Controlling the Adiabaticity of Electron-Transfer Reactions Using Nematic Liquid-Crystal Solvents

Autor:	Walter A. Svec, Michael R. Wasielewski, Gary P. Wiederrecht
Rok vydání:	1999
Předmět:	Phase transition Solvation Acceptor Surfaces Coatings and Films MBBA chemistry.chemical_compound Nuclear magnetic resonance chemistry Photoinduced charge separation Chemical physics Liquid crystal Intramolecular force Phase (matter) Materials Chemistry Physical and Theoretical Chemistry
Zdroj:	The Journal of Physical Chemistry B. 103:1386-1389
ISSN:	1520-5207 1520-6106
DOI:	10.1021/jp983907g
Popis:	Transient absorption studies of intramolecular photoinduced charge separation and thermal charge recombination were carried out on a molecule consisting of a 4-(N-pyrrolidinyl)naphthalene-1,8-imide donor (PyrNI) covalently attached to a pyromellitimide acceptor (PI) dissolved in the liquid crystal N-(4-methoxybenzylidene)-4-butylaniline (MBBA). In the isotropic phase, just above the nematic to isotropic phase transition, ordered microdomains exist that give rise to solvation dynamics that consist of collective reorientational motions of the microdomains and relatively faster reorientations of molecules within the domains. The different temperature dependence of these responses permits the assignment of collective or molecular solvent motions as mediators of the charge separation and recombination reactions. We find for PyrNI−PI in MBBA that charge separation is adiabatic and controlled by the collective microdomain reorientations, whereas the charge recombination is nonadiabatic and controlled by the fast...
Databáze:	OpenAIRE
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