Discrete trinuclear copper(II) compounds as building blocks: the influence of the peripheral substituents on the magnetic coupling in oxamato-bridged complexes.

Two new trinuclear copper(ii) complexes without end-capping ligands, (Bu4N)2[Cu(dmso)2{Cu(dnopba)(dmso)}2] () and (Bu4N)2[Cu(dmso)2{Cu(dcopba)(dmso)}2] () [dnopba = 4,5-dinitro-ortho-phenylenebis(oxamate), dcopba = 4,5-dichloro-ortho-phenylenebis(oxamate), Bu4N(+) = tetra-n-butylammonium and dmso = dimethylsulfoxide], were synthesized and their structures were determined by single crystal X-ray diffraction. The crystal structures of and consist of two outer bis(oxamato)(dmso)cuprate(ii) units which act as bidentate ligands toward a trans-bis(dmso)copper(ii) inner entity leading to centrosymmetric tricopper(ii) complexes with copper-copper separations across the oxamate bridges of 5.1916(3) …

Mononuclear lanthanide(III)-oxamate complexes as new photoluminescent field-induced single-molecule magnets: solid-state photophysical and magnetic properties.

Implementing additional optical (luminescent) properties into the well-known class of single-molecule magnets (SMMs) is considered as a promising route toward obtaining the next generation of optomagnetic materials for quantum information storage and computing. Herein, we report a joint optical and magneto-structural study for the two novel series of lanthanide(iii) complexes of general formula Bu4N[LnIII(HL)4(dmso)]·nH2O where H2L = N-(4-Xphenyl)oxamic acid with X = Cl and n = 2 [Ln = Eu (1_Cl), Gd (2_Cl), Dy (3_Cl), and Tb (4_Cl)] and X = F and n = 3 [Ln = Eu (1_F), Gd (2_F), Dy (3_F), and Tb (4_F)]. All these compounds are mononuclear species with each lanthanide(iii) cation in a low-sym…

Rational design of a new class of heterobimetallic molecule-based magnets: Synthesis, crystal structures, and magnetic properties of oxamato-bridged (M′=LiI and MnII; M=NiII and CoII) open-frameworks with a three-dimensional honeycomb architecture

Abstract Two new series of oxamato-bridged heterobimetallic coordination networks of general formula Li5[Li3M2(mpba)3(H2O)6] · 31H2O [M = NiII (1a) and CoII (1b)] and Li2[Mn3M2(mpba)3(H2O)6] · 22H2O [M = NiII (2a) and CoII (2b)] have been prepared from the metal-mediated self-assembly of the hexakis(bidentate), triple-stranded dinickel(II) and dicobalt(II) complexes [M2(mpba)3]8− [mpba = meta-phenylenebis(oxamato)] with either monovalent lithium(I) or divalent manganese(II) ions respectively, in water. X-ray structural analyses of 1a and 1b show an anionic three-dimensional network formed by an infinite parallel array of oxamato-bridged Li 3 I M 2 II (M = Ni and Co) hexagonal layers, which …

Synthesis, crystal structure and magnetic properties of [Co(bpcam)2]ClO4·dmso·H2O, [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O and [Ni(bpcam)2]·H2O [Hbpcam = bis(2-pyrimidylcarbonyl)amide]

The preparation, spectroscopic characterization, structural study and magnetic investigation of three new complexes of formula [Co(bpcam)2]ClO4·dmso·H2O (1), [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O (2) and [Ni(bpcam)2]·H2O (3) [Hbpcam = bis(2-pyrimidylcarbonyl)amide] are reported. Each bpcam group in 1–3 acts as a tridentate ligand being coordinated to the cobalt(III) (1 and 2)/nickel(II) (3) ions through three nitrogen atoms in a mer-arrangement. Six-coordinate cobalt(III) and nickel(II) occur in 1 and 3 respectively, whereas six-coordinate cobalt(III) and four-coordinate cobalt(II) coexist in 2. Cyclic voltammetry of 1 in acetonitrile shows the occurrence of one quasi reversible CoIII ↔ CoII pro…

Polymorphic Derivatives of NiII and CoII Mesocates with 3D Networks and “Brick and Mortar” Structures: Preparation, Structural Characterization, and Cryomagnetic Investigation of New Single-Molecule Magnets

In this work we describe the preparation, spectroscopic, thermal and structural characterization, and cryomagnetic investigation of four new polymorphic derivatives of the [M2(H2mpba)3]2– mesocate ...

Building-up host-guest helicate motifs and chains: a magneto-structural study of new field-induced cobalt-based single-ion magnets.

