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

AuthorsAndrade, Marta A.; Rovira, Concepció ; Belo, Dulce
KeywordsDithiolene chemistry
Substituted thiophene
Gold bisdithiolene complexes
Nickel bisdithiolene complexes
Magnetic properties
Issue Date1-Feb-2017
PublisherRoyal Society of Chemistry (UK)
CitationInorganic Chemistry Frontiers 4(2): 270-280 (2017)
AbstractThe Au and Ni monoanionic complexes of ter-buthyl and diisopropyl substituted thiophedithiolate ligand [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 monoanioc species, are easier to oxidized than the related non-substituted thiophenedithiolates and could be obtained also as stable neutral species, As expected, the peripheral alkyl groups in the ligands confer also to the complexes an high solubility in common organic solvents, The neutral gold complex [Au(α-tbtpdt)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 the intermolecular interactions in the stabilization of SOMO…SOMO interactions. While in [Au(α-tbtpdt)2] a significantr 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 an antiferromagnetic chains undergoing an AFM transition at ca. 25 K.
DescriptionAndrade, Marta A. et al.
Publisher version (URL)http://dx.doi.org/10.1039/C6QI00447D
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