European Journal of Inorganic Chemistry最新文献

The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand-protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M–M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

A metal-rich niobium oxyiodide was prepared by soft reduction of NbI₄. The structure of the new compound Nb₄OI₁₀ was determined by single-crystal X-ray diffraction and contains a rectangular Nb₄(μ₄-O) cluster that is interconnected into layers by iodide ligands. The local structure of the Nb₄OI₁₀ cluster bears a close relationship to a defect Nb₆I₁₁ structure. The two-dimensional van der Waals material $$Nb₄OI₈I_4/2] is a small band-gap semiconductor (<1 eV), as analysed by electrical conductivity measurements, photoresponse, experimental band gap determination, and band structure calculation.

Amino-functionalized β-diketiminate stabilized chlorogermylene 1 and chlorostannylene 2 have been prepared and structurally characterized. The reactions of 1 or 2 with KO^tBu afforded the β-diketiminate stabilized tert-butoxygermylene 3 and tert-butoxystannylene 4, respectively. On the other hand, the reaction of 2 with LiN(SiMe₃)₂ led to the isolation of the bis-stannylene 5 containing a four-membered Sn₂N₂ ring. All new compounds have been characterized by multiple NMR spectroscopy and single crystal X-ray analysis.

The negative impact of heavy metal pollution, specifically chromium (VI), on human health is well-documented. To solve this issue, hollow anisotropic hierarchically porous “Fish Cage”-like carbonaceous nanomaterial (N,S-HFC-180) with multi-active groups is synthesized. Hierarchically porous structure provides stepped adsorption effect. The addition of K₂C₂O₄ leads to an increase in the specific surface area of N,S-HFC-180 to 1914.21 m² g⁻¹ (an increase of ~552 times compared to HFC-180). Thiourea introduces multi-active groups that act as “Barbs” in “Fish Cage”, further reducing Cr(VI) to Cr(III) and sequestrating Cr(III) by coordination effect. Subsequent batch studies suggest that N,S-HFC-180 exhibits a high removal capacity of 164.29 mg g⁻¹ for Cr(VI) at pH=2. The kinetics and isotherm analyses display an outstanding maximum adsorption capacity of 393.88 mg g⁻¹ at 298 K. In addition, even after seven cycles, the removal rate of Cr(VI) using N,S-HFC-180 remains>85.00 %, and it effectively reduces the concentration of electroplating wastewater from 55.82 to 0.14 mg L⁻¹. Pore filling, chemical reduction and chelation, hydrogen bond and electrostatic attraction are the primary adsorption drivers. The results suggest that, the recoverable N,S-HFC-180 highlights its viability for practical applications in wastewater treatment processes.

Employing metal complex cations as the structural modifiers, three new numbers of hybrid halobismuthates family, namely [NH₄][Co(phen)₃]BiI₆ (phen=1,10-phenanthroline; 1), [Zn(phen)₂Br][Bi(phen)Br₄] ⋅ H₂O (2) and [Cu(2,2′-bipy)₂Br][Cu(2,2′-bipy)₂Bi₂Br₉] ⋅ H₂O (2,2′-bipy=2,2′-bipyridine; 3) have been solvothermally constructed and structurally characterized. X-ray crystallography analyses show that all compounds characteristic of abundant weak interactions feature the discrete anionic motifs. The obtained hybrid materials possess the semiconducting nature, with the visible light responding optical band gaps of 2.13–2.71 eV. Under the alternating light irradiation, they exhibit excellent photoelectric switching properties, whose photocurrent densities (0.85, 0.24, and 0.43 μA/cm² for compounds 1–3, respectively) compare well with some high-performance halobismuthate competitors. Further theoretical calculations of compound 1 reveal that the photosensitive [Co(phen)₃]²⁺ cations contribute greatly to the bottom of conduction bands (CBs) and the top of valence bands (VBs), which may be the important reason for its excellent photoelectric behavior. The analyses of Hirshfeld surface, thermal stability, and X-ray photoelectron spectroscopy were also discussed detailedly in this paper.

Switchable molecular materials have continued to attract the interest of chemists and physicists for decades. A prominent example are spin crossover complexes, where numerous textbooks, review articles, and special issues are available. A highly interesting alternative is the coordination-induced spin-state switching. In this concept, we will compare the two spin-state switching mechanisms and discuss common aspects and differences. Additionally, a short overview of coordination-induced spin state switching will be given.

A dinuclear cadmium(II) complex, [Cd₂(Hhqc)₂(H₂O)₄] (H₃hqc=4,8-dihydroxyquinoline-2-carboxylic acid) was synthesized and characterized by single crystal X-ray diffraction studies, elemental analyses and thermo-gravimetric studies. The metal centers are found to be six coordinated with distorted pentagonal pyramidal geometry around them. The complex shows few significant intermolecular hydrogen bonding interactions to produce a three dimensional supramolecular network comprising of T8(2) water tapes. Besides these non-covalent interactions few other supramolecular interactions are also involved within the molecular dimer like π⋅⋅⋅π stacking, Cd⋅⋅⋅π etc. They have been analyzed using DFT calculations, MEP surface analyses and NCI plot index analyses. The detailed study highlights the complex interplay of π-stacking, H-bonding, and spodium interactions in stabilizing the dimers of complex, which providing precious insights into their energetic and structural characteristics. Further more, the catalytic efficiency of the synthesized complex has been investigated as an effective heterogeneous catalyst in the Knoevenagel condensation reactionunder solvent-free conditions.

Multinuclear aluminum complexes are useful catalysts for the ring opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL), often outperforming monometallic analogues in the production of biodegradable polycaprolactone (PCL). These complexes require control over metal-metal distance, ligand structure, and substituents. Herein, we report on the preparation of mono-, bi-, and octametallic aluminum complexes through direct chelation of multidentate bis(phosphino)-2,2-dimethyl-1,3-diamino ligands Me₂C[CH₂NHR₂P(O)]₂; R=Ph(1), ⁱPr(2), ^tBu(3). Ligands 1–3 yielded bimetallic complexes with two types of coordination pockets, as well as bimetallic systems with identical coordination environments. In addition to the diversity of structural patterns within the present series, the catalytic performances of [AlR₂{κ²-N,N’,–(Me₂C{CH₂NPh₂P(O)}₂}-(κ²-O,O’-AlR₂)] (R=Me(4), Et(5), ⁱBu(6)) outperformed that of the monometallic [AlEt₂{κ²-O,O’-(Me₂C(CH₂N^tBu₂P(O))₂H} (10), showing controlled and immortal ROP of ϵ-CL in the presence of BnOH as co-initiator. DFT calculations suggest that the primary active site for 4–6 is the N−Al–N center. Gaining insight into the underlying principles that lead to high activity and controlled production of PCL in bimetallic systems can help design tailor-made complexes with enhanced performance.