کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1231516 1495259 2013 9 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Hydrogen bonding and coordination bonding in the electronically excited states of Cu2(L)2 (L = 5-(4-pyridyl)tetrazole)MeOH: A TDDFT study
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آنالیزی یا شیمی تجزیه
پیش نمایش صفحه اول مقاله
Hydrogen bonding and coordination bonding in the electronically excited states of Cu2(L)2 (L = 5-(4-pyridyl)tetrazole)MeOH: A TDDFT study
چکیده انگلیسی

The luminescent metal organic framework (MOF), Cu2(L)2·MeOH (L = 5-(4-pyridyl)tetrazole), was studied using time-dependent density functional theory (TDDFT). A combination of frontier molecular orbitals and electronic configuration analysis revealed that the emission mechanism was a ligand to metal charge transition (LMCT) rather than a metal to ligand charge transfer (MLCT). Hydrogen bonding significantly changed the nature of the frontier orbital and the luminescence. Electronic transition energies predicted that the hydrogen bonding in excited state would become weaker with an electronic spectral blue-shift. The bond lengths, frequencies, and binding energies indicated weakening of the hydrogen bonding in the excited state, which can affect emissions in two ways, including: (i) a decrease in the electronic coupling between methanol and the motif and suppressing the occurrence of the photo-induced electron transfer (PET); and (ii) increasing the energy gap between S1 and S0, leading to radiative transition. Coordination bonding was also investigated in the excited state through bond lengths, frequencies, and bond orders. Coordination bonds were found to become stronger in the excited state leading to an enhancement of the luminescence.

Figure optionsDownload as PowerPoint slideHighlights
► The luminescent metal organic framework was studied by TDDFT method.
► Ligand to metal charge transition mechanism was clarified.
► Excited-state hydrogen bond weakening induces spectral blue-shift.
► Photoinduced electron transfer decreases due to excited-state hydrogen bond weakening.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy - Volume 109, 15 May 2013, Pages 14–22
نویسندگان
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