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Structural changes accompanying excited-state electron transfer in meta- and para-dialkylaminopyridines

Paper ID Volume ID Publish Year Pages File Format Full-Text
27152 44005 2010 12 PDF Available
Title
Structural changes accompanying excited-state electron transfer in meta- and para-dialkylaminopyridines
Abstract

The electronic structure of the lowest excited singlet states and molecular geometries of a series of dialkylaminopyridines (DAAPs) representing electron donor–acceptor systems were studied by photostationary and time-resolved UV–vis spectroscopic methods and quantum chemical calculations. The comparative studies allow us to rationalize dual luminescence of 4-DAAPs in terms of the TICT state model—the analysis of the electronic transition dipole moments indicates a nearly orthogonal conformation of the fluorescent ICT states. Introduction of the amino group at meta position as in 3-diisopropylaminopyridine completely changes photophysics of these pyridine derivatives: (i) the Franck-Condon excited state initially reached upon excitation and the solvent equilibrated fluorescent state are most probably of the same nature (both excited states do not correspond to a full separation of charges) and (ii) the electronic structure and geometry of the fluorescent CT states of m-DIAP are solvent dependent.

Keywords
Dialkylaminopyridines; UV–vis spectroscopy and MCD; Dual fluorescence; IET; TICT states; INDO/S; DFT and TD-DFT calculations
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Structural changes accompanying excited-state electron transfer in meta- and para-dialkylaminopyridines
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 209, Issues 2–3, 25 January 2010, Pages 135–146
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
Get Full-Text Now
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Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
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Any Questions? feel free to contact us