Search Results (9)

The reaction of CuCl₂∙2H₂O, (E)-2-hydroxy-1,2-di(pyridin-2-yl)ethanone oxime (α-pyroxH₂) and Et₃N in refluxing MeOH gave complex [Cu₁₂Cl₁₂(mpydol)₄(pydox)₂(MeOH)₄] (1), where mpydol²⁻ is the dianion of 1,2-dimethoxy-1,2-di(pyridin-2-yl)ethane-1,2-diol and pydox²⁻ is the dianion of (E,E)-1,2-di(pyridin-2-yl)ethanedione dioxime. “Blind” experiments have proven that the transformation of α-pyroxH₂ is copper(II)-assisted. By changing the solvent from MeOH to MeCN, the polymeric compound {[Cu₄Cl₄(pic)₄]}_n (2) was isolated; pic⁻ is the pyridine-2-carboxylato(-1) ligand. The observed α-pyroxH₂ → pic⁻ transformation is also copper(II)-assisted. The topology of the metal ions in 1 can be described as consisting of four consecutive isosceles triangles in a zigzag configuration. Complex 2 is a 2D coordination polymer consisting of Cu^II₄ squares. Complete mechanistic views for the α-pyroxH₂ → mpydol²⁻, pydox²⁻ and pic⁻ transformations are critically discussed. In 1, the six Cu^II ions of the “central” triangles seem to be strongly antiferromagnetically coupled, thus cancelling out their spins ($S_{{\mathrm{Cu}}_6}$ = 0). The two local spins of S = 1/2 for each of the antiferromagnetically coupled “terminal” Cu^II₃ triangles result in an overall S = 1 ground state spin value for 1. In 2, the four Cu^II ions within each tetrameric unit are practically isolated and ferromagnetic interactions occur between these units through Cu^II–(μ-Cl)–Cu^II bridges. Full article

The reaction in reagent grade acetone of copper(II) nitrate hexahydrate, 2,2′-bipyrimidine (bpm) and potassium iodide in a 1:2:2 molar ratio afforded three different products: an unreduced Cu(II) species, a fully reduced Cu(I) species and a mixed-valent Cu(II)/Cu(I) species. Of these, only the unreduced Cu(II) complex of formula [Cu^II(bpm)₃](I₃)(I) (1) could be structurally characterized, the other two products being initially only isolated as amorphous powders. X-ray quality, beautifully shaped, quasi-black prismatic crystals of compound 2, namely {[Cu^I(I₃)Cu^II(I)(bpm)₂](I₃)}_n, and brick-reddish parallelepipeds of compound 3, namely {[Cu^I₂ (μ-I)₂(bpm)]}_n, were successively obtained through the slow diffusion in H-shaped tubes of aqueous solutions of the three reagents, after extensive optimization of the crystallization conditions. Compound 1 consists of a rare tris(2,2′-bipyrimidine)copper(II) monomeric dication, charge balanced by both iodide and triiodide anions. Compound 3, whose structure as well as optical and photocatalytic properties were recently disclosed, consists of a regular alternating μ-bpm/di-μ-iodide copper(I) chain. Finally, compound 2 consists of a rare, regular alternating mixed-valent Cu(II)-Cu(I) μ-bpm copper chain, showing unusual similarities in the metal coordination environment. The magnetic properties of compound 2 remarkably reveal a very weak antiferromagnetic coupling between the paramagnetic Cu(II) ions which are well separated both intra- and inter-chain. Full article

Four one-dimensional complexes, denoted as [NiL₁][Ni(CN)₄] (1), [CuL₁][Ni(CN)₄] (2), [NiL₂][Ni(CN)₄]·2H₂O (3), and [CuL₂][Ni(CN)₄]·2H₂O (4) (L₁ = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane; L₂ = 1,8-dipropyl-1,3,6,8,10,13-hexaazacyclotetradecane) were synthesized by reacting nickel/copper macrocyclic complexes with K₂[Ni(CN)₄]. Subsequently, the synthesized complexes were characterized using elemental analysis, infrared spectroscopy analysis, thermogravimetric analysis, and X-ray powder diffraction. Single-crystal structure analysis revealed that the Ni(II)/Cu(II) atoms were coordinated by two nitrogen atoms from [Ni(CN)₄]²⁻ with four nitrogen atoms from a macrocyclic ligand, forming a six-coordinated octahedral coordination geometry. Nickel/copper macrocyclic complexes were bridged by [Ni(CN)₄]²⁻ to construct one-dimensional chain structures in 1–4. The characterization results showed that the four complexes obeyed the Curie–Weiss law with a weak antiferromagnetic exchange coupling. Full article

