Cerium(III) Phosphinate and Cerium(IV) Phosphostibonate Acting as Catalysts for Mild, Selective Sulfoxidation.

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 [Ce(PhCHPO)]Cl(CHOH)(HO)] () and a fascinating hexanuclear oxo-cluster containing Ce(IV) ions [Ce (-ClCHSb)(μ-O)(μ-O)(-BuPO)(μ-OCH)] (). The molecular architecture of 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.

Silver-π Interaction: A Diverse Approach to Hybrid Material and Its Efficacy in Electrocatalytic Reduction of Nitrate to Ammonia.

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 η mode.

Electrocatalytic hydrogen evolution mediated by an organotelluroxane macrocycle stabilized through secondary interactions.

A discrete liphophilic organotelluroxane macrocycle has been found to catalyse the hydrogen evolution reaction (HER) by proton reduction efficiently. The macrocycle is synthesized chloride abstraction from bis(-methoxyphenyl) tellurium dichloride (-MeOCH)TeCl (1) by silver salts AgMX (MX = BF, and ClO) resulting in generated di-cationic tetraorganoditelluroxane units; two such units are held together by two weak anions μ-MX, bridging to form 12-membered di-cationic macrocycles [((-MeO-CH)Te)(μ-O)(μ-FBF)] (2) and [((-MeO-CH)Te)(μ-O)(μ-OClO)] (3) stabilized Te-(μ-BF/ClO), with secondary interactions. The charge is balanced by the presence of two more anions, one above and another below the plane of the macrocycle.

Tunable bandgaps in self-assembled transition metal-incorporated heterometallic MSb (M = V, Mn, Co, Ni, and Cu) oxo clusters.

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 MSb oxo clusters is reported herein. Single crystal X-ray diffraction revealed the formation of hexanuclear organoantimony(V) based oxo clusters [(-ClCHSb)V(O)(μ-O)(μ-O)(-BuPO)(μ-OCH)] (1), [M(-iPr-CHSb)(μ-O)(μ-O)(μ-OCH)(-BuPO)(py)]·CHOH, where M = Mn, = 2 (2), Co, = 1 (3), Ni, = 2 (4) and Cu, = 2 (5).

Discrete Molecular Aggregates Based on Zn and Sb Ions Displaying Efficient Antibacterial and Antioxidant Properties.

The reactions of [ZnCl(3,5-MePzH)(-BuPO)] with organostibonic acid in varying reaction conditions have been investigated. Single-crystal X-ray diffraction studies reveal the formation of [Zn(-ClCHSb)(O)(OCH)(-BuPO)(py)] (), [Zn(-ClCHSb)(Sb)(O)(-BuPOH)(-BuPO)(py)Cl] (), and [Zn(RSb)(O)(OCH)(-BuPO)(py)], where R = -ClCH () and R = -iPrCH (), respectively. Interestingly, in the synthesis of , 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.

Stibonic acids and related stibonate-phosphonate clusters: Synthesis, characterization and bioactivity evaluation.

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-CHSb)(OH)(BuPO)] (C1). The reaction of (p-t-butyl phenyl stibonic acid with phenyl phosphonic acid resulted in the isolation of complex with formulae [(p-t-BuCHSb)(O)(PhPO)(PhPOH)] (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.

In Situ Assembled Polynuclear Zinc Oxo Clusters Using Modified Schiff Bases as Ligands.

A series of different cores and nuclearity zinc metal clusters - have been synthesized using Zn(ClO)·6HO, 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, () [Zn(L1)(DBM)] is mononuclear; () [Zn(L2)(DBM)], () [Zn(L2)(HO)(ClO)]·2CHCl, and () [Zn(L3)(DBM)] have a cubane core; and () [Zn(L4)(MEA)(ClO)] has a ladderlike core structure.

Retrospective analysis (2009-2017) of factors associated with progression and regression of non-alcoholic fatty liver disease (Hepatic steatosis) in patients with type 2 diabetes seen at a tertiary diabetes centre in Southern India.

Aim: To identify the profiles and factors associated with progression/regression of ultrasound-derived hepatic steatosis with type 2 diabetes mellitus seen at a tertiary diabetes center in southern India.

