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) …

Ligand Effects on the Structure and Magnetic Properties of Alternating Copper(II) Chains with 2,2′-Bipyrimidine- and Polymethyl-Substituted Pyrazolates as Bridging Ligands

A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1…

Dicopper(II) Anthraquinophanes as Multielectron Reservoirs for Oxidation and Reduction: A Joint Experimental and Theoretical Study

Two new dinuclear copper(II) metallacyclophanes with 1,4-disubstituted 9,10-anthraquinonebis(oxamate) bridging ligands are reported that can reversibly take and release electrons at the redox-active ligand and metal sites, respectively, to give the corresponding mono- and bis(semiquinonate and/or catecholate) Cu(II)2 species and mixed-valent Cu(II)/Cu(III) and high-valent Cu(III)2 ones. Density functional calculations allow us to give further insights on the dual ligand- and metal-based character of the redox processes in this novel family of antiferromagnetically coupled di- copper(II) anthraquinophanes. This unique ability for charge storage could be the basis for the development of new k…

Crystal Structure and Magnetic Properties of an Oxamato‐Bridged Heterobimetallic Tetranuclear [Ni II Cu II ] 2 Complex of the Rack Type

Study of the complex formation between the [Cu(bpca)]+ secondary building unit and the aromatic N donors 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) and 1,3-bis(4-pyridyl)propane (bpp)

Two new complexes of the formula [{Cu(bpca)}2(μ-tppz)](NO3)2·5H2O (1) and [Cu(bpca)(H2O)(ClO4)(μ-bpp)Cu(bpca)(H2O)2]ClO4·H2O (2) [tppz = 2,3,5,6-tetra(2-pyridyl)pyrazine and bpp = 1,3-bis(4-pyridyl)propane] have been prepared by the reaction of the [Cu(bpca)]+ [Hbpca = bis(2-pyridylcarbonyl)imide] building block and the tppz and bpp N donors. An unusual coordination mode of the tppz ligand was observed in 1, which functions as a bis(bidentate) ligand to two copper(II) atoms each coordinated to a nitrogen atom of the pyrazine moiety and a pyridyl nitrogen atom. This compound presents a layered structure of alternating anionic (ca. 1.6 A) and cationic (ca. 10 A) slices, providing the opportun…

Dicopper(II) metallacyclophanes with photoswitchable oligoacene spacers: a joint experimental and computational study on molecular magnetic photoswitches

Dinuclear copper(II) complexes of the metallacyclophane-type, (nBu4N)4[Cu2(2,6-anba)2] (1) and (nBu4N)4[Cu2(1,5-naba)2]·4H2O (2) with photoactive 2,6-anthracene-(2,6-anba) and 1,5-naphthalenebis(oxamate) (1,5-naba) bridging ligands, are reported. They undergo a thermally reversible, solid-state photomagnetic (ON/OFF) switching between the moderately strong antiferromagnetically coupled dicopper(II) species and the corresponding magnetically uncoupled [4+4] photocycloaddition product. Density functional calculations give further insights on the intramolecular (“pseudo-bimolecular”) photocycloaddition reaction of the two facing 2,6-anthracene or 1,5-naphthalene spacers in this novel family of…

Metallosupramolecular approach toward multifunctional magnetic devices for molecular spintronics

Abstract The work presented in this review constitutes a successful extension of our group's research on the chemistry and physics of dinuclear copper(II) metallacyclophanes with aromatic polyoxalamide ligands. The design and synthesis of metallacyclic complexes that contain multiple electro- and photoactive (either metal- or ligand-based) spin carriers and the study of their spectroscopic and magnetic properties as well as their redox and photochemical activity are of large interest in the multidisciplinary field of metallosupramolecular chemistry. In doing this, a ligand design approach has been followed which is based on the copper(II)-mediated self-assembly of bis(oxamato) bridging liga…

Metamagnetic behaviour in a new Cu(ii)Re(iv) chain based on the hexachlororhenate(iv) anion

A new chloro-bridged heterobimetallic Cu(ii)Re(iv) chain of formula {Cu(pyim)(Him)2ReCl6}n·MeCN (·MeCN) has been prepared and magnetostructurally characterised. Compound is the first example of the [Re(IV)Cl6](2-) anion acting as a metalloligand towards a paramagnetic metal ion.

Self-assembly, binding ability and magnetic properties of dicopper(ii) pyrazolenophanes

A novel series of dinuclear copper(II) pyrazolenophanes of the formula [Cu2(μ-4-Mepz)2(μ-ClO4)(ClO4)(bpm)2] (1), [Cu2(μ-pz)2(μ-H2O)(ClO4)(4,7-Me2phen)2]ClO4·H2O·CH3CN (2), [Cu2(μ-pz)2(μ-H2O)(ClO4)3/2(H2O)1/2(phen)2]2[Cu2(μ-pz)2(μ-ClO4)(ClO4)2(phen)2]·8H2O (3), and [Cu2(μ-pz)2(CH3CN)2(3,4,7,8-Me4phen)2](ClO4)2 (4) (Hpz = pyrazole, H-4-Mepz = 4-methylpyrazole, bpm = 2,2'-bipyrimidine, phen = 1,10-phenanthroline, 4,7-Me2phen = 4,7-dimethyl-1,10-phenanthroline, and 3,4,7,8-Me4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been synthesized and magneto-structurally investigated. The crystal structures of 1–4 contain bis(pyrazolate)(perchlorate)- (1 and 3), bis(pyrazolate)(aqua)- (2 and 3), …

Dicopper(II) pyrazolenophanes: Ligand effects on their structures and magnetic properties

Abstract The use of simple pyrazolate anions and related polychelating acyclic or macrocyclic pyrazolate derivatives as bridging ligands, and occasionally additional blocking ligands, has led to the stereospecific Cu II -mediated self-assembly of both homo- and heteroleptic di-μ-pyrazolatodicopper(II) complexes of the metallacyclophane type, so-called dicopper(II) pyrazolenophanes. Besides their unique molecular conformation features and binding abilities toward both neutral molecules and charged anionic species, which have illustrated the putative role of weak intramolecular π–π stacking, hydrogen bonding, and coordinative interactions in the self-assembling process, dicopper(II) pyrazolen…

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