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Gold and nickel alkyl substituted bis-thiophenedithiolene complexes: anionic and neutral forms
| Content Provider | Semantic Scholar |
|---|---|
| Author | Andrade, Marta M. Silva, Rafaela Lacerda Santos, Isabel Lopes, Elsa Branco Rabaca̧, Sandra Pereira, Laura C. J. Coutinho, Joana T. Telo, João P. Rovira, Concepció Almeida, Manuel Belo, Dulce |
| Copyright Year | 2017 |
| 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. |
| Starting Page | 270 |
| Ending Page | 280 |
| Page Count | 11 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/C6QI00447D |
| Volume Number | 4 |
| Alternate Webpage(s) | http://digital.csic.es/bitstream/10261/164378/1/Andrade_InorgChemFront_2017_postprint.pdf |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/c6/qi/c6qi00447d/c6qi00447d1.pdf |
| Alternate Webpage(s) | https://doi.org/10.1039/C6QI00447D |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
