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Issue 32, 2013
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Heterometallic gold(i)–thallium(i) compounds with crown thioethers

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The polymeric Au/Tl compounds [{Au(C6X5)2}Tl]n (X = Cl, F) react with the crown thioethers 1,4,7-trithiacyclononane ([9]aneS3), 1,5,8,11-tetrathiacyclotetradecane ([14]aneS4), and 1,4,7,10,13,16,19,22-octathiacyclotetracosane ([24]aneS8) in an appropriate molar ratio to afford [{Au(C6X5)2}Tl(L)]2 [L = [9]aneS3, X = Cl (1), F (4); L = [14]aneS4, X = Cl (2), F (5)], [{Au(C6Cl5)2}2Tl2([24]aneS8)]n (3) or [{Au(C6F5)2}2Tl2([24]aneS8)] (6). X-ray diffraction studies of 3, 4 and 6 reveal polymeric (3) or tetranuclear (4, 6) structures formed via Tl–S bonds and Au⋯Tl or Au⋯Tl and Au⋯Au contacts. All the complexes are luminescent in the solid state, but not in solution, where the metal–metal interactions, which are responsible for the luminescence, are no longer present. DFT calculations on representative model systems of complexes 3, 4 and 6 have also been carried out in order to determine the origin of the electronic transitions responsible for their optical properties.

Graphical abstract: Heterometallic gold(i)–thallium(i) compounds with crown thioethers

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The article was received on 22 May 2013, accepted on 15 Jun 2013 and first published on 09 Jul 2013

Article type: Paper
DOI: 10.1039/C3DT51334C
Dalton Trans., 2013,42, 11559-11570

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    Heterometallic gold(I)–thallium(I) compounds with crown thioethers

    A. J. Blake, R. Donamaría, E. J. Fernández, T. Lasanta, V. Lippolis, J. M. López-de-Luzuriaga, E. Manso, M. Monge and M. E. Olmos, Dalton Trans., 2013, 42, 11559
    DOI: 10.1039/C3DT51334C

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