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The purpose of this paper is to assess the relationship between the core architecture of titanium(IV)-oxo complexes (TOCs) known as {Ti_aO_b} and their photocatalytic and antimicrobial activity. The following TOCs: [Ti₆O₄(OⁱBu)₈(O₂C₁₃H₉)₈] · 2(CH₃)₂CO (1), [Ti₆O₆(OⁱBu)₆(O₂C₁₃H₉)₆] (2), [Ti₆O₆(OⁱBu)₆(O₂C₁₃H₉)₆] (3), [Ti₃O(OⁱPr)₈(O₂C₁₃H₉)₂] (4), and [Ti₄O₂(OⁱBu)₁₀(O₂C₁₃H₉)₂] (5), where -O²C¹³H⁹represents 9-fluorene-carboxylate ligands, werestudied to investigate thiseffect. The structures of (1)–(5) were confirmed using single-crystal X-ray diffraction and spectroscopic methods. Since TOCs can be sensitive to hydrolysis processes, their photocatalytic and antimicrobial activity was evaluated after dispersing them in a polymer matrix, which acted as a protective agent against the aquatic environment. The results revealed that the photocatalytic activity of the studied TOCs follows the trend (2) > (5) > (4) > (1) in both the UV and visible ranges. All studied oxo complexes exhibited strong antibacterial activity against Gram-positive strains and weaker activity against Gram-negative strains. The proposed mechanism of the antimicrobial activity of TOCs assumes that this effect is associated with the generation of reactive oxygen species (ROS) on the surface of composite samples. Samples of PMMA + (1) 10 wt.% and PMMA + (5) 20 wt.%, in which both O⁻ and O₂⁻ paramagnetic species were observed in the electron paramagnetic spectroscopy (EPR) spectra, demonstrated the highest antimicrobial activity. Full article

The siderophore organic ligand N,2-dihydroxybenzamide (H₂dihybe) incorporates the hydroxamate group, in addition to the phenoxy group in the ortho-position and reveals a very rich coordination chemistry with potential applications in medicine, materials, and physical sciences. The reaction of H₂dihybe with TiCl₄ in methyl alcohol and KOH yielded the tetranuclear titanium oxo-cluster (TOC) [Ti^IV₄(μ-O)₂(HOCH₃)₄(μ-Hdihybe)₄(Hdihybe)₄]Cl₄∙10H₂O∙12CH₃OH (1). The titanium compound was characterized by single-crystal X-ray structure analysis, ESI-MS, ¹³C, and ¹H NMR spectroscopy, solid-state and solution UV–Vis, IR vibrational, and luminescence spectroscopies and molecular orbital calculations. The inorganic core Ti₄(μ-O)₂ of 1 constitutes a rare structural motif for discrete Ti^IV₄ oxo-clusters. High-resolution ESI-MS studies of 1 in methyl alcohol revealed the presence of isotopic distribution patterns which can be attributed to the tetranuclear clusters containing the inorganic core {Ti₄(μ-O)₂}. Solid-state IR spectroscopy of 1 showed the presence of an intense band at ~800 cm⁻¹ which is absent in the spectrum of the H₂dihybe and was attributed to the high-energy ν(Ti₂–μ-O) stretching mode. The ν(C=O) in 1 is red-shifted by ~10 cm⁻¹, while the ν(N-O) is blue-shifted by ~20 cm⁻¹ in comparison to H₂dihybe. Density Functional Theory (DFT) calculations reveal that in the experimental and theoretically predicted IR absorbance spectra of the ligand and Ti-complex, the main bands observed in the experimental spectra are also present in the calculated spectra supporting the proposed structural model. ¹H and ¹³C NMR solution (CD₃OD) studies of 1 reveal that it retains its integrity in CD₃OD. The observed NMR changes upon addition of base to a CD₃OD solution of 1, are due to an acid–base equilibrium and not a change in the Ti^IV coordination environment while the decrease in the complex’s lability is due to the improved electron-donating properties which arise from the ligand deprotonation. Luminescence spectroscopic studies of 1 in solution reveal a dual narrow luminescence at different excitation wavelengths. The TOC 1 exhibits a band-gap of 1.98 eV which renders it a promising candidate for photocatalytic investigations. Full article

The interest in titanium (IV) oxo-complexes is due to their potential application in photodegradation processes and environmental pollutants reduction. Titanium (IV) oxo-complexes (TOCs) of the general formula [Ti₃O(OⁱPr)₈(OOCR’)₂] (R’ = -C₁₃H₉ (1), -p-PhCl (2), -m-PhNO₂ (3), -C₄H₇ (4)) were synthesized and structurally characterized. The use of the different carboxylate ligands allowed modulating the optical band gaps of the produced microcrystals, which were measured via diffuse reflectance ultraviolet and visible spectroscopy (UV-Vis-DRS) and calculated using the density functional theory (DFT) method. The dispersion of TOCs (1–3) in the poly (methyl methacrylate) matrix (PMMA) led to the formation of polymer/TOCs composites, which in the next stage of our works have been applied in the photocatalytic activity estimation of synthesized trinuclear Ti(IV) oxo-complexes. Studies of the photocatalytic degradation of methylene blue (MB) induced by UV irradiation exhibit that the PMMA-TOCs composite containing (1) oxo-clusters is the most active, followed by the system containing the complex (3). Full article

Titanium(IV) oxo-clusters of the general formula (Ti₄O₂(OⁱBu)₁₀(O₂CR’)₂) (R’ = C₁₃H₉ (1), PhCl (2), PhNO₂ (3)) were studied in order to estimate their potential photoactivity. The structure of the resulting tetranuclear Ti(IV) oxo-complexes was then determined via single crystal X-ray diffraction, infrared and Raman spectroscopy, and electron spin resonance (ESR). An analysis of diffuse reflectance spectra (DRS) allowed for the assessment of band gap values of (1)–(3) microcrystalline samples complexes. The use of different carboxylate ligands allowed the band gap of tetranuclear Ti(IV) oxo-clusters to be modulated in the range of 3.6 eV–2.5 eV. Density functional theory (DFT) methods were used to explain the influence of substitutes on band gap and optical activity. Dispersion of (1)–(3) microcrystals in the poly(methyl methacrylate) (PMMA) matrixes enabled the formation of composite materials for which the potential photocatalytic activity was estimated through the study on methylene blue (MB) photodegradation processes in the presence of UV light. The results obtained revealed a significant influence of carboxylate ligands functionalization on the photoactivity of synthesized tetranuclear Ti(IV) oxo-complexes. Full article