Synthesis, crystal structure, and properties of multicomponent bis(ethylenedithio)tetrathiafulvalene charge-transfer salts of the [Mo SBr] cluster

A new family of bis(ethylenedithio)tetrathiafulvalene (ET) radical salts has been prepared in the presence of a triangular molybdenum sulfide cluster of formula [MoSBr], which contains highly electrophilic axial sulfur atoms. A systematic change in the experimental conditions yields five different salts, namely (ET )(ET)[MoSBr ]· CHBr (1), (ET )(ET)[MoSBr] ·1.1CHBr (2), (ET)(ET )(ET){[MoSBr]Br} ·0.5CHCl (3), (ET)((n-Bu )N)-[MoSBr] (4), and (ET)(PhP)[MoSBr]·0. 5CHCN (5), where the ET subscript denotes crystallographically independent molecules. The five compounds have been structurally characterized, and all of them crystallize in the triclinic space group P1 with Z = 2. Lattice parameters (Å, deg) are the following; a = 11.762(4), b = 12.246(4), c = 16.813(6), α = 107.572(9), β= 99.133(7), and γ = 102.856(8) for 1; a = 12.643(3), b = 13.370(4), c = 17.936(4), α = 103.884(8), β = 95.013(7), and γ = 114.396(6) for 2; a = 11.907(6), b = 12.742(6), c = 22.905(12), α = 90.053(15), β = 79.063(14), and γ = 75.802(15) for 3; a = 12.787(6), b = 13.653(6), c = 17.543(8), α = 68.398(10), β = 69.911(12), and γ = 62.377(10) for 4; a = 12.467(5), b = 13.553(6), c = 18.913(8), α = 85.378(11), β = 78.576(11), and γ = 65.858(9) for 5. Structural data combined with Raman spectral analysis shows that, in salt 1, one-third of the ET molecules, those marked as ET, are incorporated into the structure as ET and two-thirds as ET . Bonds distances and Raman frequencies for donor molecules in compounds 2-5 suggest a 1+ charge for all ET molecules, in agreement with the stoichiometries and IR and electronic spectra of these salts. In all cases the various donor-cluster, donor-donor, and cluster-cluster interactions and those involving the solvent molecules give rise to unique arrangements of the donor molecules. A general feature of structures 1-5 is the presence of alternating layers of dimerized organic donor molecules (ET:ET) and of inorganic clusters, where the long axis of the donor dimers runs almost parallel to the cluster layer. There is a strong tendency of the combination {[MoSBr]:ET} to accommodate a third bulky component. Compounds 4 and 5 incorporate [(n-Bu)N] or [PhP], respectively, with no apparent interactions with the ET layers in the solid state. Compound 2 and 4 are semiconductors, while the remaining salts are insulators. © 2005 American Chemical Society.