Isomeric ruthenium terpyridine complexes [Ru(trpy)(L)Cl](n+) containing the unsymmetrically bidentate acceptor L=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations
DSpace at IIT Bombay
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Title |
Isomeric ruthenium terpyridine complexes [Ru(trpy)(L)Cl](n+) containing the unsymmetrically bidentate acceptor L=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations
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Creator |
PATRA, S
SARKAR, B GHUMAAN, S PATIL, MP MOBIN, SM SUNOJ, RB KAIM, W LAHIRI, GK |
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Subject |
density-functional theory
effective core potentials transition-metal-complexes ray crystal-structure spectroelectrochemical properties charge-transfer molecular calculations polypyridyl complexes redox properties bridging ligand |
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Description |
The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl-3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1](n+) (tetrazine-N-t trans to Cl) and [2](n+) (pyrazolyl-N-p trans to Cl; n = 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (Ru-III) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds 1 and 2 they have the unpaired electron predominantly in the tetrazine ring of L.
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Publisher |
ROYAL SOC CHEMISTRY
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Date |
2011-08-28T12:41:45Z
2011-12-26T12:58:02Z 2011-12-27T05:47:01Z 2011-08-28T12:41:45Z 2011-12-26T12:58:02Z 2011-12-27T05:47:01Z 2005 |
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Type |
Article
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Identifier |
DALTON TRANSACTIONS, (7), 1188-1194
1477-9226 http://dx.doi.org/10.1039/b500152h http://dspace.library.iitb.ac.in/xmlui/handle/10054/11741 http://hdl.handle.net/10054/11741 |
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Language |
en
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