Synthesis and Characterization of [Acridinium][Ni(dmit)2]3 and [Phenazinium][Ni(dmit)2]3 (dmit = 2-Thioxo-1,3-dithiole-4,5-dithiolate)
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- 作者：Yvonne S. J. Veldhuizen ; Wilberth J. J. Smeets ; Nora Veldman ; Anthony L. Spek ; Christophe Faulmann ; Pascale Auban-Senzier ; Denis Jé ; rome ; Peter M. Paulus ; Jaap G. Haasnoot ; and Jan Reedijk
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：October 22, 1997
- 年：1997
- 卷：36
- 期：22
- 页码：4930 - 4937
- 全文大小：207K
- 年卷期：v.36,no.22(October 22, 1997)
- ISSN：1520-510X
文摘
Electro-oxidation of a solution of[AcrH][Ni(dmit)2] (AcrH = acridinium; dmit= 2-thioxo-1,3-dithiole-4,5-dithiolate) yields black crystals of[AcrH][Ni(dmit)2]3(1). Black crystals of[PheH][Ni(dmit)2]3 (2)(PheH =phenazinium) are obtained by slow interdiffusion of solutions ofPheHBF4 and[Bu4N][Ni(dmit)2]. Crystalsof 1are monoclinic, of space group C2/c, witha = 39.124(3) Å, b = 6.4777(5) Å,c = 20.621(1) Å, 
=110.55(1)
,and Z = 4. Crystals of 2 are triclinic, ofspace group P
, with a = 5.7795(6)Å, b = 12.056(1) Å, c =19.041(1)Å, 
= 71.98(1), = 89.47(1), 
=77.99(1), and Z = 1. The crystal structuresof the two compounds arevery different. In compound 2, regular stacks ofslightly dimerized Ni(dmit)2 units are found and shortS···Sinteractions are found in two dimensions. Compound 1,however, shows stacks built from trimers ofNi(dmit)2units, which are rotated 30 toward each other, forming a "spanningoverlapping mode". Short S···S interactionsare found in all three dimensions. Compound 1 shows aroom-temperature conductivity of 45S·cm-1 and metallicconductivity behavior from room temperature down to 0.4 K. Nosuperconductivity is observed at high pressuresof 8 and 13 kbar. Compound 2 shows a room-temperatureconductivity of 4 S·cm-1 andsemimetallic conductivitybehavior from room temperature down to 100 K. The measuredconductivity behaviors are in good agreementwith the results obtained from band-structure calculations according toa tight-binding model and including Coulombrepulsion.
=110.55(1),and Z = 4. Crystals of 2 are triclinic, ofspace group P, with a = 5.7795(6)Å, b = 12.056(1) Å, c =19.041(1)Å, = 71.98(1), = 89.47(1), =77.99(1), and Z = 1. The crystal structuresof the two compounds arevery different. In compound 2, regular stacks ofslightly dimerized Ni(dmit)2 units are found and shortS···Sinteractions are found in two dimensions. Compound 1,however, shows stacks built from trimers ofNi(dmit)2units, which are rotated 30 toward each other, forming a "spanningoverlapping mode". Short S···S interactionsare found in all three dimensions. Compound 1 shows aroom-temperature conductivity of 45S·cm-1 and metallicconductivity behavior from room temperature down to 0.4 K. Nosuperconductivity is observed at high pressuresof 8 and 13 kbar. Compound 2 shows a room-temperatureconductivity of 4 S·cm-1 andsemimetallic conductivitybehavior from room temperature down to 100 K. The measuredconductivity behaviors are in good agreementwith the results obtained from band-structure calculations according toa tight-binding model and including Coulombrepulsion.