Structurally characterized trinuclear nickel(II) and copper(II) Salamo-type complexes: syntheses,Hirshfeld analyses and fluorescent properties

Transition Metal Chemistry - Two trinuclear Ni(II) and Cu(II) coordination compounds [{Ni(L1)(C2H5OH)}2(μ-OAc)2Ni]·2C2H5OH (1) and [{Cu(L2)(CH3OH)}2(μ-OAc)2Cu]·2CH3OH (2)...     

Two Supramolecular Nickel(II) Complexes: Syntheses,Crystal Structures and Solvent Effects

Two nickel(II) complexes, namely {[NiL(MeOH)(μ‐OAc)]₂Ni} · 2CH₂Cl₂ · 2MeOH ( 1 ) and {[NiL(EtOH)(μ‐OAc)]₂Ni} · 2EtOH ( 2 ) {H₂L = 5, 5′‐dimethoxy‐2, 2′‐[(ethylene)dioxybis(nitrilomethylidyne)]diphenol}, were synthesized and structurally characterized. Two trinuclear Ni^II complexes are both hexacoordinate around the central Ni^II atoms, showing octahedral coordination arrangements, and each complex comprises three divalent Ni^II atoms, two deprotonated L^2– ligands, in which four μ‐phenoxo oxygen atoms forming two [NiL(X)] (X = MeOH or EtOH) units, and coordinated and non‐coordinated solvent molecules. Complex 1 exhibits a 2D supramolecular network through intermolecular O–H ··· O, C–H ··· O and C–H ··· π interactions, whereas complex 2 forms an infinite 1D chain by intermolecular C–H ··· O hydrogen bonding interactions.     

Family of carboxylate- and nitrate-diphenoxo triply bridged dinuclear Ni(II)Ln(III) complexes (Ln = Eu, Gd, Tb, Ho, Er, Y): synthesis, experimental and theoretical magneto-structural studies, and single-molecule magnet behavior

Seven acetate-diphenoxo triply bridged M(II)-Ln(III) complexes (M(II) = Ni(II) and Ln(III) = Gd, Tb, Ho, Er, and Y; M(II) = Zn(II) and Ln(III) = Ho(III) and Er(III)) of formula [M(μ-L)(μ-OAc)Ln(NO(3))(2)], one nitrate-diphenoxo triply bridged Ni(II)-Tb(III) complex, [Ni(μ-L)(μ-NO(3))Tb(NO(3))(2)]·2CH(3)OH, and two diphenoxo doubly bridged Ni(II)-Ln(III) complexes (Ln(III) = Eu, Gd) of formula [Ni(H(2)O)(μ-L)Ln(NO(3))(3)]·2CH(3)OH have been prepared in one pot reaction from the compartmental ligand N,N',N"-trimethyl-N,N"-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H(2)L). Moreover, Ni(II)-Ln(III) complexes bearing benzoate or 9-anthracenecarboxylate bridging groups of formula [Ni(μ-L)(μ-BzO)Dy(NO(3))(2)] and [Ni(μ-L)(μ-9-An)Dy(9-An)(NO(3))(2)]·3CH(3)CN have also been successfully synthesized. In acetate-diphenoxo triply bridged complexes, the acetate bridging group forces the structure to be folded with an average hinge angle in the M(μ-O(2))Ln bridging fragment of ~22°, whereas nitrate-diphenoxo doubly bridged complexes and diphenoxo-doubly bridged complexes exhibit more planar structures with hinge angles of ~13° and ~2°, respectively. All Ni(II)-Ln(III) complexes exhibit ferromagnetic interactions between Ni(II) and Ln(III) ions and, in the case of the Gd(III) complexes, the J(NiGd) coupling increases weakly but significantly with the planarity of the M-(O)(2)-Gd bridging fragment and with the increase of the Ni-O-Gd angle. Density functional theory (DFT) theoretical calculations on the Ni(II)Gd(III) complexes and model compounds support these magneto-structural correlations as well as the experimental J(NiGd) values, which were found to be ~1.38 and ~2.1 cm(-1) for the folded [Ni(μ-L)(μ-OAc)Gd(NO(3))(2)] and planar [Ni(H(2)O)(μ-L)Gd(NO(3))(3)]·2CH(3)OH complexes, respectively. The Ni(II)Dy(III) complexes exhibit slow relaxation of the magnetization with Δ/k(B) energy barriers under 1000 Oe applied magnetic fields of 9.2 and 10.1 K for [Ni(μ-L)(μ-BzO)Dy(NO(3))(2)] and [Ni(μ-L)(μ-9-An)Dy(9-An)(NO(3))(2)]·3CH(3)CN, respectively.     

