| Publication Type |
Journal Article |
| Title |
Gold and nickel alkyl substituted bis-thiophenedithiolene complexes: anionic and neutral forms |
| Authors |
Marta M. Andrade Rafaela A. L. Silva Isabel Cordeiro Santos Elsa B. Lopes Sandra Rabaca Laura C. J. Pereira Joana T. Coutinho J. P. Telo Concepcio Rovira Manuel Almeida Dulce Belo |
| Groups |
BioMol |
| Journal |
INORGANIC CHEMISTRY FRONTIERS |
| Year |
2017 |
| Month |
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|
| Volume |
4 |
| Number |
2 |
| Pages |
270-280 |
| Abstract |
The Au and Ni monoanionic complexes of tert-butyl and diisopropyl substituted thiophenedithiolate ligands, [M(alpha-tb-tpdt)(2)] and [M(alpha-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(alpha-tb-tpdt)(2)] presents a significant ligand asymmetry indicative of unpaired electron localization in one ligand at variance with [Au(alpha-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(alpha-tb-tpdt)(2)] a significant intermolecular interaction between paramagnetic molecules is possible leading to diamagnetic dimers of molecules, in [Au(alpha-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(alpha-dp-tpdt)(2)] units behave, at high temperatures, as antiferromagnetic chains undergoing an AFM transition at ca. 25 K. |
| DOI |
http://dx.doi.org/10.1039/c6qi00447d |
| ISBN |
|
| Publisher |
ROYAL SOC CHEMISTRY |
| Book Title |
|
| ISSN |
2052-1553 |
| EISSN |
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| Conference Name |
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| Bibtex ID |
ISI:000395802300006 |
| Observations |
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