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Titanium(IV) Oxo-Complex with Acetylsalicylic Acid Ligand and Its Polymer Composites: Synthesis, Structure, Spectroscopic Characterization, and Photocatalytic Activity.

ABSTRACT: The titanium oxo complexes are widely studied, due to their potential applications in photocatalytic processes, environmental protection, and also in the biomedical field. The presented results concern the oxo complex synthesized in the reaction of titanium(IV) isobutoxide and acetylsalicylic acid (Hasp), in a 4:1 molar ratio. The structure of isolated crystals was solved using the single-crystal X-ray diffraction method. The analysis of these data proves that [Ti₄O₂(OⁱBu)₁₀(asp)₂]·H₂O (1) complex is formed. Moreover, the molecular structure of (1) was characterized using vibrational spectroscopic techniques (IR and Raman), ¹³C NMR, and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The photocatalytic activity of the synthesized complex was determined with the use of composite foils produced by the dispersion of (1) micrograins, as the inorganic blocks, in a polycaprolactone (PCL) matrix (PCL + (1)). The introduction of (1) micrograins to the PCL matrix caused the absorption maximum shift up to 425-450 nm. The studied PCL + (1) composite samples reveal good activity toward photodecolorization of methylene blue after visible light irradiation.

SUBMITTER: Smigiel J

PROVIDER: S-EPMC9267303 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Project description:This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di-methylpropanimido-yl)-N-[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-bis-[(diethyl ether)lithium], [Li2Br2(C24H33N3)(C4H10O)2] (1) and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis-{2-(2,2-di-methylpropanimido-yl)-N-[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-1κ3N,N',N'';4κ3N,N',N''-tetra-μ-iso-propano-lato-1:2κ4O:O;3:4κ4O:O-diiso-propano-lato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N3)2(C3H7O)6] or {[NHNNH]Ti(O i Pr)3(LiBr)2}2 (2). Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O) fragment bonded to them, with the Li atom adopting a distorted tetra-hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octa-hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra-hedral coordination as in 1). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N-H groups, no hydrogen bonding is found in either one, perhaps due to the bulky groups around them. One of the ethyl groups of the ether ligand of 1 is disordered and refined in two parts with site-occupation factors of 0.812 (8) and 0.188 (8). One and a half toluene solvent mol-ecules are also present in the asymmetric unit of 2. The toluene mol-ecules were significantly disordered and could not be modeled properly, thus SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] was used to remove their contributions to the overall intensity data.

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Titanium(IV) Oxo-Complex with Acetylsalicylic Acid Ligand and Its Polymer Composites: Synthesis, Structure, Spectroscopic Characterization, and Photocatalytic Activity.

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