flask, and continuation rises to room temperature after reaction mixture is stirred 2hr. at low temperatures naturally, adds the suitable quantity of water termination reaction with N-(6-bromine normal hexane base) carbazole.Separatory is also used extracted with diethyl ether.Merge organic phase, distillation is desolvated, vacuum-drying.Resistates obtains white powder solid 3.28g with the separation of sherwood oil silica gel column chromatography.

Productive rate 53%.

Structure is identified: ¹HNMR (400MHz, CDCl ₃, TMS) δ 0.80-0.90 (m, 4H ,-CH ₂), 1.27-1.54 (m, 4H ,-CH ₂), 1.83 (t, 2H ,-CH ₂), 2.35 (s, 6H, ,-CH ₃), 4.24 (t, 2H, ,-CH ₂), 6.67 (s, 1H, thiophene-H), 7.05,7.06 (d, 1H, thiophene-H), 7.14; 7.16 (d, 1H, thiophene-H), 7.24 (t, 2H, phenyl-H), 7.32,7.34 (d, 2H; Phenyl-H), and δ 7.44 (t, 2H, phenyl-H), δ 8.09,8.11 (d, 2H, phenyl-H).

¹³CNMR(400MHz，CDCl ₃，TMS)δ：9.12，10.07，27.06，28.81，42.81，108.58，118.77，120.36，121.52，122.82，124.26，125.60，133.31，140.36。

IR(cm- ¹)629，650，720，751，843，984，1043，1084，1121，1193，1275，1340，1384，1448，1483，1594，1633，2854，2926。

6, gather [1-(2-thiotolene-3-yl), and 2-[2-methyl-5-(N-n-hexyl carbazole) thiene-3-yl-)] Perfluorocyclopentene (1a)

Get 0.2g [1-(2-thiotolene-3-yl); 2-[2-methyl-5-(N-n-hexyl carbazole) thiene-3-yl-)] Perfluorocyclopentene (1a) adopts on the platinum electrode microdisk electrode to be done solvent boron trifluoride TBuA with pure acetonitrile earlier and does ionogen; On the polymerization working electrode, can not get polymkeric substance; And adopt full boron trifluoride ether solution to get polymer powder by autopolymerization, this powder dissolution poor performance, plastic poor performance.Adopting solvent afterwards is that the acetonitrile proportioning different with BFEE come polymerization; After repeatedly attempting, find that two fragrant alkene are dissolved in the 2.5mL acetonitrile solution; Fully add the 2.5mL boron trifluoride ether solution after the dissolving, adopting two platinum electrodes and working electrode is conductive glass, through the electrochemical workstation cyclic voltammetry scan; Find that polymkeric substance redox current density increases along with the increase of the scanning number of turns, the amount of polymkeric substance is increasing on the surface electrode.Along with the carrying out of scanning, the increase along with polymkeric substance on the electrode is also explained in the drift at redox peak simultaneously, needs bigger overpotential to overcome the resistance of polymeric film.Adopt the constant-voltage method polymerization to get polymer product at last.

Claims

1. the asymmetric photochromic diaryl alkene monomer or the polymkeric substance of a carbazolyl-containing, its general formula of molecular structure is following:

Wherein R is a hydrogen.