title: Photochemistry of 1- and 2-Naphthols and Their Water Clusters: The Role of1ππ*(La) Mediated Hydrogen Transfer to Carbon Atoms.
abstract: The computational analysis of the isomer- and conformer-dependent photochemistry of 1- and 2-naphthols and their microsolvated water clusters is motivated by their very different excited state reactivities. We present evidence that 1- and 2-naphthol follow distinct excited state deactivation pathways. The deactivation of 2-naphthols, 2-naphthol water clusters, as well as of the anti conformer of 1-naphthol is mediated by the optically dark1πσ* state. The dynamics of the1πσ* surface leads to the homolytic cleavage of the OH bond. On the contrary, the excited state deactivation of syn 1-naphthol and 1-naphthol water clusters follows an uncommon reaction pathway. Upon excitation to the bright1ππ*(La) state, a highly specific excited state hydrogen transfer (ESHT) to carbon atoms C8 and C5 takes place, yielding 1,8- and 1,5-naphthoquinone methides. The ESHT pathway arises from the intrinsic electronic properties of the1ππ*(La) state of 1-naphthols.
authors.affiliation: Department of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10000, Zagreb, Croatia.
authors.forename: Jurica
authors.initials: J
authors.lastname: Novak
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015, Lausanne, Switzerland.
authors.forename: Antonio
authors.initials: A
authors.lastname: Prlj
authors.affiliation: Department of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10000, Zagreb, Croatia.
authors.forename: Nikola
authors.initials: N
authors.lastname: Basarić
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015, Lausanne, Switzerland.
authors.forename: Clémence
authors.initials: C
authors.lastname: Corminboeuf
authors.affiliation: Department of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10000, Zagreb, Croatia.
authors.forename: Nađa
authors.identifier: http://orcid.org/0000-0001-6535-9020
authors.initials: N
authors.lastname: Došlić
keywords: excited state hydrogen transfer; hydrogen/deuterium exchange; naphthols; photochemistry; water clusters