Development of Electrical Conductors with Multi-dimensionality Based on Non-planar Metal Complexes with Sulfur-rich Ligands as an Extended pi-System

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Various metal complexes with dithiolato ligands containing many sulfur atoms asan extended it-system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and their properties c1arified.[NEt_4]_2[Mo(O)(etdt)_2](etdt=C_8H_4S_4^<2->) having five-coordinate square-pyramid geometry has been prepared. The oxidized species [NEt_4]_<0.3>[Mo(O)(etdt)_2] and [Fe(C_5Me_5)_2]_<0.05>[Mo(O)(etdt)_2] exhibited high electrical conduc-tivities (0.29 and 5.9 S cm^<-1>, respectively, at room temperature for compacted pellets). In the oxidized species S-S interactions among the etdt-ligand moieties form effective electron-conduction pathways.Co(III)- and Ti(IV)- complexes having cyclopentadienyl groups and dmit (C_3S_5^<2->) or etdt ligand have been investigated.Oxidation behavior of reactions of Co (L) (dmit) (L = eta^5-C_5H_5, eta^5-C_5Me_5) with bromine and the crystal structure of the one-electron oxidized species Co(eta^5-C_5Me_5)(dmit)Br have been clarifie … More d, together with a strong antiferromagnetic interaction between the oxidized dmit-ligand moieties.Co(eta^5-C_5H_5)(etdt) and Ti(eta^5-C_5H_5)_2(etdt) have been synthesized and properties of their oxidized complexes studied. Especially, [Co(eta^5-C_5H_5)(etdt)] I_3 and [Co(eta^5-C_5H_5)(etdt)][PF_6]_<0.7> exhibited high electrical conductivities of 0.19 and 0.16 S cm^<-1>,respectively, at room temperature measured for compacted pellets.Electrical conductivities of oxidized species of dmit- and etdt-Ru(II) cpmplexes have been studied. Ru(bpy)_2(dmit) and Ru(bpy)_2(etdt) (bpy = 2,2'-bipyridine) having a bulky six-coordinate geometry have been synthesized. The oxidized species obtained by reactions with iodine, Ru(bpy)_2(etdt)] I and Ru(bpy)_2(etdt)] (I_3)_<2.1>, have electrical conductivities of 7.4 x 10^<-7> and 7.0 x 10^<-4> S cm^<-1>, respectively. Even in the highly bulky complexes coordinated with two bpy ligands, extended oxidation on the etdt-ligand moiety leads to effective molecular interaction through S-S contacts among etdt-Iigand moieties. Less