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Indexed by:期刊论文

Date of Publication:2015-01-13

Journal:CHEMICAL PHYSICS

Included Journals:SCIE、Scopus

Volume:446

Page Number:65-69

ISSN No.:0301-0104

Key Words:Luminescent metal-organic frameworks; Hydrogen bond; Excited states; Time-dependent density functional theory

Abstract:The influence of CH3OH solvent on the luminescent properties of the [Zn(sfdb)(bpy)(H2O)](n) center dot 0.5nCH(3)OH (sfdb = 4,4-sulfonyldibenzoic acid, bpy = 2,2-bipyridine) metal-organic framework (MOF) was investigated by considering the hydrogen bond between CH3OH and [Zn(sfdb)(bpy)(H2O)](n) in an electronically excited state using density functional theory and time-dependent density functional theory methods. The calculated geometry, infrared spectrum, and UV-vis spectrum in the ground state are consistent with the experimental results. The frontier molecular orbitals and electronic configuration indicated that the origin of the luminescence is ligand-to-ligand charge transfer rather than ligand-to-metal charge transfer, as has been previously proposed. We found that the O3 center dot center dot center dot H11 hydrogen bond is weaker in the excited state than in the ground state, and the weaker hydrogen bond in the electronically excited state should enhance the luminescence. The results show that the CH3OH solvent changes the luminescence properties of [Zn(sfdb)(bpy)(H2O)](n), which provides potential opportunities for the design of diverse luminescent MOFs. (C) 2014 Published by Elsevier B.V.