A tetradentate bisoxime and its supramolecular nickel(II) cluster: synthesis,crystal structure,and spectral properties

Salen-type bisoxime 5,5′-dimethoxy-2,2′-[(ethylenedioxy)bis(nitrilomethylidyne)]diphenol (H₂L) and its trinuclear Ni(II) cluster {[(NiL)(n-BuOH)]₂(μ-OAc)₂Ni}?·?n-BuOH have been synthesized and structurally characterized. The structure of H₂L adopts an L-shape conformation where the two salicylaldoxime moieties are well separated. In the trinuclear Ni(II) cluster, two acetates coordinate to three Ni(II)'s through Ni–O–C–O–Ni bridges, four μ-phenoxos from two [NiL(n-BuOH)] units also coordinate to Ni(II), and two n-butanols coordinate to two terminal Ni(II)'s forming a distorted octahedral geometry. The Ni–O–C–O–Ni and μ-phenoxo bridges play important roles in assembling Ni(II) and the ligands. H₂L forms a rectangle-like large cave structure through O–H?···?N, C–H?···?O, and C–H?···?π hydrogen-bond interactions, whereas its trinuclear Ni(II) cluster exhibits a 3-D supramolecular network structure through intermolecular O–H?···?O, C–H?···?O, and C–H?···?π hydrogen-bond interactions.     

Insight into Crystal Structures,Hirshfeld Surfaces and Fluorescent Properties of Multinuclear Co(II) and Ni(II) Salamo-Based Complexes Involving Lone Pair π-Interactions

Russian Journal of General Chemistry - Two multi-nuclear Co(II) and Ni(II) complexes, [{Co3(L)2(EtOH)2(μ-OAc)2}2]·2CH3CH2OH· CH2Cl2·CHCl3·CH3CN (1) and...     

Synthesis,crystal structures and magnetic properties of three porous coordination polymers based on a semirigid tripodal carboxylate ligand

Transition Metal Chemistry - Three new coordination polymers, namely, {[Cu2(bcpmba)(μ4-OH)]·2H2O}n (1), [Mn(Hbcpmba)]n (2), and [Co2(bcpmba)(μ3-OH)·H2O]n (3)...     

Insight into new mono- and tri-nuclear nickel(II)-based complexes supported by structural variation of salamo-like ligands

Transition Metal Chemistry - New mono- and tri-nuclear Ni(II)-based complexes, [Ni(L1)2] (1) and [{Ni(L2)(DMF)(μ-OAc)}2Ni]·2EtOH·2CH2Cl2 (2), supported by half-salamo- and...     

Supramolecular cobalt(II) complexes: syntheses,crystal structures and solvent effects

Two Co^II complexes, namely {[CoL(MeOH)(μ-OAc)]₂Co}·2MeCN·2MeOH (1) and {[CoL(EtOH)(μ-OAc)]₂Co}·3EtOH (2) (H₂L=3,3′-dimethoxy-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol), have been synthesized and characterized by X-ray crystallography. Both complexes contain octahedral coordination geometries, comprising three Co^II atoms, two deprotonated bisoxime L²⁻ units in which four μ-phenoxo oxygen atoms form two [CoL(X)] (X = MeOH or EtOH) units, two acetate ligands coordinated to three Co^II centers through Co–O–C–O–Co bridges, and coordinated and non-coordinated solvent. Both complexes exhibit 2D supramolecular networks through different intermolecular hydrogen-bonding interactions.     

Synthesis and crystal structure of two coordination polymers based on N,N′-bis(3-pyridylmethyl)pyromellitic diimide and fluorescence thiocyanate sensing

Transition Metal Chemistry - Two N,N′-bis(3-pyridylmethyl)pyromellitic diimide (3-pmpmd) coordination polymers, namely{[Hg(3-pmpmd)I2]·H2O)}n (1), {[Ni2(3-pmpmd)3 (NO3)4]·2CH3OH}n...     