Methods: Participants were individuals with type 2 diabetes mellitus with at least two consecutive ultrasound measurements available. Hepatic steatosis was assessed using high-resolution B-mode ultrasonography.

Accuracy of 1-Hour Plasma Glucose During the Oral Glucose Tolerance Test in Diagnosis of Type 2 Diabetes in Adults: A Meta-analysis.

Objective: One-hour plasma glucose (1-h PG) during the oral glucose tolerance test (OGTT) is an accurate predictor of type 2 diabetes. We performed a meta-analysis to determine the optimum cutoff of 1-h PG for detection of type 2 diabetes using 2-h PG as the gold standard.

Research Design And Methods: We included 15 studies with 35,551 participants from multiple ethnic groups (53.

Profiles of Intraday Glucose in Type 2 Diabetes and Their Association with Complications: An Analysis of Continuous Glucose Monitoring Data.

To identify profiles of type 2 diabetes from continuous glucose monitoring (CGM) data using ambulatory glucose profile (AGP) indicators and examine the association with prevalent complications. Two weeks of CGM data, collected between 2015 and 2019, from 5901 adult type 2 diabetes patients were retrieved from a clinical database in Chennai, India. Non-negative matrix factorization was used to identify profiles as per AGP indicators.

Novel subgroups of type 2 diabetes and their association with microvascular outcomes in an Asian Indian population: a data-driven cluster analysis: the INSPIRED study.

Introduction: Type 2 diabetes is characterized by considerable heterogeneity in its etiopathogenesis and clinical presentation. We aimed to identify clusters of type 2 diabetes in Asian Indians and to look at the clinical implications and outcomes of this clustering.

Research Design And Methods: From a network of 50 diabetes centers across nine states of India, we selected 19 084 individuals with type 2 diabetes (aged 10-97 years) with diabetes duration of less than 5 years at the time of first clinic visit and performed k-means clustering using the following variables: age at diagnosis, body mass index, waist circumference, glycated hemoglobin, serum triglycerides, serum high-density lipoprotein cholesterol and C peptide (fasting and stimulated).

Bismuth and Titanium Phosphinates: Isolation of Tetra-, Hexa- and Octanuclear Clusters.

The reaction of organobismuth precursors with trityl--phosphinic acid in varying reaction conditions afforded colorless crystals, whose single crystal X-ray characterization revealed the formation of monomer {(PhBi)[(PhC)(H)PO]}·/(CHCN)./HO () and butterfly shaped tetranuclear cluster Bi(μ-O)[(PhC)(H)(PO)]·2CHCl·/CHCN.2HO ().

Effect of coordination geometry on the magnetic properties of a series of Ln and Ln hydroxo clusters.

A series of three isostructural tetranuclear complexes with the general molecular formula [Ln(μ-OH)(L)(μ-piv)(MeOH)] (Ln = Gd 1, Dy 2 and Ho 3; LH = [1,3-bis(o-methoxyphenyl)-propane-1,3-dione]) were isolated and unambiguously characterized by single crystal XRD. Under similar reaction conditions, simply changing the co-ligand from pivalate to 2,6-bis(hydroxymethyl)-p-cresol (LH') led to the isolation of dinuclear Ln(iii) complexes with the general molecular formula [Ln(L)(μ-LH')]·4DMF (Ln = Gd 4, Dy 5 and Ho 6). Direct current magnetic susceptibility data studies on the polycrystalline sample of 1-6 and the results reveal the existence of weak antiferromagnetic exchange interactions between the lanthanide ions in 1 which is evident from the spin Hamiltonian (SH) parameters (J = -0.

Te4Se2O6 macrocycle stabilizing triangular planar and tetrahedral anions.

The anion exchange reactions of Cl-macrocycle 1a [(p-MeO-C6H4)2Te)2(μ-O)(μ-PhSeO2)(μ4-Cl)]2 with AgNO3, AgClO4 and AgBF4 yielded colourless solids whose single crystal X-ray diffraction studies revealed the formation of 12-membered macrocycles [(p-MeO-C6H4)2Te)2(μ-O)(μ-PhSeO2)(μ-X)]2 [X = NO3 (2), ClO4 (3), BF4 (4)]. ESI-MS studies revealed that macrocycles 2–4 retain their integrity in solution. The solution (125)Te NMR spectrum of 4 shows the appearance of a triplet ((1)JTe···F = 568 Hz) that can be assigned to coupling between (125)Te nuclei and two fluorine atoms in BF4(−) ions.

