title: A comparative study on the photochemistry of two bipyridyl derivatives: [2,2'-bipyridyl]-3,3'-diamine and [2,2'-bipyridyl]-3,3'-diol.
abstract: The two isoelectronic bipyridyl derivatives, [2,2'-bipyridyl]-3,3'-diamine and [2,2'-bipyridyl]-3,3'-diol, are experimentally known to undergo very different excited-state double-proton-transfer processes, which result in fluorescence quantum yields that differ by four orders of magnitude. Herein, density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations are used to study the double-proton-transfer processes in the ground and first singlet pi-->pi* excited state. The quantum-chemistry calculations indicate 1) the existence of only one energy minimum in the ground electronic state corresponding to reactants (thus avoiding the possibility of a fast fluorescent relaxation process from the photoproducts region), 2) an endoergic process of the complete double proton transfer, and 3) the presence of a conical intersection in the excited intermediate region of [2,2'-bipyridyl]-3,3'-diamine. These facts explain the very low fluorescence quantum yield in [2,2'-bipyridyl]-3,3'-diamine compared to [2,2'-bipyridyl]-3,3'-diol.
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
authors.forename: Juan Manuel
authors.initials: JM
authors.lastname: Ortiz-Sánchez
authors.forename: Ricard
authors.initials: R
authors.lastname: Gelabert
authors.forename: Miquel
authors.initials: M
authors.lastname: Moreno
authors.forename: José M
authors.initials: JM
authors.lastname: Lluch
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000737:chemistry; D000631:Aminopyridines / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry
chemical_list: C523915:(2,2'-bipyridyl)-3,3'-diamine; C499984:(2,2'-bipyridyl)-3,3'-diol; D000631:Aminopyridines; D015082:2,2'-Dipyridyl