Issue 2, 2017

Gold and nickel alkyl substituted bis-thiophenedithiolene complexes: anionic and neutral forms

Abstract

The Au and Ni monoanionic complexes of tert-butyl and diisopropyl substituted thiophenedithiolate ligands, [M(α-tb-tpdt)2] and [M(α-dp-tpdt)2], were synthesized and characterized namely by single crystal X-ray diffraction and magnetic susceptibility measurements. These complexes, prepared in a first step as monoanionic species, are easier to oxidize than the related non-substituted thiophenedithiolates and could be obtained also as stable neutral species. As expected, the peripheral alkyl groups in the ligands also confer a high solubility to the complexes in common organic solvents. The neutral gold complex [Au(α-tb-tpdt)2] presents a significant ligand asymmetry indicative of unpaired electron localization in one ligand at variance with [Au(α-dp-tpdt)2] that is within experimental uncertainty fully symmetric illustrating the role of intermolecular interactions in the stabilization of SOMO⋯SOMO interactions. While in [Au(α-tb-tpdt)2] a significant intermolecular interaction between paramagnetic molecules is possible leading to diamagnetic dimers of molecules, in [Au(α-dp-tpdt)2] the bulkier substituents prevent the intermolecular interactions, leading to a regular stacking of molecules in symmetrical configuration. The regular stacks of paramagnetic [Au(α-dp-tpdt)2] units behave, at high temperatures, as antiferromagnetic chains undergoing an AFM transition at ca. 25 K.

Graphical abstract: Gold and nickel alkyl substituted bis-thiophenedithiolene complexes: anionic and neutral forms

Supplementary files

Article information

Article type
Research Article
Submitted
24 Oct 2016
Accepted
28 Nov 2016
First published
29 Nov 2016

Inorg. Chem. Front., 2017,4, 270-280

Gold and nickel alkyl substituted bis-thiophenedithiolene complexes: anionic and neutral forms

M. M. Andrade, R. A. L. Silva, I. C. Santos, E. B. Lopes, S. Rabaça, L. C. J. Pereira, J. T. Coutinho, J. P. Telo, C. Rovira, M. Almeida and D. Belo, Inorg. Chem. Front., 2017, 4, 270 DOI: 10.1039/C6QI00447D

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