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1,4-Bis(2′-pyridylethynyl)benzene as a ligand in heteronuclear gold–thallium complexes. Influence of the ancillary ligands on their optical properties

AuthorsArca, Massimiliano; Gimeno, M. Concepción ; Lippolis, V.; López-de-Luzuriaga, José M.; Monge, M. Ángeles ; Olmos, M. Elena
Issue DateJan-2015
PublisherRoyal Society of Chemistry
CitationDalton Transactions 44(15): 6719-6730 (2015)
AbstractThe 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.
Publisher version (URL)http://dx.doi.org/10.1039/C4DT03413A
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