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Effects of Different Proton Donor and Acceptor Groups on Excited-State Intramolecular Proton Transfers of Amino-type and Hydroxy-type Hydrogen-Bonding Molecules: Theoretical Insights

Abstract

The effect of proton donor namely NH-type and OH-type on the excited-state intramolecular proton transfer (ESIPT) of hydrogen-bonding (H-bond) molecules was investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT) at B3LYP with TZVP basis set. The important parameters on bond distances involving the intramolecular H-bond revealed that H-bonds of OH-type are stronger than those of NH-type and supported by the more red-shift of O−H vibrational mode in the excited-state. The potential energy surfaces along the proton transfer (PT) reaction show that ESIPT of O-H type occurs with a small barrier or barrierless in the excited-state whereas those of N-H type have higher PT barrier except the one with stronger proton acceptor, resulting in a smaller barrier. On-the-fly dynamics simulations on the first excited-state were further carried out to provide the important dynamic information on PT time and probability. The results of dynamic simulations are accordance with the potential energy surfaces in which the N-H type shows no PT in APBT but slow PT in APBI and fast PT in HNHPIP while O−H type (HBI, HBT and HPIP) exhibits ultrafast PT within 80 fs. Moreover, the occurrence of ESIPT process are strongly dependent with reaction energy and activation energy, in which the H-bond molecules with thermodynamically and kinetically favorable characters always provide the ESIPT. Therefore, the type of proton donor and proton acceptor of H-bond molecules is very important to hinder or effectively facilitate ESIPT process.

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Publication details

The article was received on 24 Mar 2017, accepted on 14 Jul 2017 and first published on 14 Jul 2017


Article type: Paper
DOI: 10.1039/C7NJ00984D
Citation: New J. Chem., 2017, Accepted Manuscript
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    Effects of Different Proton Donor and Acceptor Groups on Excited-State Intramolecular Proton Transfers of Amino-type and Hydroxy-type Hydrogen-Bonding Molecules: Theoretical Insights

    N. Kanlayakan, K. Kerdpol, C. Prommin, R. Salaeh, W. Chansen, C. Sattayanon and N. Kungwan, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ00984D

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