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Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Mishra, D., Barbieri, A., Sabatini, C., Drew, M.G.B., Figgle, H.M., Sheldrick, W.S. and Chattopadhyay, S.K. (2007) Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations. Inorganica Chimica Acta, 360 (7). pp. 2231-2244. ISSN 0020-1693

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To link to this item DOI: 10.1016/j.ica.2006.11.009

Abstract/Summary

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11489
Uncontrolled Keywords:ruthenium(II) complexes, benzimidazolyl derivatives, luminescence, spectra redox properties, X-ray structures, DFT calculations, INHOMOGENEOUS ELECTRON-GAS, PHOTOPHYSICAL PROPERTIES, POLYPYRIDYL, COMPLEXES, DINUCLEAR RUTHENIUM, CORRELATION-ENERGY, CRYSTAL-STRUCTURE, MOLECULAR SWITCH, LIGANDS, PYRIDINE, BIBENZIMIDAZOLE

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