Photochemistry of hydrogen bonded heterocycles probed by photodissociation experiments and ab initio methods

0360624 - ÚFCH JH 2012 RIV GB eng J - Journal Article
Slavíček, Petr - Fárník, Michal
Photochemistry of hydrogen bonded heterocycles probed by photodissociation experiments and ab initio methods.
Physical Chemistry Chemical Physics. Roč. 13, č. 26 (2011), s. 12123-12137. ISSN 1463-9076. E-ISSN 1463-9084
R&D Projects: GA ČR GA203/09/0422; GA ČR GAP208/11/0161
Institutional research plan: CEZ:AV0Z40400503
Keywords : photochemistry * hydrogen bonded heterocycles * ab initio methods
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.573, year: 2011

In this perspective article, we focus on the photochemistry of five-membered nitrogen containing heterocycles (pyrrole, imidazole and pyrazole) in clusters. These heterocycles represent paradigmatic structures for larger biologically active heterocyclic molecules and complexes. The dimers of the three molecules are also archetypes of different bonding patterns: N–Hπ interaction, N–HN hydrogen bond and double hydrogen bond. We briefly review available data on photochemistry of the title molecules in the gas phase, but primarily we focus on the new reaction channels opened upon the complexation with other heterocycles or solvent molecules. Based on ab initio calculations we discuss various possible reactions in the excited states of the clusters: (1) hydrogen dissociation, (2) hydrogen transfer between the heterocyclic units, (3) molecular ring distortion, and (4) coupled electron–proton transfer.
Permanent Link: http://hdl.handle.net/11104/0198133