Crystal, Molecular and Electronic Structure of N,N'-diphenyl-N,N'-bis(2,4-dimethylphenyl)-(1,1'-biphenyl)-4,4'-diamine and the Corresponding Radical Cation

Low, P.J.; Paterson, M.A.J.; Puschmann, H.; Goeta, A.E.; Howard, J.A.K.; Lambert, C.; Cherryman, J.C.; Tackley, D.R.; Leeming, S.; Brown, B.

doi:10.1002/chem.200305200

Crystal, Molecular and Electronic Structure of N,N'-diphenyl-N,N'-bis(2,4-dimethylphenyl)-(1,1'-biphenyl)-4,4'-diamine and the Corresponding Radical Cation

Low, P.J.; Paterson, M.A.J.; Puschmann, H.; Goeta, A.E.; Howard, J.A.K.; Lambert, C.; Cherryman, J.C.; Tackley, D.R.; Leeming, S.; Brown, B.

Authors

P.J. Low

M.A.J. Paterson

H. Puschmann

A.E. Goeta

J.A.K. Howard

C. Lambert

J.C. Cherryman

D.R. Tackley

S. Leeming

B. Brown

Abstract

Oxidation of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD, 1a) and N,N'-diphenyl-N,N'-bis(2,4-dimethylphenyl)- (1,1'-biphenyl)-4,4'-diamine (1b) with SbCl5 affords the corresponding radical cations quantitatively. The crystal and molecular structure of 1b and [1b]SbCl6, the first tetraphenyl benzidene derivatives to be characterised crystallographically in both the neutral and radical cation states, reveal molecular parameters in agreement with the predictions made on the basis of DFT studies. Analysis of the NIR transition in the radical cations [1](+.) allows an estimate of the electronic coupling parameter V (1a(+.) 3200 cm(-1); 1b(+.) 3300 cm(-1)), the reorganisation energy lambda(1a(+.) 7500 cm(-1); 1b(+.) 7800 cm(-1)), and the linear coupling constant I (1a(+.) 3100 cm(-1); 1b(+.) 2700 cm(-1)) of the symmetric mode.

Citation

Low, P., Paterson, M., Puschmann, H., Goeta, A., Howard, J., Lambert, C., …Brown, B. (2004). Crystal, Molecular and Electronic Structure of N,N'-diphenyl-N,N'-bis(2,4-dimethylphenyl)-(1,1'-biphenyl)-4,4'-diamine and the Corresponding Radical Cation. Chemistry - A European Journal, 10(1), 83-91. https://doi.org/10.1002/chem.200305200

Journal Article Type	Article
Publication Date	Jan 5, 2004
Deposit Date	Apr 25, 2007
Journal	Chemistry - A European Journal
Print ISSN	0947-6539
Electronic ISSN	1521-3765
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	10
Issue	1
Pages	83-91
DOI	https://doi.org/10.1002/chem.200305200