4,5-Bis(methylthio)-1,3-dithiole-2-thione, a versatile sulphur-rich building block for the self-assembly of Cu(I) and Ag(I) coordination polymers: Dithioether versus thiocarbonyl bonding

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• 作者：Auré ; lien Hameau^a ; Fabrice Guyon^a ; ^{fabrice.guyon@univ-fcomte.fr} ; Abderrahim Khatyr^a ; Michael Knorr^a ; ^{michael.knorr@univ-fcomte.fr} ; Carsten Strohmann^b
• 关键词：S ligand ; Coordination modes ; Coordination polymers ; Copper complex ; Silver complex ; Luminescence
• 出版年：2012
• 出版时间：15 June, 2012
• 年：2012
• 卷：388
• 期：Complete
• 页码：60-70
• 全文大小：1756 K

文摘

Reported herein is the investigation of the coordination chemistry of the ligand 4,5-bis(methylthio)-1,3-dithiole-2-thione (L) towards several Ag(I) salts (AgNO₃, AgClO₄, AgCF₃SO₃ and Ag-p-MeC₆H₄SO₃) and Cu(I) (CuBr and [Cu(MeCN)₄](PF₆)). Six polymeric complexes have been characterised by single-crystal X-ray diffraction, FT-IR spectra and elemental analysis. This work evidences five different coordination modes for L. The sulphur-rich ligand always coordinates via the thiocarbonyl group. Additional metal-thioether interactions give rise in some cases to a polymeric structure such as in the molecular wire-like 1D polymer {[Cu(¦Ì₂-L)(MeCN)](PF₆)}_n. Supramolecular structures arise from a combination of metal¡¤¡¤¡¤ligand and short S¡¤¡¤¡¤S Van der Waals interactions. Furthermore, the emission spectra of the strongly luminescent 2D coordination polymer [Ag(¦Ì₂-L){¦Ì₂-(p-CH₃C₆H₄SO₃)}]_n have been recorded.