Electronic structure, cationic, and excited states of nitrogen-containing spiroborates

Context This paper presents the results of the study of the electronic structure and cationic and excited states of three spiroborate complexes (2-acetylacetonato-1,3,2-benzodioxaborol, its NH- and NMe-derivatives) and three corresponding ligands (acetylacetone, 4-aminopent-3-en-2-one, and 4-methyla...

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Published in:Journal of molecular modeling 2023-03, Vol.29 (3), p.69-69, Article 69
Main Authors: Sidorin, Andrey E., Tikhonov, Sergey A., Samoilov, Ilya S., Osmushko, Ivan S., Svistunova, Irina V., Tretyakova, Galina O., Puzyr’kov, Zahar N., Vovna, Vitaliy I.
Format: Article
Language:English
Subjects:
Absorption spectra
Absorption spectroscopy
Acetylacetone
Cations
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Computer Appl. in Life Sciences
Computer Applications in Chemistry
Density functional theory
Drug carriers
Electron density
Electron transitions
Electronic structure
Excitation
Functional groups
Green's functions
Ionic liquids
Ligands
Mathematical analysis
Molecular Medicine
Molecular orbitals
Original Paper
Oxygen
Photoelectrons
Quantum chemistry
Software packages
Spectroscopic analysis
Spectrum analysis
Theoretical and Computational Chemistry
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Summary:Context This paper presents the results of the study of the electronic structure and cationic and excited states of three spiroborate complexes (2-acetylacetonato-1,3,2-benzodioxaborol, its NH- and NMe-derivatives) and three corresponding ligands (acetylacetone, 4-aminopent-3-en-2-one, and 4-methylaminopent-3-en-2-one). Materials based on spiroborates are used in medicine, for example, as a drug carrier. In industry, spiroborate anions are used in ionic liquids and as alternative high performance lubricants. Analysis of experimental and calculated data allowed determining the influence of functional groups on the parameters of the electronic structure and energy of electronic transitions. Compared to acetylacetone and its NH- and NMe-derivatives, the upper filled molecular orbitals of the corresponding spiroborates are stabilized at 0.4–1.7 eV, which is due to the positive charge of the ligand due to the acceptor properties of the dioxyphenylene fragment. Among the studied compounds, when replacing the oxygen atom in the α-position with the NH- or NMe-group, a bathochromic shift of intense bands in the absorption spectra is observed, since the energy intervals between the orbitals of the π 3 and π 4 ligand are reduced. In addition, in a number of spiroborates, the violation of C 2v symmetry when replacing an oxygen atom leads to the appearance of a low-intensity maximum in the long-wave part of the absorption spectrum, due to the π 2 X  →  π 4 transition. Method Complexes were studied by photoelectron spectroscopy, absorption spectroscopy, and high-level ab initio quantum chemical computations, including the algebraic diagrammatic construction method for the polarization propagator of the second order (ADC(2)), the outer-valence Green’s function (OVGF), the density functional theory (DFT), the time-dependent density functional theory (TDDFT) and the domain-based local pair natural orbital (EOM-DLPNO) methods. X-ray photoelectronic spectra of two spiroborates in the condensed state were measured using a two-chamber high-vacuum system MXPS XP (Omicron, Germany). UV–visible absorption spectra were recorded using a spectrophotometer 2550 (Shimadzu-UV, Japan). The geometry of all studied compounds was optimized by the DFT/B3LYP/Def2-SVP method. The energy of electron levels in the S 0 state and the distribution of electron density at each MO were obtained by the DFT/CAMB3LYP/cc-pVDZ method. The energies of excited states were obtained by the TDDFT/CAMB3LYP/cc-p
ISSN:1610-2940
0948-5023
DOI:10.1007/s00894-023-05465-z