Issue 5, 2015

Synthesis, luminescence and electrochemical properties of luminescent dinuclear mixed-valence gold complexes with alkynyl bridges

Abstract

A series of luminescent dinuclear mixed-valence gold alkynyl complexes, [(tBuC^N^CtBu)AuIII(C[triple bond, length as m-dash]C)AuI(PPh3)], [(RC^N^CR)AuIII(C[triple bond, length as m-dash]CC[triple bond, length as m-dash]C)AuI(PPh3)] (R = H, tBu), [(RC^N^CR)AuIII(C[triple bond, length as m-dash]CC6H4C[triple bond, length as m-dash]C)AuI(PPh3)] (R = H, tBu), and [(RC^N^CR)AuIII(C[triple bond, length as m-dash]CC6H4C[triple bond, length as m-dash]C)AuI(P(C6H4R′-p)3)] (R = H; R′ = OMe, Cl) as well as the precursor complexes, [AuIII(tBuC^N^CtBu)(C[triple bond, length as m-dash]CSiMe3)] and [AuIII(tBuC^N^CtBu)(C[triple bond, length as m-dash]CH)], have been synthesized and their electrochemical properties have been investigated. The molecular structures of a number of dinuclear mixed-valence gold alkynyl complexes have been determined by X-ray crystallography. For complexes with a butadiynyl bridge, the emission was derived from an admixture of metal-perturbed triplet intraligand (3IL) [π–π* (RC^N^CR)] and [π–π* (C[triple bond, length as m-dash]C–C[triple bond, length as m-dash]C)] states while for complexes with a 1,4-diethynylbenzene bridge, the emission was assigned as derived from the excited state of the 3IL [π → π* (C[triple bond, length as m-dash]CC6H4C[triple bond, length as m-dash]C)] origin. Computational studies have also been performed for selected complexes to support the assignment of the spectroscopic origin and the nature of the photophysical properties.

Graphical abstract: Synthesis, luminescence and electrochemical properties of luminescent dinuclear mixed-valence gold complexes with alkynyl bridges

Supplementary files

Article information

Article type
Research Article
Submitted
01 feb 2015
Accepted
01 mar 2015
First published
16 mar 2015

Inorg. Chem. Front., 2015,2, 453-466

Synthesis, luminescence and electrochemical properties of luminescent dinuclear mixed-valence gold complexes with alkynyl bridges

L. Hung, W. H. Lam, K. M. Wong, E. C. Cheng, N. Zhu and V. W. Yam, Inorg. Chem. Front., 2015, 2, 453 DOI: 10.1039/C5QI00017C

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