Filatre-Furcate Agathe, Roisnel Thierry, Fourmigué Marc, Jeannin Olivier, Bellec Nathalie, Auban-Senzier Pascale, Lorcy Dominique
Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042, Rennes cedex, France.
Laboratoire de Physique des Solides UMR 8502, CNRS-Université de Paris-Sud, Bât 510, 91405, Orsay cedex, France.
Chemistry. 2017 Nov 13;23(63):16004-16013. doi: 10.1002/chem.201703172. Epub 2017 Oct 19.
Among single component molecular conductors, neutral radical gold dithiolene complexes [(R-thiazdt) Au] derived from the N-alkyl-1,3-thiazoline-2-thione-4,5-dithiolate (R-thiazdt) ligand provide an extensive series of conducting, non-dimerized, half-filled band systems. Analogues of the known R=isopropyl (iPr) derivative were investigated here with R=NMe , cyclopropyl (cPr) and n-propyl (nPr), aiming at rationalizing the different solid state structures adopted by these compounds despite very closely related substituents on the heterocyclic nitrogen atom. An original crisscross organization within dimerized chains is observed with R=NMe , differing however from the analogous iPr derivative by a 180° rotation of the heterocyclic nitrogen substituent. On the other hand, the cyclopropyl and n-propyl substituents lead to robust, uniform, non-dimerized chains with a strongly 1 D electronic structure and a formal half-filled electronic structure. The semiconducting behaviour of these two radical complexes is characteristic of a Mott insulator, whose sensitivity to external pressure has been evaluated up to 2.5 GPa.
在单组分分子导体中，由N-烷基-1,3-噻唑啉-2-硫酮-4,5-二硫醇盐（R-thiazdt）配体衍生的中性自由基金二硫纶配合物[(R-thiazdt)Au]提供了一系列广泛的导电、非二聚化、半填充能带体系。本文研究了已知的R =异丙基（iPr）衍生物的类似物，其中R = NMe、环丙基（cPr）和正丙基（nPr），目的是解释尽管这些化合物在杂环氮原子上的取代基非常相近，但它们所采用的不同固态结构。当R = NMe时，在二聚化链中观察到一种原始的交叉结构，然而，它与类似的iPr衍生物的不同之处在于杂环氮取代基旋转了180°。另一方面，环丙基和正丙基取代基导致形成具有强一维电子结构和形式上半填充电子结构的坚固、均匀、非二聚化链。这两种自由基配合物的半导体行为是莫特绝缘体的特征，其对外部压力的敏感性已在高达2.5 GPa的压力下进行了评估。
