Structure and magnetism of [M3](6/7+) metal chain complexes from density functional theory: analysis for copper and predictions for silver

The ground-state electronic structure of the trinuclear complex Cu3(dpa)4Cl2 (1), where dpa is the anion of di(2-pyridyl)amine, has been investigated within the framework of density functional theory (DFT) and compared with that obtained for other known M3(dpa)4Cl2 complexes (M = Cr, Co, Ni) and for the still hypothetical Ag3(dpa)4Cl2 compound. Both coinage metal compounds display three singly occupied x2-y2-like (delta) orbitals oriented toward the nitrogen environment of each metal atom, generating antibonding M-(N4) interactions. All other metal orbital combinations are doubly occupied, resulting in no delocalized metal-metal bonding. This is at variance with the other known symmetric M3(dpa)4Cl2 complexes of the first transition series, which all display some delocalized bonding through the metal backbone, with formal bond multiplicity decreasing in the order Cr > Co > Ni. An antiferromagnetic coupling develops between the singly occupied MOs via a superexchange mechanism involving the bridging dpa ligands. This magnetic interaction can be considered as an extension to the three aligned Cu(II) atoms of the well-documented exchange coupling observed in carboxylato-bridged dinuclear copper compounds. Broken-symmetry calculations with approximate spin projection adequately reproduce the coupling constant observed for 1. Oxidation of 1 removes an electron from the magnetic orbital located on the central Cu atom and its ligand environment; 1+ displays a much weaker antiferromagnetic interaction coupling the terminal Cu-N4 moieties via four ligand pathways converging through the x2-y2 orbital of the central metal. The silver homologues of 1 and 1+ display similar electronic ground states, but the calculated magnetic couplings are stronger by factors of about 3 and 4, respectively, resulting from a better overlap between the metal centers and their equatorial ligand environment within the magnetic orbitals.     

Oxidation of Ni3(dpa)4Cl2 and Cu3(dpa)4Cl2: nickel-nickel bonding interaction,but no copper-copper bonds

Of the known trinuclear dipyridylamido complexes of the first-row transition metals, M(3)(dpa)(4)Cl(2) (dpa is the anion of di(2-pyridyl)amine, M = Cr, Co, Ni, Cu), the one-electron-oxidation products of only Cr(3)(dpa)(4)Cl(2) and Co(3)(dpa)(4)Cl(2) have been isolated previously. Here we report one-electron-oxidation products of Ni(3)(dpa)(4)Cl(2) (1) and Cu(3)(dpa)(4)Cl(2) (3): Ni(3)(dpa)(4)(PF(6))(3) (2) and [Cu(3)(dpa)(4)Cl(2)]SbCl(6) (4). While there are no Ni-Ni bonds in 1, the Ni-Ni distances in 2 are 0.15 A shorter than those in 1, very suggestive of metal-metal bonding interactions. In contrast, the oxidation of 3 to 4 is accompanied by a lengthening of the Cu-Cu distances, as expected for an increase in electrostatic charge between positively charged nonbonded metal ions, which is further evidence against Cu-Cu bonding in either 3 or 4. A qualitative model of the electronic structures of all [M(3)(dpa)(4)Cl(2)](n+) (n = 0, 1) compounds is presented and discussed.     

Isotropic non-Heisenberg behavior in M3(dpa)4Cl2 extended metal atom chains

Isotropic deviations to the standard Heisenberg Hamiltonian have been extracted for a series of trinuclear extended metal atom chain complexes, namely, [Ni(3)(dpa)(4)Cl(2)], and the hypothetical [NiPdNi(dpa)(4)Cl(2)] and [Pd(3)(dpa)(4)Cl(2)], following a scheme recently proposed by Labe?guerie and co-workers (J. Chem. Phys 2008, 129, 154110) within the density functional theory framework. Energy calculations of broken symmetry monodeterminantal solutions of intermediate M(s,tot.) values can provide an estimate of the magnitude of the biquadratic exchange interaction (λ) that accounts for these deviations in systems with S = 1 magnetic sites. With the B3LYP functional, we obtain λ = 1.37, 13.8, and 498 cm(-1) for the three molecules, respectively, meaning that a simple Heisenberg Hamiltonian is enough for describing the magnetic behavior of the Ni(3) complex but definitely not for Pd(3). In the latter case, the origin of such extreme deviation arises from (i) an energetically affordable local non-Hund state (small intrasite exchange integral, K ～ 1960 cm(-1)) and (ii) a very effective overlap between Pd-4d orbitals and a large J. Furthermore, this procedure enables us to determine the relative weights of the two types of magnetic interactions, σ- and δ-like, that contribute to the total magnetic exchange (J = J(σ) + J(δ)). In all of the systems, J is governed by the σ interaction by 95-98%.     

