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Type: Journal article
Title: Ruthenium complexes of hexakis(cyanophenyl)[3]radialenes and their di(cyanophenyl)methane precursors: Synthesis, photophysical, and electrochemical properties
Author: Hollis, C.
He, X.
Sumby, C.
Citation: Journal of Coordination Chemistry, 2014; 67(8):1367-1379
Publisher: Taylor & Francis
Issue Date: 2014
ISSN: 0095-8972
Statement of
C.A. Hollis, X. He and C.J. Sumby
Abstract: The coordination chemistry of cross-conjugated ligands and the effect of cross-conjugation on the nature of metal–metal and metal–ligand interactions have received limited attention. To explore the effects of cross-conjugation eight ruthenium complexes were synthesized, mononuclear complexes of two isomeric cross-conjugated [3]radialenes [RuCp(PPh3)2(L)]PF6 and [{RuCp*(dppe)}(L)]PF6 (L = hexakis(4-cyanophenyl)[3]radialene, 2; hexakis(3-cyanophenyl)[3]radialene, 3), and dinuclear complexes [{RuCp(PPh3)2}2(L)](PF6)2 and [{RuCp*(dppe)}2(L)](PF6)2 of the diarylmethane precursors (L = 4,4′-dicyanodiphenylmethane, 4; 3,3′-dicyanodiphenylmethane, 5) to the [3]radialenes. Considerable synthetic challenges allowed only clean isolation of mononuclear complexes of the multidentate radialenes 2 and 3. As expected, coordinating a positively charged metal induces a red shift for the π–π* transition in complexes of ligand 2, but unexpectedly a blue shift for the same transition in complexes of 3 was observed. This points to conformational differences for the [3]radialene in the ruthenium complexes of the para- (2) versus meta- (3) substituted hexaaryl[3]radialenes. Cyclic voltammetry indicates that the methylene spacer in 4 and 5 does not enable any interaction between metal centers and the absorption behavior is essentially as observed for [Ru(NCPh)(PPh3)2Cp]PF6 and [Ru(NCPh)(dppe)Cp*]PF6 but generally with a slight red shift in absorbance maxima.
Keywords: Ruthenium complexes, [3]Radialenes, Nitrile donors, Fluorescence, Cyclic voltammetry
Description: Published online: 19 May 2014
Rights: © 2014 Taylor & Francis
DOI: 10.1080/00958972.2014.915965
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