In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt(II) compounds of formulas [Co(H2O)6][Co2(H2mpba)3]·2H2O·0.5dmso (1), [Co(H2O)6][Co2(H2mpba)3]·3H2O·0.5dpss (2), [Co2(H2mpba)2(H2O)4]n·4nH2O (3), and [Co2(H2mpba)2(CH3OH)2(H2O)2]n·0.5nH2O·2ndpss (4) [dpss = 2,2′-dipyridyldisulfide and H4mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl2] (Pre-I) as the source of cobalt(II). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt(II) : H2mpba2− molar ratio used 1 : …

A CuIICoII Metallacyclophane-Based Metamagnet with a Corrugated Brick-Wall Sheet Architecture

Solvent effects on the dimensionality of oxamato-bridged manganese(II) compounds

Two new oxamate-containing manganese(II) complexes, [{Mn(H2edpba)(H2O)2}2]n (1) and [Mn(H2edpba)(dmso)2]∙dmso∙CH3COCH3∙H2O (2) (H4edpba = N,N′-ethylenediphenylenebis(oxamic acid) and dmso = dimethylsulfoxide), have been synthesized and the structures of 1 and 2 were characterized by single crystal X-ray diffraction. The structure of 1 consists of neutral honeycomb networks in which each manganese(II) is six-coordinate by one H2edpba2− ligand and two carboxylate–oxygens from two other H2edpba2− ligands building the equatorial plane. Each manganese is connected to its nearest neighbor through two carboxylate(monoprotonated oxamate) bridges in an anti-syn conformation. A dmso solution of singl…

Unexpected formation of a dodecanuclear {CoII6CuII6} nanowheel under ambient conditions: magneto-structural correlations.

We report the unique heterobimetallic dodecanuclear oxamate-based {CoII6CuII6} nanowheel obtained using an environmentally friendly synthetic protocol. The effective Hamiltonian methodology employed herein allows the rationalisation of magnetic isotropic or anisotropic metal clusters, being a significant advance for future studies of exciting properties only observed at low and ultralow temperatures.

A pH-triggered bistable copper(II) metallacycle as a reversible emulsion switch for biphasic processes.

A unique bistable copper-metallacyclic complex is used as an elegant molecular switch for the reversible formation of emulsions by simple pH variation. This switch may have several exciting applications in biphasic processes such as catalysis and separation science technologies.

A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture

CCDC 1830425: Experimental Crystal Structure Determination

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CCDC 1898457: Experimental Crystal Structure Determination

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CCDC 1958348: Experimental Crystal Structure Determination

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CCDC 1898455: Experimental Crystal Structure Determination

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CCDC 1830430: Experimental Crystal Structure Determination

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CCDC 951253: Experimental Crystal Structure Determination

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CCDC 1449346: Experimental Crystal Structure Determination

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CCDC 1883575: Experimental Crystal Structure Determination

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CCDC 2002706: Experimental Crystal Structure Determination

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CCDC 1449347: Experimental Crystal Structure Determination

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CCDC 1958349: Experimental Crystal Structure Determination

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CCDC 951150: Experimental Crystal Structure Determination

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CCDC 1883574: Experimental Crystal Structure Determination

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CCDC 1883576: Experimental Crystal Structure Determination

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CCDC 927505: Experimental Crystal Structure Determination

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CCDC 1898454: Experimental Crystal Structure Determination

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CCDC 1993352: Experimental Crystal Structure Determination

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CCDC 927507: Experimental Crystal Structure Determination

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CCDC 1830421: Experimental Crystal Structure Determination

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CCDC 1031229: Experimental Crystal Structure Determination

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CCDC 927506: Experimental Crystal Structure Determination

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CCDC 1958345: Experimental Crystal Structure Determination

Related Article: Raphael C. A. Vaz, Isabela O. Esteves, Willian X. C. Oliveira, João Honorato, Felipe T. Martins, Lippy F. Marques, Guilherme L. dos Santos, Ricardo O. Freire, Larissa T. Jesus, Emerson F. Pedroso, Wallace C. Nunes, Miguel Julve, Cynthia L. M. Pereira|2020|Dalton Trans.|49|16106|doi:10.1039/D0DT02497J

CCDC 1898456: Experimental Crystal Structure Determination

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CCDC 1883577: Experimental Crystal Structure Determination

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CCDC 1480787: Experimental Crystal Structure Determination

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CCDC 1958347: Experimental Crystal Structure Determination

Related Article: Raphael C. A. Vaz, Isabela O. Esteves, Willian X. C. Oliveira, João Honorato, Felipe T. Martins, Lippy F. Marques, Guilherme L. dos Santos, Ricardo O. Freire, Larissa T. Jesus, Emerson F. Pedroso, Wallace C. Nunes, Miguel Julve, Cynthia L. M. Pereira|2020|Dalton Trans.|49|16106|doi:10.1039/D0DT02497J