Abstract
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.
Highlights
The unique physicochemical and biological properties of titanium dioxide favor its wide application in a variety of fields in our lives
We have focused on synthesis, structure determination, and photocatalytic activity studies of tetranuclear oxo-complexes [19,27]
Structural studies of (1)–(3) complexes proved that their central part was formed by {Ti4O2} core that consisted of two μ-oxo bridges, i.e., μ4 –O connecting all four Ti(IV) atoms in distorted tetrahedral that consisted of two μ-oxo bridges, i.e., μ4–O connecting all four Ti(IV) atoms in distorted environment and μ–O bridging two of the closest titanium atoms (Figure 1) similar to the structure tetrahedral environment and μ–O bridging two of the closest titanium atoms (Figure 1) similar to the of (4) [27]
Summary
The unique physicochemical and biological properties of titanium dioxide favor its wide application in a variety of fields in our lives. The optical properties and photocatalytic activity of materials based of TiO2 have especially been intensively studied in recent times [1,2,3]. Much attention has been devoted to the use of titanium oxo-clusters (TOCs) as compounds exhibiting similar properties to TiO2 but characterized by a discrete molecular structure [6,7,8,9,10]. The unique properties of oxo-clusters, e.g., photochromicity, catalytic/biological or magnetic activity, can give entirely new properties to the composite material compared to the base polymer [11,12,13,14,15,16,17,18,19,20,21,22]. Studies on Materials 2018, 11, 1661; doi:10.3390/ma11091661 www.mdpi.com/journal/materials
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