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Pregled bibliografske jedinice broj: 590115

Časopis

Autori: Basarić, Nikola; Došlić, Nađa; Ivković, Jakov; Wang, Yu-Hsuan; Mališ, Momir; Wan, Peter
Naslov: Very Efficient Generation of Quinone Methides through Excited State Intramolecular Proton Transfer to a Carbon Atom
Izvornik: Chemistry : a European journal (0947-6539) 18 (2012), 34; 10617-10623
Vrsta rada: članak
Ključne riječi: ab initio calculations · deuterium exchange · naphthols · photochemistry · quinone methides
Sažetak:
Irradiation of 2-phenyl-1-naphthol (6) in CH3 CN/D2O (3:1)leads to very efficient incorporation of deuterium at the ortho-positions of the adjacent phenyl ring (overall F=0.73+-0.07), along with minor incorporation at the naphthalene positions 5 and 8. These finding are explained by excited state intramolecular proton transfer (ESIPT) from the phenolic OH group to the corresponding carbon atoms, the main pathway giving rise to quinone methide (QM) 7, which has been characterized by LFP (t ~20 ns ; 460 nm). The ESIPT reaction paths have been explored with the second order approximate coupled cluster (CC2) method. In nonprotic solvents the ESIPT from the naphthol O-H to the ortho-position of the phenyl ring proceeds in a barrierless manner along the 1La energy surface via a conical intersection with the S0 state, delivering 7. In aqueous solvent, clusters with H2O are formed wherein proton transfer (PT) to solvent and a H2O-mediated relay mechanism gives rise to naphtholates and QMs. The results are compared with 2-phenylphenol (3) that also undergoes barrierless ESIPT giving a QM via a conical intersection. However, due to an unfavorable conformation in the ground state, the quantum efficiency for ESIPT of 3 is significantly lower (F for D-exchange=0.041). These results show that ESIPT from phenol to carbon need not be an intrinsically inefficient proces.
Projekt / tema: 02.05/25, 098-0352851-2921
Izvorni jezik: ENG
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Science Citation Index Expanded (SCI-EXP) (sastavni dio Web of Science Core Collectiona)
Kategorija: Znanstveni
Znanstvena područja:
Kemija
URL Internet adrese: http://onlinelibrary.wiley.com/doi/10.1002/chem.201201144/abstract;jsessionid=4885C8C86E3A9E8E755D43170DA40A98.d03t04
http://dx.doi.org/10.1002/chem.201201144
Broj citata:
Altmetric:
DOI: 10.1002/chem.201201144
URL cjelovitog teksta:
Google Scholar: Very Efficient Generation of Quinone Methides through Excited State Intramolecular Proton Transfer to a Carbon Atom
Upisao u CROSBI: eluksa@irb.hr (eluksa@irb.hr), 22. Kol. 2012. u 13:19 sati



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