Copper-Azide-Thioarylazoimidazoles – Structure, Spectra, Redox Properties, Magnetism and Theoretical Interpretation

✍ Scribed by Prasenjit Bhunia; Debasis Banerjee; Papia Datta; Pallepogu. Raghavaiah; Alexandra M. Z. Slawin; John D. Woollins; Joan Ribas; Chittaranjan Sinha

• Book ID: 102828161
• Publisher: John Wiley and Sons
• Year: 2010
• Tongue: English
• Weight: 917 KB
• Volume: 2010
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200900648

✦ Synopsis

Abstract

Azido‐copper(II) and ‐copper(I) complexes of 1‐alkyl‐2‐[(o‐thioalkyl)phenylazo]imidazole (SRaaiNR′) have been prepared and studied. Complex 2 [Cu(SRaaiNR′)(μ~1,1~‐N~3~)(N~3~)]~2~ dimerises via end‐to‐end (μ~1,3~)‐N~3~ to form a tetrameric structure. Azido‐copper(I) complexes of the ligands are obtained as MeOH‐bridged dimers, [Cu(SRaaiNR′)(N~3~)(μ‐OHMe)]~2~ (3). The electronic spectra suggest that a small reorganisation energy (0.08 eV) is associated with the change in electronic configuration, structure and oxidation state from Cu^II^ to Cu^I^. Redox interconversion, Cu^II^ ↔ Cu^I^, [Cu(SMeaaiNMe)(μ‐N~3~)(N~3~)]~2~ (2a) ↔ [Cu(SMeaaiNMe)(N~3~)(μ‐OHCH~3~)]~2~ (3a), has been performed in one case. The tetranuclear complex shows ferromagnetic and antiferromagnetic interactions. The spectra, redox chemistry and magnetism are explained by DFT studies.