Document Detail

Thermodynamics and Conformations in the Formation of Excited States and Their Interconversions for Twisted Donor-Substituted Tridurylboranes.
MedLine Citation:
PMID:  23032965     Owner:  NLM     Status:  Publisher    
We synthesized a series of donor-substituted tridurylboranes containing different types and number of chromophores including 1-pyrene (PB1-3), 3-carbazole (CBC1-3), or substituted p-carbazol-N-phenyl (CBN3a-c) as various donor-acceptor (D-A) molecules. The photophysical and electrochemical properties of these twisted D-A molecules were investigated by means of UV/Vis absorption and fluorescence spectroscopy as well as cyclic voltammetry (CV). Solvent polarity, viscosity, and temperature effects on the fluorescence emission reveal the existence of three types of excited states, and their equilibria and interconversions between three excited states. In increasing order of the charge-separated extent and the conformational change, three excited states are the locally excited (LE) state, the more planar intramolecular charge-transfer (ICT) state, and the more twisted ICT (TICT) state as compared to the ground state. The TICT state undergoes a conformational change with a higher energy barrier over the ICT state. The solvent polarity effect on the state conversion is opposite to the viscosity effect, and temperature effects derive from its resulting changes of polarity and viscosity. For example, the increase of the polarity of the solvent results in excited-state conversions from the LE state to the ICT state, and/or from the ICT to the TICT state, and an increased viscosity leads to the opposite conversions. On the basis of electrochemical and spectral data, thermodynamics of a possible ICT process were estimated, and correlated with the excited-state character. Finally, three excited states have been characterized by the conformation, the photophysical properties, and the thermodynamics of the ICT processes.
Mao Mao; Ming-Guang Ren; Qin-Hua Song
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-2
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-3     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Department of Chemistry, Joint Laboratory of Green Synthetic Chemistry, University of Science and Technology of China, Hefei 230026, Anhui (P. R. China), Fax: (+86) 551-3601592.
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