Electron delocalization in nickel metallic wires: a DFT investigation of Ni(3)(dpa)(4)Cl(2) and [Ni(3)(dpa)(4)](3+) (dpa = dipyridylamide) and extension to higher nuclearity chains

The electronic structure of Ni(3)(dpa)(4)Cl(2) (1) has been investigated within the framework of the density functional theory (DFT), using two types of exchange-correlation functionals and various basis sets. The "broken-symmetry" approach proposed by Noodleman for the characterization of electronic states displaying an antiferromagnetic coupling has been applied to 1. All calculations lead to the conclusion that the ground state results from an antiferromagnetic coupling between the terminal Ni atoms, both displaying a high-spin electronic configuration. The central Ni atom is in a low-spin configuration, but is involved in a superexchange interaction connecting the two magnetic centers. These results are in agreement with the assignments recently proposed by the group of F. A. Cotton on the basis of magnetic measurements. It is shown that the ground state electronic configuration calculated for 1 provides the trinickel framework with some delocalized sigma bonding character. The observed geometry of 1 is accurately reproduced by the broken-symmetry solution. The doublet ground state assigned to the oxidized species [Ni(3)(dpa)(4)](3+) (2) and the dramatic contraction of the coordination sphere of the terminal metals observed upon oxidation are also confirmed by the calculations. However, the formal Ni-Ni bond order is not expected to increase in the oxidized species. The contraction of the Ni-Ni distance in 2 is shown to result in part from the vanishing of the important trans influence originating in the axial ligands, and for the rest from a more efficient shielding of the metal nuclear charge along the Ni-Ni-Ni axis. The conclusions deduced from the analysis of the bonding in 1 and 2 can be extended to their homologues with higher nuclearity. More specifically, it is predicted that the single occupancy of the most antibonding sigma orbital, extending over the whole metal framework, will provide the (Ni(p))(2)(p)(/(2)(p)(+1)+) chains with some delocalized bonding character and, possibly, with electrical conduction properties.     

A rational design for imidazolate-bridged linear trinuclear compounds from mononuclear copper(II) complexes with 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL): syntheses, structures, and magnetic properties of [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = ZnII, CuII, MnII)

Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variable-temperature magnetic data are well reproduced for one-dimensional infinite regular chain systems with J = -60.3 cm(-1) and g = 2.02 for 3 and J = -69.5 cm(-1) and g = 2.06, for 4. When 1 is used as a "ligand complex" for [M(hfac)2] (M = Cu(II), Ni(II), Mn(II), Zn(II)) in a basic medium, only the imidazolate-bridged trinuclear complexes [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = Zn(II), Cu(II)) (5, 6) can be isolated. Nevertheless, the analogous complex containing Mn(II) as the central metal (7) can be prepared from the precursor [Cu(HL)Cl2] (2). All the trinuclear complexes are isostructural. The structures of 5 and 6 have been solved by X-ray crystallographic methods and consist of well-isolated molecules with Ci symmetry, the center of symmetry being located at the central metal. Thus, the copper(II) fragments are in trans positions, leading to a linear conformation. The magnetic susceptibility data (2-300 K), which reveal the occurrence of antiferromagnetic interactions between copper(II) ions and the central metal, were quantitatively analyzed for symmetrical three-spin systems to give the coupling parameters JCuCu = -37.2 and JCuMn = -3.7 cm(-1) with D = +/-0.4 cm(-1) for 6 and 7, respectively. These magnetic behaviors are compared with those for analogous systems and discussed on the basis of a localized-orbital model of exchange interactions.     

