含苯甲酸基的四硫富瓦烯衍生物的合成、结构及性质研究

Synthesies,Structures and Properties of TTF Derivatives with Benzoyloxy

以亚磷酸三乙酯为偶合剂,通过偶联反应得到苯甲酸(酯)修饰的四硫富瓦烯(TTF)衍生物TTF-ph-COOCH3(7),由电子给体7水解得到含苯甲酸的电子给体TTF-ph-COOH(8)。利用1H NMR、1 3C NMR、MS等对化合物7和8进行了表征。化合物7和8的电化学性质表现出TTF体系特有的两对氧化可逆的单电子峰。同时,化合物7和8在UV-Vis光谱上都有D-A的分子内电荷转移(ICT)吸收峰,从ICT吸收的强度比较,化合物8中存在更强的D-A相互作用,即相对电子给体7,电子给体8具有更高的氧化电位相。同时,还得到了制备化合物7和8的关键中间体化合物5的单晶,并对其单晶结构进行了解析。

Two tetrathiafulvalenes substituted with a phenyl （Pb） （TTF-A） [ A = Ph-COOCH3 （7） and A = Ph- COOH （8） I have been synthesized to clear the nature of the donor-acceptor interaction between the TTF unit and the aeceptor group. Their structures were characterized by J H NMR,13C N MR and mass spectra. The synthesized compounds both display two reversible redox peaks eorresponding to the TTF/TTF ＋ and TTF＋/TTF2＋ and show the similar redox potentials comparable to other Ph-substituted TTF derivatives. And the results indicated thai compound 7 and 8 are good donor moleeules. We also got the crystal of the key intermediate 5 for the synthesis of compound 7 and 8. Compound 5 behmgs to monoelinie space group Pc with cell parameters of a =0. 3890 （ 1 ） urn, b =1.065 （1） ran, c = 1.318 （1） nm, Z=2, V=534.5 （2） nm^3, D,. =1.542 g-em 3, F（000） =260, R = 0.0467, toR=0. 0739 （1 〉2σ（1））.