Pregled bibliografske jedinice broj: 594899
Excited State Intramolecular Proton Transfer (ESIPT) from Phenol to Carbon in Selected Phenylnaphthols and Naphthylphenols
Excited State Intramolecular Proton Transfer (ESIPT) from Phenol to Carbon in Selected Phenylnaphthols and Naphthylphenols // Journal of organic chemistry, 78 (2013), 5; 1811-1823 doi:10.1021/jo301456y (međunarodna recenzija, članak, znanstveni)
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Naslov
Excited State Intramolecular Proton Transfer (ESIPT) from Phenol to Carbon in Selected Phenylnaphthols and Naphthylphenols
Autori
Basarić, Nikola ; Došlić, Nađa ; Ivković, Jakov ; Wang, Yu-Hsuan ; Veljković, Jelena ; Mlinarić-Majerski, Kata ; Wan, Peter
Izvornik
Journal of organic chemistry (0022-3263) 78
(2013), 5;
1811-1823
Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni
Ključne riječi
ab initio calculations; deuterium exchange; excited state intramolecular proton transfer (ESIPT); quinone methides; solvent-assisted PT
Sažetak
ESIPT and solvent-assisted ESPT in isomeric phenyl naphthols and naphthyl phenols 5-8 were investigated by preparative photolyses in CH3CN-D2O, fluorescence spectroscopy, LFP, and ab initio calculations. ESIPT takes place only in 5 (D-exchange Φ = 0.3), whereas 6-8 undergo solvent-assisted PT with much lower efficiencies. The efficiency of the ESIPT and solvent-assisted PT is mainly determined by different populations of the reactive conformers in the ground state and the NEER principle. The D-exchange experiments and calculations using RI-CC2/cc-pVDZ show that 5 in S1 deactivate by direct ESIPT from the OH to the naphthalene position 1 through a conical intersection with S0, delivering QM 14 that was detected by LFP (τ = 26 ± 3 ns). ESIPT to the position 3 in 5 is possible but it proceeds from a less-populated conformer and involves an energy barrier on S1. In solvent-assisted PT to the naphthalene position 4 in 5, zwitterion 17 is formed that cyclizes to stable naphthofuran photoproducts 9-12. The regiochemistry of the deuteration in solvent-assisted PT was correlated with the NBO charges of the corresponding phenolates/naphtholates 5- - 8-. Combined experimental and theoretical data indicate that solvent-assisted PT takes place via a sequential mechanism involving first deprotonation of the phenol/naphthol, followed by the protonation by H2O in the S1 state of phenolate/naphtholate. The site of protonation by H2O is mostly at the naphthalene α-position.
Izvorni jezik
Engleski
Znanstvena područja
Kemija
POVEZANOST RADA
Projekti:
02.05/25 - Fotokemija policikličkih molekula: od istraživanja mehanizama reakcije do novih lijekova i medicinskih primjena (Basarić, Nikola, HRZZ ) ( CroRIS)
098-0352851-2921 - Kontrola atomske i molekulske dinamike oblikovanim elektromagnetskim poljima (Došlić, Nađa, MZOS ) ( CroRIS)
098-0982933-2911 - Kavezasti spojevi: ugradbene jedinice u molekularnim sustavima (Majerski, Kata, MZOS ) ( CroRIS)
Ustanove:
Institut "Ruđer Bošković", Zagreb
Citiraj ovu publikaciju:
Časopis indeksira:
- Current Contents Connect (CCC)
- Web of Science Core Collection (WoSCC)
- Science Citation Index Expanded (SCI-EXP)
- SCI-EXP, SSCI i/ili A&HCI
- Scopus
- MEDLINE
