The reaction of hydrated salts of paramagnetic lanthanides (GdCl3, DyCl3, and HoCl3) with sterically hindered phosphinic acid (trityl-H-phosphinic acid) in a stoichiometric ratio of 1:2 afforded dinuclear gadolinium {Gd2[Ph3C(H)(PO2)]4(CH3OH)8}(CH3OH)8Cl2 (1), isostructural paddlewheel-type trinuclear dysprosium {Dy3[(Ph3C)(H)(PO2)]8(H2O)6} (2), and holmium {Ho3[(Ph3C)(H)(PO2)]8(DMF)4(H2O)2} (3) complexes. The direct current (dc) magnetic measurements indicate potentially very weak magnetic interactions at low temperatures for all complexes (1-3). Alternating current (ac) magnetic susceptibility measurements show field-induced out-of-phase magnetic susceptibility signals for the isotropic GdIII complex (1). Slow magnetic relaxation in this case is attributed to either a direct process or a phonon bottleneck effect. The DyIII complex (2) also exhibits the single-molecule magnet behavior under an applied magnetic field of 2200 Oe, with slow magnetic relaxation occurring through a combination of Raman and Orbach processes, while the small n exponent value also suggests the participation of the phonon bottleneck effect. Additionally, detailed theoretical studies are provided to explain and understand the observed magnetic properties of these complexes.

A Ce(III) phosphinate and a Ce(IV) phosphostibonate have been assembled by the reaction of a phosphinic acid and phosphostibonate with Ce(III) salts. Single crystal X-ray diffraction (SCXRD) studies reveal the formation of a rare triangular Ce(III) oxo-cluster [CeIII3(Ph3CHPO2)]6Cl3(CH3OH)(H2O)8] (1) and a fascinating hexanuclear oxo-cluster containing Ce(IV) ions [CeIV6 (p-ClC6H4SbV)4(μ4-O)4(μ3-O)4(t-BuPO3)8(μ2-OCH3)8] (2). The molecular architecture of 2 showcased an interesting correlation with platonic solids, wherein the Ce(IV), Sb(V), and P(V) ions were found to be present in vertices of an octahedron, a tetrahedron, and a cube, respectively. Under mild conditions, 1 and 2 exhibited the capability to act as catalysts for sulfoxidation in the presence of hydrogen peroxide, with 1 acting as a homogeneous catalyst and 2 acting as a heterogeneous catalyst. Both 1 and 2 showed high conversion for various substrates, with 1 showing moderate selectivity while 2 showcased high selectivity. Moreover 1 and 2 catalyzed the oxidation of 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with high selectivity.

Organotellurium-based macrocycles have been synthesized with different capping halides. The variation of halide ions brought a change in the optical bandgap and they act as catalysts for effective detoxification of a mustard gas simulant.

The reaction of telluric acid with di-organotellurium di chloride (R2TeCl2) and tri-organoantimony dichloride (R3SbCl2) has been carried out in binary solvent using solvothermal synthesis method and isolated high-phase purity compounds. Single crystal X-ray diffraction studies revealed the formation of a novel mixed valent tellurium (VI) containing clusters TeVI[OTeIV(p-MeOC6H4)2Cl]6 (R = p-MeOC6H4) (1) and [Te(µ2-O5SbPh3)(OSbh3Cl)]2 (2). Cluster 1 has a central Te(VI) atom which is connected to six oxygen atoms octahedrally, further this oxygens bridging to six other tellurium atoms (IV). Cluster 2 is an octanuclear heterometallic cluster that is built up of a [Te (VI), Sb (V)] Te2Sb6 oxo-centered butterfly core. The products have been analyzed using single crystal X-ray diffractions, powder X-ray diffraction, and IR spectroscopic and analytical methods. A star-shaped mixed valent tellurium [(VI), (IV)] cluster TeVI[OTeIV(p-MeOC6H4)2Cl]6 (1) has been synthesized in binary solvent (Acetonitrile/DMF) medium. Cluster [Te(µ2-O5SbPh3)(OSbh3Cl)]2 (2) is an octanuclear heterometallic assembly built up of Te (VI) and Sb (V) ions, containing an oxo-centered butterfly core.

Inspired by the intriguing nature of the metal-π interaction in organometallic chemistry, a novel 1D hybrid material has been designed. Herein, a functionalized tellurium allyl macrocycle (TAM) acts as a molecular building block and is knit together via silver-π interaction to obtain Ag-TAM. Ag is coordinated to two allyl groups and a phenyl ring in η2 mode. Instead of the conventional polymerization strategy, a metal-π interaction is employed to interlink macrocycles. TAM and Ag-TAM showed electrocatalytic capability for the conversion of nitrate to ammonia. Ag-TAM showed an NH3 yield rate 2-fold greater than TAM with a high faradaic efficiency of 94.6% with good durability, proving that interlinking of macrocycles via metal-π interaction improves the catalytic activity. Detailed periodic density functional theory (DFT) calculations unveil novel mechanistic insights, suggesting cooperative catalysis between neighboring Ag sites and contributing to the enhanced efficiency.

Tetranuclear [2 x 2] square-grid-like Ln(III) clusters have been synthesized by reacting LnCl(3)6H(2)O salts with bis[alpha-hydroxy(p-bromophenyl)methyl]phosphinic acid [R2PO2H, where R = CH(OH)PhBr] and pivalic acid. Single-crystal X-ray diffraction studies show the formation of [Me4N](2)[Ln(4)(mu(2)-eta(1):eta(1)-PO2R2)(8)(eta(2)-CO2But)(4)(mu(4)-CO3)] [Ln = Er (1), Dy (2), and Tb (3)]. Direct-current studies reveal significant ferromagnetic interactions between Dy-III in 2 and Tb-III in 3 and an antiferromagnetic interaction between Er-III in 1. Dynamic magnetic susceptibility measurements confirm a single-molecule magnet (SMM) behavior in both 0 and 1200 Oe applied magnetic fields for 2. Complexes 2 and 3 show single molecular toroic (SMT) behavior with a mixed magnetic moment.

A discrete liphophilic organotelluroxane macrocycle has been found to catalyse the hydrogen evolution reaction (HER) by proton reduction efficiently. The macrocycle is synthesized via chloride abstraction from bis(p-methoxyphenyl) tellurium dichloride (p-MeOC6H5)2TeCl2 (1) by silver salts AgMX4 (MX4 = BF4-, and ClO4-) resulting in in situ generated di-cationic tetraorganoditelluroxane units; two such units are held together by two weak anions μ2-MX4, bridging to form 12-membered di-cationic macrocycles [((p-MeO-C6H4)2Te)2(μ-O)(μ2-F2BF2)2]2+ (2) and [((p-MeO-C6H4)2Te)2(μ-O)(μ2-O2ClO2)2]2+ (3) stabilized via Te-(μ2-BF4/ClO4), with secondary interactions. The charge is balanced by the presence of two more anions, one above and another below the plane of the macrocycle. Similar reaction at higher temperatures leads to the formation of telluronium salts R3TeX [X = BF4- (4), ClO4- (5)] as a major product. The BF4- anion containing macrocycle and telluronium salt were monitored using 19F NMR. HRMS confirmed the structural stability of all the compounds in the solution state. The organotelluroxane macrocycle 2 has been found to act as an efficient electrocatalyst for proton reduction in an organic medium in the presence of p-toluene sulfonic acid as a protic source.

This paper investigates the reactivity and optical properties of transition metal-incorporated organoantimony(V) clusters prepared by a solvothermal route. The detailed structural characterization of novel heterometallic M2Sb4 oxo clusters is reported herein. Single crystal X-ray diffraction revealed the formation of hexanuclear organoantimony(V) based oxo clusters [(p-ClC6H4Sb)4V2(O)2(μ3-O)2(μ2-O)2(t-BuPO3)4(μ2-OCH3)4] (1), [M2(p-iPr-C6H4Sb)4(μ3-O)2(μ2-O)2(μ2-OCH3)4(t-BuPO3)4(py)2]·xCH3OH, where M = Mn, x = 2 (2), Co, x = 1 (3), Ni, x = 2 (4) and Cu, x = 2 (5). The magnetic behaviour of the clusters was probed by magnetic susceptibility measurements. Optical absorption studies showed that bandgap reduction can be achieved by incorporating an appropriate transition metal into the homometallic Sb6 oxo cluster.

The reactions of [Zn3Cl2(3,5-Me2PzH)4(t-BuPO3)2] with organostibonic acid in varying reaction conditions have been investigated. Single-crystal X-ray diffraction studies reveal the formation of [Zn2(p-ClC6H4Sb)2(O)2(OCH3)2(t-BuPO3)3(py)2] (1), [Zn2(p-ClC6H4SbV)4(SbIII)2(O)8(t-BuPO3H)4(t-BuPO3)2(py)2Cl2] (2), and [Zn2(RSb)4(O)4(OCH3)4(t-BuPO3)4(py)2], where R = p-ClC6H4 (3) and R = p-iPrC6H4 (4), respectively. Interestingly, in the synthesis of 2, complete dearylation of organoantimony moieties followed by C-F bond formation, a reduction from Sb (V) to Sb (III), and Sb···Cl weak intermolecular interactions have been observed. ESI-MS studies suggested that clusters 1-4 maintained their structural integrity in the solution state also. Solution NMR studies (1H, 31P, and 13C) support well the observed solid-state structures. 1-4 were tested for antibacterial activity using a microdilution assay. 1 and 4 showed the best activity with lower MIC values (0.78-6.25 μg/mL) against all the tested pathogens. The total antioxidant activity of 1-4 was evaluated through the phosphomolybdenum assay, which showed a total antioxidant activity ranging from 28.96 to 86.46 mg AAE/g compound with the ascorbic acid standard.

Four cadmium phosphinate complexes were synthesized based on Bis-[alpha-hydroxy(p-methylphenyl) methyl]phosphinic acid (L) ligand. These complexes [Cd(L)2(H2O)2] (1), [Cd(L)2(py)3].py (2), [Cd(L)2(4,4'-bpy)4]n (3), [Cd(L)4(4,4'-azo-bpy)(H2O)]n (4), were well characterized by single crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction, elemental analysis and TGA. 1 and 2 are zero-dimensional(0D) structures while 3 and 4 are two dimensional net-like(2D), one dimensional chain-like(1D) structures, respectively. N-donor co-ligands(py, 4,4'-bpy, 4,4'-azo-bpy) contribute to the formation of these architec-tures.(c) 2022 Published by Elsevier B.V.

A multicomponent reaction involving Lu halide hydrate with modified schiff base and coligand were carried in presence of base. The ligand and coligand chosen were primarily targeted to cause structural changes in the end product obtained by varying the steric electronic factors of the ligands. A variety of structural forms ranging from dimeric to tetrameric based clusters have been isolated. All structures are elucidated by single crystal X-ray diffraction studies.

The reaction of 4-(azobenzene)phenylstibonic acid with t-butylphosphonic acid led to the isolation of the tetranuclear oxo-hydroxo antimony cluster of formulae [(4-azobenzene-C6H4Sb)4(OH)4(tBuPO3)6] (C1). The reaction of (p-t-butyl phenyl stibonic acid with phenyl phosphonic acid resulted in the isolation of complex with formulae [(p-t-BuC6H4Sb)4(O)2(PhPO3)4(PhPO3H)4] (C2). Based upon the initial results from docking studies, parent stibonic acids, t-butyl-phenylstibonic acid, p-isopropylphenylstibonic acid, 4-azobenzenephenylstibonic acid, and the derived tetranuclear organoantimonate-phosphonate clusters were screened against different cancer cell lines, various Gram-positive and Gram-Negative bacteria and mycobacteria for possible bioactivity profile.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A series of different cores and nuclearity zinc metal clusters 1-5 have been synthesized using Zn(ClO4)(2)center dot 6H(2)O, Schiff-base primary ligands, and dibenzoyl methane (DBM) or monoethanolamine (MEA) as co-ligand in a room-temperature reaction. The structure of the complexes is characterized using single-crystal X-ray diffraction. Among them, (1) [Zn(L1)(DBM)] is mononuclear; (2) [Zn-4(L2)(2)(DBM)(4)], (3) [Zn-4(L2)(4)(H2O)(2)(ClO4)(2)]center dot 2CH(2)Cl(2), and (4) [Zn-4(L3)(2)(DBM)(4)] have a cubane core; and (5) [Zn-4(L4)(4)(MEA)(2)(ClO4)(2)] has a ladderlike core structure. Compounds 1-5 have also been characterized using UV-vis absorption and emission spectroscopies. For an in-depth understanding of the absorption spectra of 1 and 3, density functional theory (DFT) calculations have been performed, which suggest that the transitions correspond to the pi -> pi* intraligand charge transfer (ILCT) transitions.

Isolation and structural characterization of novel organoantimony(V)-based oxo clusters are reported. (RSb)4(OH)4(t-BuPO3)6 and (RSb)2(O)(t-BuPO3H)6 independently in the presence of pyridine under solvothermal conditions afford the hexanuclear organoantimonate clusters [(RSb)6(μ3-O)2(μ2-O)6(t-BuPO3)4], where R = p-i-PrC6H4 (1), p-ClC6H4 (2). Further, reaction of organostibonate phosphonate with Ti(OiPr)4 in the presence of pyridine under solvothermal conditions afforded the mixed-metal titanium stibonate hexanuclear clusters [(RSb)2Ti4(μ3-O)2(μ2-O)2(t-BuPO3)4(μ-OCH3)4(OCH3)4], where R = p-i-PrC6H4 (3), p-ClC6H4 (4). Band gap measurements were performed on 1-4. They reveal a remarkable reduction in the band gap on moving from the heavier main-group-based oxo cages (1 and 2) to the titanium-incorporated oxo cages (3 and 4).

The reaction of organobismuth precursors with trityl-H-phosphinic acid in varying reaction conditions afforded colorless crystals, whose single crystal X-ray characterization revealed the formation of monomer {(Ph3Bi)[(Ph3C)(H)PO2]2}·3/2(CH3CN)2.1/2H2O (1) and butterfly shaped tetranuclear cluster Bi4(μ3-O)2[(Ph3C)(H)(PO2)]8·2CH2Cl2·1/2CH3CN.2H2O (2). The reaction of titanium isopropoxide with two different phosphinic acids trityl-H-phosphinic acid and cycP(O)(OH) led to isolation of cubane type octahedral complex {Ti8(μ2-O)8(μ2-OH)4[(Ph3C)(H)PO2]12}[3C7H8] (3) and hexanuclear complex Ti6(μ2-cycPO2)9(μ2-O)6(μ2-OH)3·4CH3CN·4H2O (4) respectively.

The reaction of DyCl3.6H2O with the mixed ligand system consisting of o-vanillin based Schiff base ligand H2L [2-(2-hydroxy-3-methoxybenzylideneamino) phenol], dibenzoylmethane (Ph2acac) and acetylacetone (Acac) in the presence of triethylamine as the base afforded, di and tetranuclear dysprosium hydroxo clusters having formulae [Dy2(L)2(Ph2acac)2(H2O)2]3 (1) and [Dy4(L)4(acac)2(OH)2(H2O)2(C6H5N)4] (2) respectively. The solid state structures of these products were established by Single Crystal X-ray diffraction technique. Magnetism studies reveal Dy4 exhibits slow magnetic relaxation behavior.

The reactions of organoantimony(V) halides with N,O-donor ligands in presence of a base were investigated. The synthesis and crystal structure of three novel organoantimony(V) compounds \((\hbox {Ph}_{2}\hbox {Sb})_{2}(\hbox {Q})_{2}(\hbox {O})_{2}\) 1, (\(\hbox {Ph}_{3}\hbox {Sb}\))(PM)Cl 2 and (\(\hbox {Ph}_{2}\hbox {Sb}\))(TEA) 3 [where \(\hbox {Q} = \hbox {8-hydroxyquinoline}\), \(\hbox {PM} = \hbox {2-pyridinemethanol}\) and \(\hbox {TEA} = \hbox {triethanolamine}\)] are reported herein. 1 crystallizes as a dimer resulting in the formation of a four-membered \(\hbox {Sb}_{2}\hbox {O}_{2}\) ring while 2 and 3 are monomeric in the solid state. Interestingly, compound 3 crystallizes in orthorhombic chiral space group \(P2_{1}2_{1}2_{1}\) and is a rare example of spontaneous chirality exhibited in organoantimony(V) compounds.