Synthesis, crystal structures and properties of silver(I) complexes assembled with dmit and TTF derivatives

In this paper, dmit (dmit = 4,5-disulfanyl-1,3-dithio-2-thionate) and TTF (TTF = tetrathiafulvalene) derivatives, i.e., bedt (bedt = 4,5-bis(ethylsulfanyl)-1,3-dithiole-2-thione), CE-TTF (CE-TTF = 2,3-bis(cyanoethylsulfanyl)-6,7-bis(ethylsulfanyl)-TTF) and tces-TTF (tces-TTF = 2,3,6,7-tetra(cyanoethylsulfanyl)-TTF) were reacted with different silver salts to produce four novel coordination polymer crystals: [Ag(bedt)]ClO4 (1), [Ag2(bedt)2acetone](SbF6)2 (2), [Ag(CE-TTF)](CF3SO3)acetone (3) and [Ag(tces-TTF)2]SbF6 (4). The crystallographic studies indicate that polymer 1 exhibits a 2D sheet structure with a (4,4) network, polymer 2 possesses a 2D lamellar structure with a (6,3) network, polymer 3 exhibits a 2D porous framework with novel meso-helix motifs and complex 4 consists of tetramers with S⋯S interactions, which result in the formation of a 2D supramolecular coordination polymer. Polymer 4 also exhibits semi-conductive behavior with a σ value of 2.29 × 10−5 S cm−1 due to the extensive S⋯S contacts.