Optical properties and electronic structure of Eu(III) complexes with HMPA and TPPO.

Autor: Shurygin AV; Far Eastern Federal University, 8 Sukhanova St., Vladivostok, Russia., Vovna VI; Far Eastern Federal University, 8 Sukhanova St., Vladivostok, Russia. Electronic address: shurygin.av@dvfu.ru., Korochentsev VV; Far Eastern Federal University, 8 Sukhanova St., Vladivostok, Russia., Mirochnik AG; Institute of Chemistry, FEB RAS, 159 Prosp. 100-letiya Vladivostoka, Vladivostok, Russia., Kalinovskaya IV; Institute of Chemistry, FEB RAS, 159 Prosp. 100-letiya Vladivostoka, Vladivostok, Russia., Sergienko VI; Far Eastern Branch, RAS, 50 Svetlanskaya St., Vladivostok, Russia.
Jazyk: angličtina
Zdroj: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy [Spectrochim Acta A Mol Biomol Spectrosc] 2021 Apr 05; Vol. 250, pp. 119397. Date of Electronic Publication: 2020 Dec 30.
DOI: 10.1016/j.saa.2020.119397
Abstrakt: Two adducts of Eu(III) tris-hexofluoroacetylacetonate with HMPA (OP(N(CH 3 ) 2 ) 3 , hexamethylphosphotriamide) and TPPO (OP(C 6 H 5 ) 3 , triphenylphosphine oxide) were studied by optical spectroscopy and quantum chemistry (DFT/TD-DFT). The structure of the higher occupied molecular orbitals (MO) of the two adducts determines differences in the position of the excitation band maximum of hfac ligands. According to the calculation data, all excited states are caused by the transition to 3 vacant π 4 * MOs of hfac ligands. Optical spectra of absorption, excitation and luminescence are obtained and interpreted. The peculiarity of the HOMO-LUMO structure, the low value of the energy gap, and the broadened absorption region of hfac ligands compensate the low absorbance ability of the groups N(CH 3 ) 2 in a region of 220-360 nm for the adduct Eu(hfac) 3 (HMPA) 2 , reducing the luminescence intensity by only 5-10% relative to the adduct of the Eu(III) complex with TPPO ligands.
Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2020 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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