Three new tripod tetradentate phenolate-amines (H₂L¹, H₂L⁴ and H₂L⁹), together with seven more already related published ligands, were synthesized, and characterized. With these ligands, two new dinuclear doubly-bridged-phenoxido copper(II) complexes (3, 4), and six more complexes (1, 2, 5–8), a new trinuclear complex (9) with an alternative doubly-bridged-phenoxido and –methoxido, as well as the 1D polymer (10) were synthesized, and their molecular structures were characterized by spectroscopic methods and X-ray single crystal crystallography. The Cu(II) centers in these complexes exhibit distorted square-pyramidal arrangement in 1–4, mixed square pyramidal and square planar in 5, 6, and 9, and distorted octahedral (5+1) arrangements in 7 and 8. The temperature dependence magnetic susceptibility study over the temperature range 2–300 K revealed moderate–relatively strong antiferromagnetic coupling (AF) (|J| = 289–145 cm⁻¹) in complexes 1–6, weak-moderate AF (|J| = 59 cm⁻¹) in the trinuclear complex 9, but weak AF interactions (|J| = 3.6 & 4.6 cm⁻¹) were obtained in 7 and 8. No correlation was found between the exchange coupling J and the geometrical structural parameters of the four-membered Cu₂O₂ rings. Full article

Ferromagnetic coupling exists in an uneven chain-like copper(II) complex with both end-on azido and syn-syn carboxylato bridges, (Cu₃(L)₂(N₃)₄(H₂O)₃)_n (1, HL = 6-hydroxynicotinic acid). It is the first example of one-dimensional (1D) chain-like copper(II) coordination polymer showing both metamagnetic behavior and long-range magnetic ordering (T_c = 6.7 K), thanks to the interchain hydrogen bonds, which make a three-dimensional (3D) supramolecular array of the entire molecular structure and mediate the interchain antiferromagnetic interaction. Full article

Two novel copper(II) complexes of formulas {[Cu(4-Hmpz)₄][Cu(4-Hmpz)₂(µ₃-ox-κ²O¹,O²:κO^2′:κO^1′)(ClO₄)₂]}_n (1) and {[Cu(3,4,5-Htmpz)₄]₂[Cu(3,4,5-Htmpz)₂(µ₃-ox-κ²O¹,O²:κO^2′:κO^1′)(H₂O)(ClO₄)]₂[Cu₂(3,4,5-Htmpz)₄(µ-ox-κ²O¹,O²:κ²O^2′,O^1′)]}(ClO₄)₄·6H₂O (2) have been obtained by using 4-methyl-1H-pyrazole (4-Hmpz) and 3,4,5-trimethyl-1H-pyrazole (3,4,5-Htmpz) as terminal ligands and oxalate (ox) as the polyatomic inverse coordination center. The crystal structure of 1 consists of perchlorate counteranions and cationic copper(II) chains with alternating bis(pyrazole)(µ₃-κ²O¹,O²:κO^2′:κO^1′-oxalato)copper(II) and tetrakis(pyrazole)copper(II) fragments. The crystal structure of 2 is made up of perchlorate counteranions and cationic centrosymmetric hexanuclear complexes where an inner tetrakis(pyrazole)(µ-κ²O¹,O²:κ²O^2′,O^1′-oxalato)dicopper(II) entity and two outer mononuclear tetrakis(pyrazole)copper(II) units are linked through two mononuclear aquabis(pyrazole)(µ₃-κ²O¹,O²:κO^2′:κO^1′-oxalato)copper(II) units. The magnetic properties of 1 and 2 were investigated in the temperature range 2.0–300 K. Very weak intrachain antiferromagnetic interactions between the copper(II) ions through the µ₃-ox-κ²O¹,O²:κO^2′:κO^1′ center occur in 1 [J = −0.42(1) cm⁻¹, the spin Hamiltonian being defined as H = −J∑S_1,i · S_2,i+1], whereas very weak intramolecular ferromagnetic [J = +0.28(2) cm⁻¹] and strong antiferromagnetic [J’ = −348(2) cm⁻¹] couplings coexist in 2 which are mediated by the µ₃-ox-κ²O¹,O²:κO^2′:κO^1′ and µ-ox-κ²O¹,O²:κ²O^2′,O^1′ centers, respectively. The variation in the nature and magnitude of the magnetic coupling for this pair of oxalato-centered inverse copper(II) complexes is discussed in the light of their different structural features, and a comparison with related oxalato-centered inverse copper(II)-pyrazole systems from the literature is carried out. Full article

