TY - JOUR

T1 - Electronic structure of binuclear acetylacetonates of boron difluoride

AU - Tikhonov, Sergey A.

AU - Svistunova, Irina V.

AU - Samoilov, Ilya S.

AU - Osmushko, Ivan S.

AU - Borisenko, Aleksandr V.

AU - Vovna, Vitaliy I.

N1 - Funding Information: This work was supported by the Ministry of Education and Science of the Russian Federation within the framework of project part of the state task (Project No. 3.2168.2017/4.6 ) Publisher Copyright: © 2018 Copyright: Copyright 2018 Elsevier B.V., All rights reserved.

PY - 2018/5/15

Y1 - 2018/5/15

N2 - The electronic structure of boron difluoride acetylacetonate and its three derivatives was studied using photoelectron and absorption spectroscopy, as well as the density functional theory. In a series of binuclear acetylacetonate complexes containing bridge-moieties of sulfur and selenium atoms, it was found an appreciable mixing of the π3-orbital of the chelate cycle with atomic orbitals S 3p and Se 4p resulting in destabilization of the HOMO levels by 0.4–0.6 eV, in comparison with the monomer. The positively charged fragment C(CH3)-CX-C(CH3) causes the field effect, which leads to stabilization of the LUMO levels by 0.3–0.4 eV and C 1s-levels by 0.5–1.2 eV. An analysis of the research results on the electronic structure made it possible to determine the effect of substituents in the γ position on the absorption spectra, which is mainly determined by the electron density transfer from the chalcogen atoms to the chelate cycles. It is shown that the calculated energy intervals between electron levels correlate well with the structure of the photoelectron spectra of valence and core electrons.

AB - The electronic structure of boron difluoride acetylacetonate and its three derivatives was studied using photoelectron and absorption spectroscopy, as well as the density functional theory. In a series of binuclear acetylacetonate complexes containing bridge-moieties of sulfur and selenium atoms, it was found an appreciable mixing of the π3-orbital of the chelate cycle with atomic orbitals S 3p and Se 4p resulting in destabilization of the HOMO levels by 0.4–0.6 eV, in comparison with the monomer. The positively charged fragment C(CH3)-CX-C(CH3) causes the field effect, which leads to stabilization of the LUMO levels by 0.3–0.4 eV and C 1s-levels by 0.5–1.2 eV. An analysis of the research results on the electronic structure made it possible to determine the effect of substituents in the γ position on the absorption spectra, which is mainly determined by the electron density transfer from the chalcogen atoms to the chelate cycles. It is shown that the calculated energy intervals between electron levels correlate well with the structure of the photoelectron spectra of valence and core electrons.

KW - Electronic structure

KW - Photoelectron spectroscopy

KW - Absorption spectra

KW - Density functional theory

KW - Boron difluoride β-diketonates

UR - http://www.scopus.com/inward/record.url?scp=85041433915&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2018.02.005

DO - 10.1016/j.molstruc.2018.02.005

M3 - Article

AN - SCOPUS:85041433915

VL - 1160

SP - 92

EP - 100

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -