| 1. |
- Buvailo, Halyna, et al.
(author)
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Facile one-pot synthesis of hybrid compounds based on decavanadate showing water oxidation activity
- 2020
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In: Inorganic Chemistry Communications. - : Elsevier BV. - 1387-7003 .- 1879-0259. ; 119
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Journal article (peer-reviewed)abstract
- Herein, we report the synthesis of two hybrid compounds based on decavanadate anion, namely, [Cu(dien)(Hdien)]2[V10O28]·2H2O (1) and (H3dien)2[V10O28]·4H2O (2), where dien = diethylenetriamine, obtained under mild conditions. Both compounds were characterized by elemental, TG/DTA, single crystal and powder X-ray diffraction analyses, IR and EPR spectroscopies. The compound 1 was found to be active as homogeneous photochemical oxidation catalyst of water to dioxygen.
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| 2. |
- Buvailo, Halyna I., et al.
(author)
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Copper-containing hybrid compounds based on extremely rare [V2Mo6O26]6- POM as water oxidation catalysts
- 2019
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In: Inorganic Chemistry Frontiers. - : Royal Society of Chemistry (RSC). - 2052-1545 .- 2052-1553. ; 6:7, s. 1813-1823
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Journal article (peer-reviewed)abstract
- Herein, we report two approaches to the synthesis of heterometallic complexes (NH4)(2n)(H(2)en)(n){[Cu(en)(2)][alpha-V2Mo6O26]}center dot 4nH(2)O (1), (NH4)(2){[Cu(dien)(H2O)](2)[alpha-V2Mo6O26]}center dot 5H(2)O (2) and (NH4)(2){[Cu(dien)(H2O)](2)[alpha-V2Mo6O26]}center dot 8H(2)O (3) that have been employed in homogeneous photochemical oxidation of water to dioxygen. In these hybrid metalorganic-inorganic compounds, copper-containing complex fragments are covalently bound to the rare vanadium-disubstituted alpha-octamolybdate cluster. They exhibit variable catalytic activity controlled by the local coordination environment of copper reaching a notably high turnover frequency of 0.24 s(-1) for 3 in combination with a relatively low water oxidation overpotential. The complexes have been also used as precursors for the preparation of mixed oxide phases that have proven to be active heterogeneous water oxidation catalysts.
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| 3. |
- Pavliuk, Mariia V., et al.
(author)
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Structural, magnetic, thermal and visible light-driven water oxidation studies of heterometallic Mn/V complexes
- 2015
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In: Polyhedron. - : Elsevier BV. - 0277-5387 .- 1873-3719. ; 88, s. 81-89
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Journal article (peer-reviewed)abstract
- In this paper a novel synthetic route, being a paradigm of the "direct synthesis" approach, is proposed for the preparation of heterometallic Mn/V compounds by a one-pot reaction. Two synthesized complexes, (NH4)(2)[Mn-2(HGly)(H2O)(10)][V10O28]center dot(HGlY)center dot 2H(2)O (1) and (NR4)(2)[Mn(beta-HAIa)(H2O)(5)](2)[V10O28]center dot 2H(2)O (2) (HGly = glycine, beta-HAla = beta-alanine) have been fully characterized by elemental analysis, single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, FTIR and EPR spectroscopy. Thermal degradation of these compounds lead to the formation of porous, solid mixed oxides V2O5/MnV2O6 in a ratio of 3:2, which were analyzed by X-ray phase analysis and scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Additionally the ability of 1 and 2 to act as oxygen evolving water oxidation catalysts under visible light-driven conditions have been studied in a Clark type cell and by ex situ EPR spectroscopy.
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| 4. |
- Wojciechowska, Agnieszka, et al.
(author)
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Chelidamic acid tautomers in copper(ii) compounds : one-pot synthesis, crystal structure, spectroscopic and dft studies
- 2023
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In: Polyhedron. - : Elsevier. - 0277-5387 .- 1873-3719. ; 230
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Journal article (peer-reviewed)abstract
- Two copper(II) chelidamate compounds with 2,2'-bipyridine were obtained as crystals [Cu(Hcda)(bpy)(H2O)]∙2H2O (1) and [Cu(H2cda)(bpy)(H2O)](H2cda) (2) (H3L = H3cda = chel = chelidamic acid, bpy = 2,2′-bipyridine) through one-pot synthesis. In 1, the tridentate Hcda2− ligand, an enol tautomer of the 4-hydroxypyridine type, and a bpy molecule coordinate the Cu(II). In 2, the same tautomer of the tridentate H2cda− ligand (with one deprotonated carboxylic acid), along with bpy, forms a cationic [Cu(H2cda)(bpy)(H2O)]+ complex. It is charge-balanced by an H2chel− anion, featuring the rare keto tautomer of the 4-pyridone type. The alternately protonated and deprotonated carboxylic groups of both tautomers are involved in hydrogen bonds leading to 1D chains. The adjacent chains are connected to form 2D chain by hydrogen bonds between two different tautomers of chel. As confirmed by the DFT calculations, the crystal structures of 1 and 2 are mainly stabilised by hydrogen bonds and electrostatic interactions, the latter being especially noticeable in the [Cu(H2cda)(bpy)(H2O)]+ cationic complex (2). Additionally, π⋯π stack is formed between aromatic ring fragments. The presence of each particular tautomer in the crystal structures of 1 and 2 can be explained by the relative energies of the respective structural moieties in the aqueous environment, combined with coordination and intermolecular interaction preferences.
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