DSpace
 

DSpace at IIT Bombay >
IITB Publications >
Article >

Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/12829

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
Authors: ROY, S
SARKAR, B
DUBOC, C
FIEDLER, J
SARPER, O
LISSNER, F
MOBIN, SM
LAHIRI, GK
KAIM, W
Keywords: transition-metal-complexes
discotic liquid-crystals
bridging-ligand
radical complexes
epr
mononuclear
ferrocene
copper(i)
1,6,7,12,13,18-hexaazatrinaphthylene
quinoxalines
Issue Date: 2009
Publisher: WILEY-V C H VERLAG GMBH
Citation: CHEMISTRY-A EUROPEAN JOURNAL, 15(28), 6932-6939
Abstract: 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).
URI: http://dx.doi.org/10.1002/chem.200802655
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12829
http://hdl.handle.net/10054/12829
ISSN: 0947-6539
Appears in Collections:Article

Files in This Item:

There are no files associated with this item.

View Statistics

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

 

Valid XHTML 1.0! DSpace Software Copyright © 2002-2010  Duraspace - Feedback