Constructing Phenoxo-Bridged Heterobimetallic [Zn(II)2M(II)] (M = Sr and Ba) Salamo-Based Complexes

Russian Journal of General Chemistry - Two new phenoxo-bridged heterobimetallic [Zn(II)2M(II)] (M = Sr and Ba) salamo-based complexes, [{Zn(L)(μ2-OAc)}2Sr]·0.33CH3OH·H2O (1) and...     

Syntheses,structures and magnetic properties of three cobalt(II) coordination polymers based on flexible itaconic acid ligands

Transition Metal Chemistry - Three Co(II) coordination polymers, namely [Co(ia)(bpe)0.5(H2O)]n (1), {[Co(ia)(bib)(H2O)]·H2O}n (2) and {[Co(ia)(btmb)(H2O)]·H2O}n (3)...     

Strategy for the rational design of asymmetric triply bridged dinuclear 3d-4f single-molecule magnets

Three triply bridged M(II)-Dy(III) dinuclear complexes, [Ni(μ-L)(μ-OAc)Dy(NO(3))(2)] 1, [Zn(μ-L)(μ-OAc)Dy(NO(3))(2)] 2, and [Ni(μ-L)(μ-NO(3))Dy(NO(3))(2)]·2CH(3)OH 3 were prepared with a new and flexible compartmental ligand, N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylene triamine (H(2)L), containing N(3)O(2)-inner and O(4)-outer coordination sites. These complexes have diphenoxo/acetate (1 and 2) or diphenoxo/nitrate (3) asymmetric bridging fragments. Compounds 1 and 3 exhibit ferromagnetic interaction between Ni(2+) and Dy(3+) ions and frequency dependence of the out-of-phase (χ″(M)) alternating current (ac) susceptibility signal characteristic of single-molecule-magnet behavior. The energy barriers Δ/k(B) for compound 3 under zero and 1000 Oe applied direct current (dc) magnetic fields were estimated from the Arrhenius plots to be 7.6 and 19.1 K, respectively.     

A heterometallic (Ni(II)-Cu(II)) decanuclear cluster containing two distorted cubane-like pentanuclear cores: synthesis, structure, and magnetic properties

A new heterometallic Ni(II)-Cu(II) decanuclear cluster, {[Ni(4)Cu(6)(μ-OH(2))(2)(dpkO(2))(8)(OAc)(4)(H(2)O)(4)]·2CH(3)OH·17H(2)O} (1), has been synthesized by self-assembly of the constituent metal ions and the precursor di-2-pyridylketone (dpk) of multinucleating ligand dpkO(2)(2-) and is structurally characterized. The cluster 1 is formed by the union of two symmetry-related distorted cubane-like pentanuclear cores. A magnetic study of 1 reveals strong antiferromagnetic interactions operating through the Ni-O-Ni pathway, which is independent of the assumption D = 0 or D ≠ 0. The pentanuclear cores are ferromagnetically coupled, as supported by density functional theory calculations.     

Syntheses,crystal structures,and magnetic properties of five new coordination compounds bearing ferrocenedicarboxylate ligands

Five new coordination compounds, {[Mn(L)(CH₃OH)₂] · CH₃OH · H₂O} _n (1), {[Cd(L)(DMF)₂(H₂O)] · H₂O} _n (2), {[Co(L)(CH₃OH)₄] · CH₃OH}₂ (3), {[Cd(L)(phen)(CH₃OH)] · CH₃OH} _n (4), and {[Mn(L)(phen)(H₂O)] · CH₃OH} _n (5) (L = 5-ferrocene-1,3-benzenedicarboxylic acid, phen = 1,10-phenanthroline) were obtained from different metal salts and L with or without 1,10-phen under mild conditions. Complex 1 is a 1-D ladder-like chain composed of 8-membered rings A and 16-membered rings B, which arrange alternately. Complex 2 is an infinite linear chain, further bridged to form a parallel double chain through different hydrogen-bond interactions. Complex 3 is a discrete dinuclear structure, while 4 is a neutral 1-D infinite zigzag coordination chain. Complex 5 is a 1-D linear chain with phen and ferrocene groups of L as pendants hanging on the different sides of the main chain. Variable temperature magnetic susceptibilities of 1 were measured and weak antiferromagnetic exchange interactions between the neighboring Mn(II) ions were found with J = ?0.95 cm^?1.     