Heterospin systems have a great advantage in frontier orbital engineering since they utilize a wide diversity of paramagnetic chromophores and almost infinite combinations and mutual geometries. Strong exchange couplings are expected in 3d–2p heterospin compounds, where the nitroxide (aminoxyl) oxygen atom has a direct coordination bond with a nickel(II) ion. Complex formation of nickel(II) salts and tert-butyl 2-pyridyl nitroxides afforded a discrete 2p–3d–2p triad. Ferromagnetic coupling is favored when the magnetic orbitals, nickel(II) dσ and radical π*, are arranged in a strictly orthogonal fashion, namely, a planar coordination structure is characterized. In contrast, a severe twist around the coordination bond gives an orbital overlap, resulting in antiferromagnetic coupling. Non-chelatable nitroxide ligands are available for highly twisted and practically diamagnetic complexes. Here, the Ni–O–N–C_sp² torsion (dihedral) angle is supposed to be a useful metric to describe the nickel ion dislocated out of the radical π* nodal plane. Spin-transition complexes exhibited a planar coordination structure in a high-temperature phase and a nonplanar structure in a low-temperature phase. The gradual spin transition is described as a spin equilibrium obeying the van’t Hoff law. Density functional theory calculation indicates that the energy level crossing of the high- and low-spin states. The optimized structures of diamagnetic and high-spin states well agreed with the experimental large and small torsions, respectively. The novel mechanism of the present spin transition lies in the ferro-/antiferromagnetic coupling switch. The entropy-driven mechanism is plausible after combining the results of the related copper(II)-nitroxide compounds. Attention must be paid to the coupling parameter J as a variable of temperature in the magnetic analysis of such spin-transition materials. For future work, the exchange coupling may be tuned by chemical modification and external stimulus, because it has been clarified that the parameter is sensitive to the coordination structure and actually varies from 2J/k_B = +400 K to −1400 K. Full article

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H₃L and H₅L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu₄(HL²⁻)₂(N₃)₄]·4CH₃OH·56H₂O (1) and [Cu₄(L³⁻)₂(OH)₂(H₂O)₂] (2), dinuclear [Cu₂(H₃L1²⁻)(N₃)(H₂O)(NO₃)] (3), polynuclear {[Cu₂(H₃L1²⁻)(H₂O)(BF₄)(N₃)]·H₂O}_n (4), heptanuclear [Cu₇(H₃L1²⁻)₂(O)₂(C₆H₅CO₂)₆]·6CH₃OH·44H₂O (5), and decanuclear [Cu₁₀(H₃L1²⁻)₄(O)₂(OH)₂(C₆H₅CO₂)₄] (C₆H₅CO₂)₂·20H₂O (6). X-ray studies have revealed that the basic building block in 1, 3, and 4 is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL²⁻ or H₃L1²⁻, and one μ-1,1-azido (N₃⁻) ion and in 2, 5, and 6 by μ-phenoxide oxygen of L³⁻ or H₃L1²⁻ and μ-O²⁻ or μ₃-O²⁻ ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (1 and 6), 2D-sheets (3), and 3D-structures (4). In 5, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In 1, 3, and 5, Cu(II) ions in [Cu₂] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm⁻¹. Full article

Three new dinuclear copper(II) complexes [Cu₂(μ–HLⁿ)₂(μ-Cl)₂Cl₂]Cl₂ (1–3) have been synthesized and structurally characterized by single-crystal X-ray diffraction, where HL^x, (HL¹ = N⁶-propyladeninium, HL² = N⁶-butyladeninium and HL³ = N⁶-isobutyladeninium) are N⁶-alkyl bidentate NN donor adenine bases. Complexes 1–3 exhibit a coplanar arrangement of both N⁶-alkyladeninium moieties with UD conformation, with the terms U(up) or D(down) referring to the coordination of each pyrimidinic N³ atoms to the upper or lower metal center. In the three complexes, both copper atoms are five-coordinated (N₂Cl₃ donor set), resembling a compressed trigonal bipyramid. Each adenine moiety is protonated in N¹ and the positive charge balanced by chloride counterions. Magnetic measurements of complexes 1 and 3 in the 2–300 K temperature range indicate antiferromagnetic coupling with J = −156.1(7) and J = −151(2) cm⁻¹, respectively. Density functional theory calculations have also been performed in order to estimate the exchange coupling constants in these complexes. The theoretically calculated J values are in good agreement with the experimental values. Full article