Naslov
Photochemistry of 1- and 2-Naphthols and Their Water Clusters : The Role of 1 ππ*(La ) Mediated Hydrogen Transfer to Carbon Atoms

Autori
Novak, Jurica ; Prlj, Antonio ; Basarić, Nikola ; Corminboeuf, Clémence ; Došlić, Nađa

Izvornik
Chemistry : a European journal (0947-6539) 23 (2017), 34; 8244-8251

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
excited state hydrogen transfer ; hydrogen/deuterium exchange ; naphthols ; photochemistry ; water clusters

Sažetak
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 dark (1)pi sigma* state. The dynamics of the (1)pi sigma* 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 bright (1)pi pi*(L-a) 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 the (1)pi pi*(L-a) state of 1-naphthols.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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