Issue 16, 2012
From the journal:

Dalton Transactions

Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species†

Suresh Bhargava,*a   Kunihiko Kitadai,b   Takahashi Masashi,b   Daniel W. Drumm,ac   Salvy P. Russo,ac   Vivian Wing-Wah Yam,d   Terence Kwok-Ming Lee,d   Jörg Waglere  and  Nedaossadat Mirzadeha  

* Corresponding authors

a Advanced Materials & Industrial Chemistry, School of Applied Sciences, RMIT University, GPO Box 2476V, Melbourne, Victoria, Australia
E-mail: Suresh.bhargava@rmit.edu.au

b Department of Chemistry, Toho University, Chiba, Japan

c Applied Physics, School of Applied Sciences, RMIT University, GPO Box 2476V, Melbourne, Victoria, Australia

d Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee (Hong Kong)), and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, PR China

e Institut für Anorganische Chemie, Technische Universität Bergakademie, Freiberg D-09596, Germany

Abstract

A mixture of cyclic gold(I) complexes [Au2(μ-cis-dppen)2]X2 (X = OTf 1, PF63) and [Au(cis-dppen)2]X (X = OTf 2, PF64) is obtained from the reaction of [Au(tht)2]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au3(μ-trans-dppen)3]X3 (X = OTf 11, PF612) and tetranuclear [Au4(μ-dppa)4]X4 (X = OTf 13, PF614, ClO415) gold complexes, respectively. Recrystallization of 15 from CH2Cl2/MeOH yielded a crystal of the octanuclear gold cluster [Au8Cl2(μ-dppa)4](ClO4)216. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au2X2(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX2(cis-dppen)]PF6 (X = I 6, Br 8) complexes. Complexes 11–14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.

Graphical abstract: Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

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Article information

DOI
https://doi.org/10.1039/C2DT11722C
Article type
Paper
Submitted
12 Sep 2011
Accepted
24 Jan 2012
First published
02 Mar 2012

Dalton Trans., 2012,41, 4789-4798

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Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

S. Bhargava, K. Kitadai, T. Masashi, D. W. Drumm, S. P. Russo, V. W. Yam, T. K. Lee, J. Wagler and N. Mirzadeh, Dalton Trans., 2012, 41, 4789 DOI: 10.1039/C2DT11722C

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