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Excited State Intramolecular Proton Transfer (ESIPT) from Phenol to Carbon in Selected Phenylnaphthols and Naphthylphenols


Basarić, Nikola; Došlić, Nađa; Ivković, Jakov; Wang, Yu-Hsuan; Veljković, Jelena; Mlinarić-Majerski, Kata; Wan, Peter
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)


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


Projekt / tema
02.05/25
098-0352851-2921 - Kontrola atomske i molekulske dinamike oblikovanim elektromagnetskim poljima (Nađa Došlić, )
098-0982933-2911 - Kavezasti spojevi: ugradbene jedinice u molekularnim sustavima (Kata Majerski, )

Ustanove
Institut "Ruđer Bošković", Zagreb

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


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