The Length of Substituents on Ligands Regulates the Structural Diversity of Coordination Polymers

Russian Journal of Coordination Chemistry - Three coordination polymers, namely, {[Co(L1)(HBTC)]·0.5L1}n (I), {[Co(L2)(HBTC)]·H2O}n (II), {[Co(L3)(HBTC)]·H2O}n (III), have been...     

Syntheses,structural characterization,and thermal behaviour of metal complexes with 3-aminopyridine as co-ligands

Transition Metal Chemistry - Six mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-{[M(μ2-3-ampy)(H2O)4]SO4·H2O} (M=Ni (1) and Co (2)),...     

Synthesis,Crystal Structure,and Photoluminescent Properties of Two Porous Pillared-layer Metal-organic Frameworks Constructed by Benzene-1,3,5-tricarboxylic Acid and Bisimidazole Ligands

Russian Journal of Coordination Chemistry - Two pillared layer metal organic frameworks, namely {[Co3(Btc)2(Bib)3(H2O)2] · 7H2O}n(I) and {[Cd2(Btc)(Bib)2(Fma)(H2O)] · H2O}n (II), where...     

Solution and solid state characterization of oxo-centered trinuclear iron(III) acetate complexes [Fe3(μ3-O)(μ-OAc)6(L)3]+

[Fe(3)(μ(3)-O)(μ-OAc)(6)(py)(3)][FeBr(4)](2)[py·H], complex (1), (OAc is acetate) was prepared from the reaction of FeBr(3) with pyridine in 1.2 molar aqueous HBr and 2.4 molar aqueous CH(3)COOH. Recrystallization of 1 in acetonitrile produced the [Fe(3)(μ(3)-O)(μ-OAc)(6)(py)(3)][FeBr(4)] complex (2). Both complexes were characterized by IR and (1)H NMR spectroscopies and their structures were studied using the single-crystal diffraction method. There is a lack of thorough characterization of the titled compounds in solution. Paramagnetic (1)H NMR is introduced as a good probe for the characterization of a family of titled compounds in solution when the L ligand coordinated to iron varies as: CH(3)OH, CH(3)CN, DMSO, H(2)O, py and acetone.     

Chiral Ni(II) coordination polymers: structure-driven effects of temperature and polyvinylpyrrolidone

Chiral Ni(II) coordination compounds with structures of [NiL(H(2)O)(3)] (1) and {[NiL(H(2)O)]·0.5H(2)O}(n) (2) (H(2)L = thiazolidine 2,4-dicaboxlic acid) have been successfully synthesized by the reaction of Ni(CH(3)COO)(2)·4H(2)O and H(2)L in aqueous solution at 25 and 80 °C, respectively. From the same procedure with polyvinylpyrrolidone (PVP) as a surfactant, another corresponding micrometer-scale Ni(II) coordination polymer, {[NiL(H(2)O)(2)]·H(2)O}(n) (3), has been obtained at both 25 and 80 °C, which shows a different structure (one-dimensional, 1D) than both 1 (discrete molecule) and 2 (3D). The conversions of structures and conformations are directed by temperature and surfactant (PVP), as confirmed by powder and single-crystal X-ray diffraction. Circular Dichroism (CD) and Second Harmonic Generation (SHG) measurements of the products have been investigated as well, which indicate the potential applications of these products in chiral and nonlinear optical (NLO) areas.     

Structure of a new trinuclear nickel(II) complex with a salen-type bisoxime ligand

A new trinuclear Ni(II) complex {[NiL(DMF)]₂(OAc)₂Ni}·2DMF (H₂L = 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol) is synthesized and characterized by elemental analyses, IR spectra, UV-Vis spectra and X-ray crystallography. The results show that the Ni(II) complex consists of three Ni(II) ions, two tetradentate (μ-L)^2? units, two coordinated μ-acetate ions, two coordinated DMF molecules, and two crystallization DMF molecules. All hexacoordinated Ni(II) ions of the complex have a slightly distorted octahedral geometry. The crystal packing of the Ni(II) complex reveals a notable feature of this structure: the formation of an infinite supramolecular 2D layered structure by virtue of intermolecular C-H…O hydrogen bonding.