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

  1. Arca, M. 3
  2. Donamaría, R. 1
  3. Gimeno, M.C. 2
  4. Lippolis, V. 3
  5. López-De-Luzuriaga, J.M. 1
  6. Manso, E. 1
  7. Monge, M. 1
  8. Olmos, M.E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Universidad de Zaragoza
    info

    Universidad de Zaragoza

    Zaragoza, España

    ROR https://ror.org/012a91z28

  3. 3 University of Cagliari
    info

    University of Cagliari

    Cagliari, Italia

    ROR https://ror.org/003109y17

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Revista:
Dalton Transactions

ISSN: 1477-9226

Any de publicació: 2015

Volum: 44

Número: 15

Pàgines: 6719-6730

Tipus: Article

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DOI: 10.1039/C4DT03413A SCOPUS: 2-s2.0-84926483391 WoS: WOS:000352271900007 GOOGLE SCHOLAR

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Resum

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.