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Charge Transfer Pathways in Three Isomers of Naphthalene-Bridged Organic Mixed Valence Compounds

Schmidt, Hauke C. and Spulber, Mariana and Neuburger, Markus and Palivan, Cornelia G. and Meuwly, Markus and Wenger, Oliver S.. (2016) Charge Transfer Pathways in Three Isomers of Naphthalene-Bridged Organic Mixed Valence Compounds. Journal of Organic Chemistry, 81 (2). pp. 595-602.

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Official URL: http://edoc.unibas.ch/41796/

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Abstract

Naphthalene was substituted at different positions with two identical triarylamine moieties to result in species which are mixed-valence compounds in their one-electron oxidized forms. They were investigated by cyclic voltammetry, optical absorption, EPR spectroscopy, X-ray crystallography, and DFT calculations. When the two redox-active triarylamine moieties are connected to the 2- and 6-positions of the naphthalene bridge, their electronic communication is significantly stronger than when they are linked to the 1- and 5-positions, and this can be understood on the basis of a simple through-bond charge transfer pathway model. However, this model fails to explain why electronic communication between triarylamine moieties in the 1,5- and 1,8-isomers is similarly strong, indicating that through-space charge transfer pathways play an important role in the latter. In particular, charge transfer in the 1,8-isomer is likely to occur between the triarylamino C atoms in α-position to the naphthalene linker because the respective atoms are only about 3 Å apart from each other, and because they carry significant spin density in the one-electron oxidized forms of triarylamines. This particular through-space charge transfer pathway might be generally important in molecular structures based on the 1,8-disubstituted naphthalene pillaring motif.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0022-3263
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:11 Jun 2018 06:21
Deposited On:25 Apr 2016 12:36

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