1,4-Bis(2′-pyridylethynyl)benzene as a ligand in heteronuclear gold-thallium complexes. Influence of the ancillary ligands on their optical properties
- Arca, M. 3
- Donamaría, R. 1
- Gimeno, M.C. 2
- Lippolis, V. 3
- López-De-Luzuriaga, J.M. 1
- Manso, E. 1
- Monge, M. 1
- Olmos, M.E. 1
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1
Universidad de La Rioja
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2
Universidad de Zaragoza
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3
University of Cagliari
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ISSN: 1477-9226
Datum der Publikation: 2015
Ausgabe: 44
Nummer: 15
Seiten: 6719-6730
Art: Artikel
beta Ver similares en nube de resultadosAndere Publikationen in: Dalton Transactions
Projekte im Zusammenhang
Zusammenfassung
The reaction of 1,4-bis(2′-pyridylethynyl)benzene (L) with [{Au(C6X5)2}Tl]n affords new heterometallic AuI/TlI complexes with different stoichiometries, structural arrangements and optical properties depending on the halogens present in the aryl group. The chlorinated derivative [{Au(C6Cl5)2}Tl(L)]n (1) displays polymeric chains built thanks to unsupported Au⋯Tl interactions and bridging bidentate ligands between adjacent chains, while in the fluorinated species [{Au(C6F5)2}2Tl2(L)2]n (2), also containing N-donor bridging ligands and Au⋯Tl contacts, polymerization occurs via Tl⋯Caryl non-bonding interactions between neighbouring molecules. The optical properties of 1 and 2 have been studied experimentally and theoretically, concluding that the luminescence of 1 in the solid state has its origin in the Au⋯Tl interactions, and that the Tl⋯Caryl interactions in 2 favour a non-radiative deactivation pathway that avoids luminescence. The strength of the non-bonding interactions present in 1 has also been theoretically studied at the HF and MP2 levels, revealing the metallophilic contact as the strongest one. This journal is © The Royal Society of Chemistry 2015.