Design, Synthesis, Magnetic Properties, and Hydrogen Evolution Reaction of a Butterfly-like Heterometallic Trinuclear [CuMn] Cluster.

A novel heterometallic trinuclear cluster [CuMn(cpdp)(NO)(Cl)] () has been designed and synthesized by employing a molecular library approach that uses CuCl·2HO and Mn(NO)·4HO as inorganic metal salts and Hcpdp as a multifunctional organic scaffold (Hcpdp = ,'-bis[2-carboxybenzomethyl]-,'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol). This heterometallic cluster has emerged as an unusual ferromagnetic material and promising electrocatalyst for hydrogen evolution reaction (HER) in the domain of inorganic and materials chemistry. Crystal structure analysis establishes the structural arrangement of , revealing a butterfly-like topology with an unusual seven-coordinated Mn(II) center.

Effect of diamagnetic Zn(II) ions on the SMM properties of a series of trinuclear ZnDy and tetranuclear ZnDy (Ln = Dy, Tb, Gd) complexes: combined experimental and theoretical studies.

To study the effect of diamagnetic ions on magnetic interactions, utilizing a compartmental ligand ()-2-(hydroxymethyl)-4-methyl-6-((quinolin-8-ylimino)methyl)phenol (LH), two different series of Zn-Ln complexes, namely the trinuclear series of [DyZn(L)(μ-OAc)(CHOH)]·NO·MeOH (1), [TbZn(L)(μ-OAc)(CHOH)]·NO·5MeOH·HO (2), and [GdZn(L)(μ-OAc)(CHOH)]·NO·MeOH·CHCl (3) and the tetranuclear series of [DyZn(LH)(NO)(μOAc)]·NO·MeOH·HO (4), [TbZn(LH)(NO)(μ-OAc)]·NO·MeOH·2HO (5), and [GdZn(LH)(NO)(μ-OAc)]·NO·MeOH·2HO (6), were synthesized. Trinuclear Zn-Ln complexes 1-3 consist of one Ln ion sandwiched between two peripheral Zn ions forming a bent type Zn-Dy-Zn array with an angle of 110.64°.

Hexa- and octanuclear copper(II) complexes with a tetraeicosaaza amine macrocycle.

One hexa- and two octanuclear Cu(II) complexes were synthesised from different metal salts and a very large (8 + 8) tetraeicosaaza macrocycle. These nitrate, chloride and sulphate coordination compounds were characterised by taking elemental analysis, spectroscopy, crystallography and magnetic susceptibility measurements. Their crystal structures revealed different interesting coordination modes of Cu(II) cations and nuclearity in these centrosymmetric complexes.

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands.

Mono-substituted cage-like silsesquioxanes of the T-type can play the role of potential ligands in the coordination chemistry. In this paper, we report on imine derivatives as ligands for samarium, terbium, and erbium cations and discuss their efficient synthesis, crystal structures, and magnetic and optical properties. X-ray analysis of the lanthanide coordination entities [MCl(POSS)]·2THF [M = Er (), Tb (), Sm ()] showed that all three compounds crystallize in the same space group with similar lattice parameters.

Multinuclear Ni(II) and Cu(II) complexes of a 6 + 6 macrocyclic amine derived from -1,2-diaminocyclopentane and 2,6-diformylpyridine.

Four hexanuclear chloride and sulphate Ni(II) and Cu(II) complexes 1, 2, 4 and 5 and one tetranuclear nitrate Cu(II) complex 3 have been synthesised from appropriate metal salts and 6 + 6 octadecaaza macrocyclic ligands. All obtained coordination compounds have been characterised by elemental analysis, spectroscopic methods (ESI MS, NMR and EPR), magnetic susceptibility measurements and X-ray crystallography. Their X-ray crystal structures reveal different coordination modes of metal cations involved in the obtained centro-symmetrical coordination compounds.

Synthesis, Crystal Structures, and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities.

In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li(OSiPh)(THF)] (), and sodium [Na(OSiPh)] () species, which were later used in obtaining novel gadolinium [Gd(OSiPh)(THF)]·THF (), and erbium [Er(OSiPh)(THF)]·THF () configuration, it can result in res were determined for all - compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for and lanthanide compounds.

A 3D MOF based on Adamantoid Tetracopper(II) and Aminophosphine Oxide Cages: Structural Features and Magnetic and Catalytic Properties.

