NDLI: Thermodynamics and Conformations in the Formation of Excited States and Their Interconversions for Twisted Donor-Substituted Tridurylboranes

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Thermodynamics and Conformations in the Formation of Excited States and Their Interconversions for Twisted Donor-Substituted Tridurylboranes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Mao, Mao Song, Qin-hua Ren, Ming-guang
Description	Author Affiliation: Mao M ( Department of Chemistry, Joint Laboratory of Green Synthetic Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, P. R. China.)
Abstract	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.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	48
Volume Number	18
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2012-11-26
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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