新型四硫富瓦烯（TTF）和π-扩展四硫富瓦烯（exTTF）二硫化物的合成、电化学及自组装单分子层

Synthesis, electrochemistry and self-assembled monolayers of novel tetrathiafulvalene (TTF) and pi-extended TTF (exTTF) disulfides.

作者信息

Herranz M Angeles, Yu Lei, Martín Nazario, Echegoyen Luis

机构信息

Department of Chemistry, Clemson University, Clemson, South Carolina 29634, USA.

出版信息

J Org Chem. 2003 Oct 31;68(22):8379-85. doi: 10.1021/jo034894s.

DOI:10.1021/jo034894s

PMID:14575461

Abstract

The synthesis of a new series of tetrathiafulvalene (TTF) and pi-extended TTF (exTTF) disulfides and the electrochemical properties of self-assembled monolayers derived from these compounds are described. When the intermediate bromides 3 and 7 were reacted with thiourea, followed by basic hydrolysis, the expected thiol formation was not observed and only disulfides were obtained. A mechanism is proposed to explain the self-oxidation process of these compounds. For the first time SAMs of exTTF derivatives were prepared. Electrochemical data for SAMs of 6 and 8 reveal a single two-electron chemically reversible oxidation process to form a dicationic state, typical of the exTTF system. The SAMs are stable over extended periods of time and show electrochemical stability upon repeated potential scans.

摘要

描述了一系列新型四硫富瓦烯（TTF）和π-扩展四硫富瓦烯（exTTF）二硫化物的合成以及由这些化合物衍生的自组装单分子层的电化学性质。当中间体溴化物3和7与硫脲反应，随后进行碱性水解时，未观察到预期的硫醇生成，仅得到二硫化物。提出了一种机制来解释这些化合物的自氧化过程。首次制备了exTTF衍生物的自组装单分子层。6和8的自组装单分子层的电化学数据揭示了一个单一的两电子化学可逆氧化过程，形成双阳离子状态，这是exTTF体系的典型特征。这些自组装单分子层在较长时间内稳定，并且在重复电位扫描时显示出电化学稳定性。