Synthesis, structural and physicochemical characterization of a new type Ti<sub>6</sub>-oxo cluster protected by a cyclic imide dioxime ligand

“…In the ngerprint region, the changes in the structure due to the coordination to titanium are evidenced by the appearance of two new bands at 787 and 843 cm À1 that can be attributed to Ti-O stretching. 28 The IR data conrm that the products are pure. NMR spectra for (I) are shown in ESI as Fig.…”

Section: Ir and Nmr Spectroscopymentioning

confidence: 99%

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters

et al. 2021

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“…Chemical exchange between the two coordinated Hdihybe − ligands is supported by the much broader 1 H peaks of 1 than the respective peaks of H 2 dihybe. The carbonylic 13 C NMR peak of the CD 3 OD solution of 1, determined by 2D grHSQC and gr HMBC spectroscopies (Figures S3-S6), shows the largest shift compared to the respective peak of the ligand, ∆δ = −3.9 ppm, suggesting coordination of Ti IV to the carbonylic oxygen atom [24,[58][59][60][61].…”

Section: Nmr Spectroscopymentioning

confidence: 99%

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

et al. 2021

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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) [TiIV4(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 TiIV4 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 TiIV 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.

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Synthesis, structural and physicochemical characterization of a new type Ti₆-oxo cluster protected by a cyclic imide dioxime ligand

Abstract: A new type of Ti6-oxo cluster with a structural motif TiIV6O5 was synthesized of which the cyclo-Ti3 metallic cores exhibit metallaromaticity.

Cited by 18 publications

References 77 publications

The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters

The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

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Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand

Abstract: A new type of Ti6-oxo cluster with a structural motif TiIV6O5 was synthesized of which the cyclo-Ti3 metallic cores exhibit metallaromaticity.

Cited by 18 publications

References 77 publications

The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters

The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

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Synthesis, structural and physicochemical characterization of a new type Ti₆-oxo cluster protected by a cyclic imide dioxime ligand