Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Stabilization of Complexes of Redox-Active Guanidino-Functionalized Aromatic Compounds (GFAs) by Hydrogen-Bonding

Christoph Krämer A , Ute Wild A , Olaf Hübner A , Christiane Neuhäuser A , Elisabeth Kaifer A and Hans-Jörg Himmel A B
+ Author Affiliations
- Author Affiliations

A Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.

B Corresponding author. Email: hans-jorg.himmel@aci.uni-heidelberg.de

Australian Journal of Chemistry 67(7) 1044-1055 https://doi.org/10.1071/CH14175
Submitted: 27 March 2014  Accepted: 7 May 2014   Published: 12 June 2014

Abstract

The guanidino-functionalized 1,2,4,5-tetrakis(N,N′-diisopropylguanidino)benzene could act as a redox-active switch, and reversibly forms hydrogen-bond aggregates upon two-electron oxidation. Herein the influence of hydrogen bonding on the structure and electronic properties of the first transition metal complexes of the neutral and oxidized compound are studied. Reaction with CuCl2 leads by coupled redox- and coordination processes to a dinuclear CuII complex of the dicationic guanidine, in which CuCl2 counterions are locked through strong hydrogen-bonds in positions above and below the C6 ring plane. The electronic situation in the electronic ground and excited states of this complex were analysed by quantum chemical calculations.


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