具有[M（dcdmp）<sub>2</sub> ]阴离子（M = Au，Cu和Ni）的四硫富瓦烯和四甲基四硒富烯富瓦烯盐：高电导率和异常的化学计量比,Crystal Growth & Design

当前位置： X-MOL 学术 › Cryst. Growth Des. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

具有[M（dcdmp）₂ ]阴离子（M = Au，Cu和Ni）的四硫富瓦烯和四甲基四硒富烯富瓦烯盐：高电导率和异常的化学计量比
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2019-09-25 , DOI: 10.1021/acs.cgd.9b00958
Rafaela A. L. Silva ₁ , Isabel C. Santos ₁ , Vasco Gama ₁ , Elsa B. Lopes ₁ , Pascale Auban-Senzier ₂ , Manuel Almeida ₁ , Dulce Belo ₁

Affiliation

四种基于四硫富富瓦烯（TTF）或四甲基四富硒富瓦烯（TMTSF）供体和过渡金属配合物[M（dcdmp）₂ ]（dcdmp = 2,3-dicyano-5,6-dimercaptopyrazine），TMTSF ₅ [Cu（dcdmp ）₂ ] ₄（1），（TMTSF）₂ [Ni（dcdmp）₂ ]（2）和（TTF）₇ [M（dcdmp）₂ ] ₆（M = Au（3）和Cu（4））通过电结晶制备。这些化合物的特征是具有各种不同的晶体结构，具有不同的供体/受体化学计量比。尽管观察到不常见的结构类型，但这些盐仍具有很高的导电性。化合物1在分离的TMTSF叠层中结晶，显示1D金属性能，室温电导率为134 S / cm。化合物2在供体二聚体和受体的套准混合列排列中结晶。化合物3和4在单晶X射线衍射中显示为同构结构，由TTF六聚体的列组成，这些列被单个TTF层破坏并被[M（dcdmp）₂ ]包围^-与六聚体堆叠垂直排列的单阴离子对。但是，单晶中电输运性质的测量表明存在两相。虽然相2具有半导电性，但是相1显然与铜络合物4更具导电性，铜络合物4在210 K附近表现出金属半导体跃迁，室温电导率约为210 S / cm。

"点击查看英文标题和摘要"

Tetrathiafulvalene and Tetramethyltetraselenafulvalene Salts with [M(dcdmp)2] Anions (M = Au, Cu, and Ni): High Conductivity and Unusual Stoichiometries

Four new charge transfer salts based on tetrathiafulvalene (TTF) or tetramethyltetraselenafulvalene (TMTSF) donors and transition metal complexes [M(dcdmp)₂] (dcdmp = 2,3-dicyano-5,6-dimercaptopyrazine), TMTSF₅[Cu(dcdmp)₂]₄ (1), (TMTSF)₂[Ni(dcdmp)₂] (2), and (TTF)₇[M(dcdmp)₂]₆ (M = Au (3) and Cu (4)) were prepared by electrocrystallization. These compounds are characterized by a rich variety of crystal structures with unusual donor/acceptor stoichiometries. In spite of the uncommon structural types observed, these salts can be highly conducting. Compound 1 crystallizes with segregated TMTSF stacks, showing 1D metallic properties with a room temperature conductivity of 134 S/cm. Compound 2 crystallizes in an out-of-registry mixed column arrangement of donor dimers and acceptors. Compounds 3 and 4 appear in single crystal X-ray diffraction as isostructural and composed of columns of TTF hexamers that are disrupted by a single TTF layer and surrounded by [M(dcdmp)₂]⁻ monoanionic pairs, aligning perpendicularly to the hexamer stacks. However, measurements of the electric transport properties in single crystals suggest the existence of two phases. While phase 2 has a semiconducting behavior, phase 1 is clearly more conductive with copper complex 4 presenting a metal semiconductor transition around 210 K and room temperature conductivity of ∼210 S/cm.

更新日期：2019-09-26

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南