Preparation, crystal structure, and properties of novel TTF-pyridyl thiolato silver(I) complexes

Abstract

Novel supramolecular silver(I) complexes with EDT-TTF-4-py, L1, (EDT-TTF-4-py = 4-ethylenedithiotetrathiafulvalenyl-pyridine) as the ligand, [Ag(L1)]2(NO3)2 1 and [Ag(L1)2]3(CF3SO3)4·2H2O 2 were prepared by the self-assembly method. These two complexes were characterized by elemental analysis, X-ray diffraction. In 1, L1 acts as bis-bidentate ligand linking two silver ions through N and S atoms and forms a bimetallic macrocycle, and the bimetallic macrocycle is bridged by the weak Ag⋯O interactions to form a cyclic R22 (14) supramolecular, resulting 1-dimensional loop chain along c axis. And there are S⋯S and CH⋯O contacts between the loop chain. While in complex 2, two different types of Ag(L1)2 cations are coordinated by the Npyridine atom from L1 in a linear fashion and formed a trimer by weak Ag⋯Ag interaction. At room temperature, the electrical conductivity of complex 2 was 20 S·cm−1 and showed a semi-conductive behavior, whereas complex 1 is an insulator. Structural analyses of these two complexes suggest that the interactions between the cation and anion play a significant role in stabilizing the structures, and also indicate that the frameworks and the electrical conductivity of the silver(I) complexes with TTF-py can be adjusted by variations counter anion.