Interactions of Neutral and Cationic Transition Metals with the Redox System of Hydroquinone and Quinone: Theoretical Characterization of the Binding Topologies, and Implications for the Formation of Nanomaterials

✍ Scribed by Hai-Bo Yi; Martin Diefenbach; Young Cheol Choi; Eun Cheol Lee; Han Myoung Lee; Byung Hee Hong; Kwang S. Kim

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 224 KB
• Volume: 12
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200501551

✦ Synopsis

Abstract

To understand the self‐assembly process of the transition metal (TM) nanoclusters and nanowires self‐synthesized by hydroquinone (HQ) and calix[4]hydroquinone (CHQ) by electrochemical redox processes, we have investigated the binding sites of HQ for the transition‐metal cations TM^n+^=Ag^+^, Au^+^, Pd^2+^, Pt^2+^, and Hg^2+^ and those of quinone (Q) for the reduced neutral metals TM^0^, using ab initio calculations. For comparison, TM^0^–HQ and TM^n+^–Q interactions, as well as the cases for Na^+^ and Cu^+^ (which do not take part in self‐synthesis by CHQ) are also included. In general, TM–ligand coordination is controlled by symmetry constraints imposed on the respective orbital interactions. Calculations predict that, due to synergetic interactions, silver and gold are very efficient metals for one‐dimensional (1D) nanowire formation in the self‐assembly process, platinum and mercury favor both nanowire/nanorod and thin film formation, while palladium favors two‐dimensional (2D) thin film formation.