• Manashi Panda

      Articles written in Journal of Chemical Sciences

    • Synthesis, structure, redox and spectra of green iridium complexes of tridentate azo-aromatic ligands

      Manashi Panda Chayan Das Chen-Hsiung Hung Sreebrata Goswami

      More Details Abstract Fulltext PDF

      Reactions of IrCl$_3 \cdot x$H2O with the ligands, 2-[(phenylamino)phenylazo]pyridine (HL$^{1a}$) and 2-[(𝑝-tolylamino)phenylazo]pyridine (HL$^{1b}$) produce [Ir(L1)2]Cl (L1 = L$^{1a}$, [1]Cl and L1 = L$^{1b}$, [2]Cl) along with many unidentified products. The iridium complexes have been characterized by various techniques such as X-ray crystallography, mass spectrometry, 1H and 13C NMR, cyclic voltammetry and absorption studies. The complex [1]ClO4 crystallises in triclinic space group. The crystallographic data have been determined. Notably, the Ir-N (azo) lengths are short (av. 1.9875(4) Å) as compared to the remaining four Ir-N lengths (av. 2.052(5) Å). There is significant degree of ligand backbone conjugation in the coordinated ligands, which result in shortening of the C-N lengths on the other side of the middle phenyl ring and also in lengthening of the diazo (N=N) lengths. The complexes display multiple low energy transitions ranging between 1010 and 450 nm. These are electro active and show three reversible redox responses in the potential range, +1.5 V to -1.5 V. The cathodic potential responses are ascribed as ligand reductions, while the redox process at the anodic potential occurs at a mixed metal-ligand (HOMO) orbital.

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