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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 π3 and π4 ligand are reduced. In addition, in a number of spiroborates, the violation of C2v 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 π2X → π4 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 S0 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-pVDZ, ADC(2)/cc-pVDZ and EOM-DLPNO/cc-pVDZ methods. All DFT and TDDFT calculations were carried out in the GAMESS (US) software computing package. ADC(2) calculations of excited states were performed using the Orca 4.0.1 software package. EOM-DLPNO and OVGF calculations were carried out in the Gaussian 16 software package. [ABSTRACT FROM AUTHOR]