This work describes an unexpected generation of a new 3D metal-organic framework (MOF), [Cu(μ-Cl)(μ-O)Cu(OH)(μ-PTA═O)]·2Cl-EtOH·2.5HO, from copper(II) chloride and 1,3,5-triaza-7-phosphaadamantane 7-oxide (PTA═O). The obtained product is composed of diamandoid tetracopper(II) [Cu(μ-Cl)(μ-O)] cages and monocopper(II) [Cu(OH)] units that are assembled, via the diamandoid μ-PTA═O linkers, into an intricate 3D net with an topology.

Synthesis, Structural, and Cytotoxic Properties of New Water-Soluble Copper(II) Complexes based on 2,9-Dimethyl-1,10-Phenanthroline and Their One Derivative Containing 1,3,5-Triaza-7-Phosphaadamantane-7-Oxide.

A series of water-soluble copper(II) complexes based on 2,9-dimethyl-1,10-phenanthroline (dmphen) and mixed-ligands, containing PTA=O (1,3,5-triaza-7-phosphaadamantane-7-oxide) have been synthesized and fully characterized. Two types of complexes have been obtained, monocationic [Cu(NO)(O-PTA=O)(dmphen)][PF] (), [Cu(Cl)(dmphen)][PF] (), and neutral [Cu(NO)(dmphen)] (). The solid-state structures of all complexes have been determined by single-crystal X-ray diffraction.

Copper(II) Coordination Polymers Self-Assembled from Aminoalcohols and Pyromellitic Acid: Highly Active Precatalysts for the Mild Water-Promoted Oxidation of Alkanes.

Three novel water-soluble 2D copper(II) coordination polymers-[{Cu2(μ2-dmea)2(H2O)}2(μ4-pma)]n·4nH2O (1), [{Cu2(μ2-Hedea)2}2(μ4-pma)]n·4nH2O (2), and [{Cu(bea)(Hbea)}4(μ4-pma)]n·2nH2O (3)-were generated by an aqueous medium self-assembly method from copper(II) nitrate, pyromellitic acid (H4pma), and different aminoalcohols [N,N-dimethylethanolamine (Hdmea), N-ethyldiethanolamine (H2edea), and N-benzylethanolamine (Hbea)]. Compounds 2 and 3 represent the first coordination polymers derived from H2edea and Hbea. All the products were characterized by infrared (IR), electron paramagnetic resonance (EPR), and ultraviolet-visible light (UV-vis) spectroscopy, electrospray ionization-mass spectroscopy (ESI-MS(±)), thermogravimetric and elemental analysis, and single-crystal X-ray diffraction (XRD), which revealed that their two-dimensional (2D) metal-organic networks are composed of distinct dicopper(II) or monocopper(II) aminoalcoholate units and μ4-pyromellitate spacers.

New Tetracopper(II) Cubane Cores Driven by a Diamino Alcohol: Self-assembly Synthesis, Structural and Topological Features, and Magnetic and Catalytic Oxidation Properties.

Two new coordination compounds with tetracopper(II) cores, namely, a 1D coordination polymer, [Cu4(μ4-H2edte)(μ5-H2edte)(sal)2]n·10nH2O (1), and a discrete 0D tetramer, [Cu4(μ4-Hedte)2(Hpmal)2(H2O)]·7.5H2O (2), were easily self-assembled from aqueous solutions of copper(II) nitrate, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (H4edte), salicylic acid (H2sal), or phenylmalonic acid (H2pma). The obtained compounds were characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, and single-crystal X-ray diffraction.

Trinuclear Cu(II) complexes of a chiral N6O3 amine.

Enantiopure trinuclear Cu(II) complexes 3 and 4 of macrocyclic amine 1 derived from the 3 + 3 condensation of 2,6-diformyl-4-methylphenol and (1S,2S)-1,2-diaminocyclohexane have been synthesized and characterized by ESI MS and NMR spectroscopy. The X-ray crystal structures of both complexes have been determined. The structure of the chloride derivative 3 indicates unusual combination of distorted tetragonal bipyramidal, square pyramidal and square geometries of the three Cu(II) ions bound by macrocycle 1.

Trinuclear thiocyanate-bridged compounds of the type [ML]2[Mn(NCS)4](ClO4)2 (where M = Cu(II), Ni(II); L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene).

The complexes of general formula [ML]2[Mn(NCS)4](ClO4)2 (where M = Cu(II), Ni(II); L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) were obtained and the crystal structures of both heteronuclear compounds were determined at 173 K. Complex [CuL]2[Mn(NCS)4](ClO4)2 (1) crystallizes in a monoclinic space group, C2/c, with a = 41.297(9) A, b = 7.