N,N'-乙二水杨酰胺合铜(II)酸根和N,N'-1,2-丙二水杨酰胺全铜(II)酸根的双核Cu(II)-Fe(III)配合物的合成和磁性

本文合成了四个新型双核配合物、[Cu(samen)Fe(L)Cl]和[Cu(sampn)Fe(L)Cl]。经元素分析、IR, 电导、磁性测量等手段推定配合物具有酚氧桥结构, Cu(II)及Fe(III)的配位环境分别为平面四方及四角锥的构型, Fe(III)离子的自旋态S=3/2。测定了配合物[Cu(samen)Fe(L)Cl]的变温磁化率(4-300K), 参数J和θ值表明两个双核配合物中金属离子之间有中等程度的反铁磁性超交换作用和双核单元之间有弱的分子间相互作用。     

Molecular metamagnet [Ni(4ImNNH)(2)(NO(3))(2)] (4ImNNH = 4-imidazolyl nitronyl nitroxide) and the related compounds showing supramolecular H-bonding interactions

A new chelating radical ligand 4ImNNH (2-(4-imidazolyl)-4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide) was prepared, and complexation with divalent transition metal salts gave complexes, [M(4ImNNH)(2)X(2)], which showed intermolecular ferromagnetic interaction in high probability (7 out of 10 paramagnetic compounds investigated here). The nitrate complexes (X = NO(3); M = Mn (1), Co (2), Ni (3), Cu (4)) crystallize isomorphously in monoclinic space group P2(1)/a. The equatorial positions are occupied with two 4ImNNH chelates and the nitrate oxygen atoms are located at the axial positions. Magnetic measurements revealed that the intramolecular exchange couplings in 1, 2, and 4 were antiferromagnetic, while that in 3 was ferromagnetic with 2J/k(B) = +85 K, where the spin Hamiltonian is defined as H = -2J(S(1).S(2) + S(2).S(3)) based on the molecular structures determined as the linear radical-metal-radical triads. The intramolecular ferromagnetic interaction in 3 is interpreted in terms of orthogonality between the radical pi and metal dsigma orbitals. Compounds 1-3 exhibited intermolecular ferromagnetic interaction ascribable to a two-dimensional hydrogen bond network parallel to the crystallographic ab plane. Complex 3 became an antiferromagnet below 3.4 K and exhibited a metamagnetic transition on applying a magnetic field of 5.5 kOe at 1.8 K. The complexes prepared from metal halides, [M(4ImNNH)(2)X(2)] (X = Cl, Br; M = Mn, Co, Ni, Cu), showed intramolecular antiferromagnetic interactions, which are successfully analyzed based on the radical-metal-radical system. The crystal structures determined here on 1-4, [Mn(4ImNNH)(2)Cl(2)], and [Cu(4ImNNH)(2)Br(2)] always have intermolecular hydrogen bonds of H(imidazole).X(axial ligand)-M, where X = NO(3), Cl, Br. This interaction seems to play an important role in molecular packing and presumably also in magnetic coupling.     

Further structural and magnetic studies of tricopper dipyridylamido complexes

The compound Cu3(dpa)4Cl2, 1 (dpa = the anion of dipyridylamine), which was first synthesized and characterized in 1990, has been structurally characterized in three new crystal forms having Cu...Cu separations of 2.47-2.49 A. Its magnetic properties have been studied fully. Reaction of Cu3(dpa)4Cl2 with 2 equiv of silver tetrafluoroborate yields Cu3(dpa)4(BF4)2 (2), a compound with a similar linear trinuclear structure but coordinated BF4 anions in each axial position and having shorter Cu...Cu distances of 2.40 A but similar magnetic properties. Least squares fitting of the magnetic susceptibility data for 1 and 2 gave isotropic g values of 2.007 and 2.130 and exchange parameters of -373 and -411 cm-1, respectively. This suggests the possible existence of an exchange pathway in which the metal atoms interact directly with each other.     

Oxidation of linear trinuclear ruthenium complexes [Ru(3)(dpa)(4)Cl(2)] and [Ru(3)(dpa)(4)(CN)(2)]: synthesis, structures, electrochemical and magnetic properties

The neutral, monocationic, and dicationic linear trinuclear ruthenium compounds [Ru(3)(dpa)(4)(CN)(2)], [Ru(3)(dpa)(4)(CN)(2)][BF(4)], [Ru(3)(dpa)(4)Cl(2)][BF(4)], and [Ru(3)(dpa)(4)Cl(2)][BF(4)](2) (dpa=the anion of dipyridylamine) have been synthesized and characterized by various spectroscopic techniques. Cyclic voltammetric and spectroelectrochemical studies on the neutral and oxidized compounds are reported. These compounds undergo three successive metal-centered one-electron-transfer processes. X-ray structural studies reveal a symmetrical Ru(3) unit for these compounds. While the metal--metal bond lengths change only slightly, the metal--axial ligand lengths exhibit a significant decrease upon oxidation of the neutral complex. The electronic configuration of the Ru(3) unit changes as the axial chloride ligands are replaced by the stronger "pi-acid" cyanide axial ligands. Magnetic measurements and (1)H NMR spectra indicate that [Ru(3)(dpa)(4)Cl(2)] and [Ru(3)(dpa)(4)Cl(2)][BF(4)](2) are in a spin state of S=0 and [Ru(3)(dpa)(4)Cl(2)][BF(4)], [Ru(3)(dpa)(4)(CN)(2)], and [Ru(3)(dpa)(4)(CN)(2)][BF(4)] are in spin states of S=1/2, 1, and 3/2, respectively. These results are consistent with molecular orbital (MO) calculations.     

