Heterohexanuclear (Cu(3)Fe(3)) Complexes of Substituted Hexaazatrinaphthylene (HATN) Ligands: Twofold BF(4)(-) Association in the Solid and Stepwise Oxidation (3e) or Reduction (2e) to Spectroelectrochemically Characterized Species
DSpace at IIT Bombay
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Title |
Heterohexanuclear (Cu(3)Fe(3)) Complexes of Substituted Hexaazatrinaphthylene (HATN) Ligands: Twofold BF(4)(-) Association in the Solid and Stepwise Oxidation (3e) or Reduction (2e) to Spectroelectrochemically Characterized Species
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Creator |
ROY, S
SARKAR, B DUBOC, C FIEDLER, J SARPER, O LISSNER, F MOBIN, SM LAHIRI, GK KAIM, W |
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Subject |
transition-metal-complexes
discotic liquid-crystals bridging-ligand radical complexes epr mononuclear ferrocene copper(i) 1,6,7,12,13,18-hexaazatrinaphthylene quinoxalines copper epr spectroscopy ferrocene compounds heterocycles spectroelectrochemistry supramolecular chemistry |
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Description |
New tris(ferrocenylcopper) compounds [(mu(3)-dqp){Cu(dppf)}(3)][X](3) (dppf =1,1'-bis(diphenylphosphinoferrocene), dqp=hexamethyl-, hexachloro- or un-substituted diquinoxalino[2,3-a:2',3'-c]phenazine=hexaazatrinaphthylene (HATN), X(-)=BF(4)(-) or PF(6)(-)) undergo at least two different, reversible one-electron reductions and three very closely spaced one-electron oxidations. While the latter are attributed to the stepwise ferrocene -> ferrocenium conversions, the first electron addition occurs in the ligand bridge to yield EPR detectable radical complexes. X-band EPR measurements at 9.5 GHz showed a partially resolved hyperfine structure, while high-frequency EPR measurements at 95 or 115 GHz revealed a small but variable axial g tensor anisotropy. All reversible steps were investigated by optically transparent thin-layer electrode (OTTLE) spectroelectrochemistry (UV/Vis/NIR regions), revealing very low energy transitions for the reduced forms in agreement with the frontier MO arrangement. A crystal structure of the compound with unsubstituted dqp shows notable deviation from the trigonal symmetry and the close association of two tetrafluoroborate anions with the complex trication along the quasi-trigonal axis to yield [(mu(3)-dqp){Cu(dppf)}(3)(BF(4))(2)]BF(4).
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Publisher |
WILEY-V C H VERLAG GMBH
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Date |
2011-09-01T17:21:22Z
2011-12-26T12:59:44Z 2011-12-27T05:52:30Z 2011-09-01T17:21:22Z 2011-12-26T12:59:44Z 2011-12-27T05:52:30Z 2009 |
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Type |
Article
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Identifier |
CHEMISTRY-A EUROPEAN JOURNAL, 15(28), 6932-6939
0947-6539 http://dx.doi.org/10.1002/chem.200802655 http://dspace.library.iitb.ac.in/xmlui/handle/10054/12829 http://hdl.handle.net/10054/12829 |
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Language |
en
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