Assembling anionic Sb(V)/(III) containing polyoxostibonates stabilized by triphenyltellurium cations.

Reactions of diphenyltellurium oxide with organostibonic acid and polymeric triphenylantimony oxide have been investigated independently. Single crystal X-ray diffraction studies have revealed the formation of novel and rare mixed valent Sb(v)/(iii) containing polyoxostibonates {(C6H5)3Te}2{Na2(H2O)2(p-Br-C6H4Sb(V))10(Sb(III))4[(C6H5)2Te]4(O)30(OH)4} and {(C6H5)3Te}4{[(C6H5)2Sb(V)]4(Sb(III))4(O)12(OH)4} . Solution (125)Te NMR supports the solid state structures presented.

Hexa- and trinuclear organoantimony oxo clusters stabilized by organosilanols.

Reactions of Ph2SbCl3 with RSi(OH)3 [where R = tert-Bu, cyclo-C6H11] and Ph2Si(OH)2 in toluene in the presence of triethylamine as a base were performed. Single-crystal X-ray structural elucidation of the products revealed the formation of hexanuclear antimony(V) and mixed-valent antimony (III/V) oxo-hydroxo clusters built up of an incomplete cubane subunit. Interestingly, in all the reactions, at least one Sb-C bond cleavage has been observed, leading to the formation of novel cluster assemblies [(Ph2Sb)4(PhSb)2(C4H9SiO3)2(O)6(OH)2] (1), [(Ph2Sb)4(PhSb)2(C6H11SiO3)2(O)6(OH)2] (2), [(Ph2Sb)(PhSb)2(Ph2SiO2)2(O)3(OH)2](-)Et3NH(+) (3), and [(Ph2Sb)4(Sb)2(Ph2SiO2)2(O)6(OH)2] (4), respectively.

New structural form of a tetranuclear lanthanide hydroxo cluster: Dy4 analogue display slow magnetic relaxation.

A series of tetranuclear lanthanide (Ln = Tb, Dy, Ho) hydroxo clusters has been synthesized by reaction of LnCl3·6H2O (Ln = Tb (1), Dy (2), Ho (3)) with o-vanilin based schiff base ligand 2-(2,3 dihydroxpropyl imino methyl) 6-methoxy phenol (H3L) in methanol and in the presence of triethylamine as base. The solid state structures of all the products were established by single crystal X-ray diffraction technique. Magnetism studies reveal that Dy4 analogue exhibits slow magnetic relaxation at low temperatures.

Tetranuclear stiboxanes (RSb)4O6, exhibiting an adamantane-type structure.

Depolymerization reactions of organostibonic acids with protic ligands have been investigated. Reaction of arylstibonic acids with 8-hydroxyquinoline (8-HQ), or {2-[1H-pyrazol-5(3)-yl]naphthalene-1-ol} (H(2)naphpz) in a 1 : 1 stoichiometry in refluxing toluene affords adamantane-like L(4)(RSb)(4)O(6) clusters [(p-XC(6)H(4)Sb)(4)(O)(6)(Q)(4)] (where X = Cl (1), Br (2), QH = 8-hydroxyquinoline), [(p-ClC(6)H(4)Sb)(4)(O)(6)(Hnaphpz)(4)]·H(2)naphpz (3) and [(p-Br-C(6)H(4)Sb)(4)(O)(6)(Hnaphpz)(4)](2)·H(2)naphpz (4). Further a tetrameric organoantimony oxo cluster, L(4)(RSb)(4)O(4) [(p-ClC(6)H(4)Sb)(4)(O)(4)(naphpz)(4)] (5) has also been isolated as a side product in the reaction of arylstibonic acid with naphthylphenolic pyrazole.

3d-4f clusters with large spin ground states and SMM behaviour.

Three new Cu-Ln cage complexes bridged by phosphonates and acetates are reported; one--a Cu(24)Dy(8) cage--is a new single molecule magnet (SMM).

Mixed antimonate-phosphonate ligands as polydentate bridging oxygen donors.

A new class of oxygen donor ligands is described and preliminary results using these ligands are given which show they can be used to make polymetallic cages.