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1-(2′-Pyridylazo)-2-naphtholate (PAN) complexes of rhodium(III): Synthesis,structure and spectral studies
Authors:Kausikisankar Pramanik  Basab Adhikari
Institution:Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700032, India
Abstract:The ligating properties 1-(2′-pyridylazo)-2-naphthol (HPAN) toward Rh(III) have been examined. The reaction of RhCl3·3H2O with HPAN in presence of excess PPh3 afforded trans-Rh(PAN)Cl(PPh3)2]PF6 (3PF6). Intermediate cis-Rh(PAN)Cl2(PPh3)] (4) has also been isolated. Solid state structures were authenticated by X-ray analyses revealing that monoanionic PAN is coordinated to rhodium in meridional fashion. Both the compounds were spectroscopically characterized in both solution and solid states, which include IR, NMR (1H and 31P), and optical spectra. The diamagnetic complexes show multiple CT transitions in the visible region. Low-energy transitions (λ ≈ 550–650 nm) occurred in the absorption spectra are predominantly ligand centered in nature. The rhodium(III)–PAN compounds are red emissive (λem ≈ 650 nm) at room temperature and the nature of the emission level is probably an ILCT level. Complexes are electro-active in acetonitrile and display irreversible oxidative and reductive waves and these responses are ascribed to be PAN ligand centered in character.
Keywords:Rh(III) complexes  1-(2&prime  -Pyridylazo)-2-naphthol  Crystal structures  Spectral studies  Ligand redox
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