Anion influence on the structure and magnetic properties of a series of multidimensional pyrimidine-2-carboxylato-bridged copper(II) complexes

Seven new polynuclear copper(II) complexes of formula [Cu(mu-pymca)2] (1) (pymca(-) = pyrimidine-2-carboxylato), [Cu(mu-pymca)Br] (2), [Cu(mu-pymca)Cl] (3), [Cu(mu-pymca)(SCN)(H2O)] x 4 H2O (4), [Cu(mu-pymca)N3] (5), [Cu2(mu1,5-dca)2(pymca)2] (6) (dca = dicyanamide), and K{[mu-Au(CN)2]2[(Cu(NH3)2)2(mu-pymca)]}[Au(CN)2]2 (7) have been synthesized by reactions of K-pymca with copper(II) ions in the presence of different counteranions. Compound 1 is a linear neutral chain with a carboxylato bridging ligand in a syn-anti coordination mode, whereas complexes 2 and 3 consist of cationic linear chains with cis and trans bis(chelating) pymca bridging ligands. Complex 4 adopts a helical pymca-bridged chain structure. In complex 5, zigzag pymca-bridged chains are connected by double end-on azide bridging ligands to afford a unique honeycomb layer structure. Complex 6 is a centrosymmetric dinuclear system with double mu 1,5-dicyanamide bridging ligands and pymca end-cap ligands. Complex 7 is made of pymca-bridged dinuclear [Cu(NH3)2(mu-pymca)Cu(NH3)2](3+) units connected by [Au(CN)2](-) anions to four other dinuclear units, giving rise to cationic (4,4) rectangular nets, which are linked by aurophilic interactions to afford a singular 3D network. Variable-temperature magnetic susceptibility measurements show that complex 1 exhibits a very weak antiferromagnetic coupling through the syn-anti (equatorial-axial) carboxylate bridge (J = -0.57 cm(-1)), whereas complexes 2-4 and 7 exhibit weak to strong antiferromagnetic couplings through the bis(chelating) pymca bridging ligand J = -17.5-276.1 cm(-1)). Quantum Monte Carlo methods have been used to analyze the experimental magnetic data for 5, leading to an antiferromagnetic coupling (J = -34 cm(-1)) through the pymca ligand and to a ferromagnetic coupling (J = 71 cm(-1)) through the azide bridging ligands. Complex 6 exhibits a very weak antiferromagnetic coupling through the dicyanamide bridging ligands (J = -5.1 cm(-1)). The magnitudes of the magnetic couplings in complexes 2-5 have been explained on the basis of the overlapping between magnetic orbitals and DFT theoretical calculations.     

New tetranuclear Cu(II) complexes: synthesis, structure, and magnetic properties

The synthesis, structure, and magnetic properties of two new tetranuclear Cu(II) complexes containing N,N,N',N'-tetraethylpyridine-2,6-dithiocarboxamide (S-dept) of formula [Cu(2)Cl(2)(mu-S-dept)(2)][Cu(2)Cl(4)(mu-Cl)(2)] (1) and [Cu(2)(mu-Cl)(2)(S-dept)(2)][CuCl(3)(EtOH)](2) (2) are reported. Their X-ray crystal structures reveal that the complexes are composed of anionic and cationic dimers, that in both cases contain the metal centers which interact via Coulombic and/or hydrogen bonding interactions. In both cases, the Cu centers in the anionic moieties adopt a slightly distorted tetrahedral geometry whereas for the cationic moieties they adopt a square-pyramidal type of geometry. Magnetic susceptibility data show that compounds 1 and 2 present an overall antiferromagnetic behavior arising from the contribution of both anionic and cationic moieties. For 1, the best fit obtained gave J(1) = -2.62 +/- 0.19 cm(-1), J(2) = -19.54 +/- 0.47 cm(-1), and g(2) = 2.164 +/- 0.004 cm(-1) (R = 8.28 x 10(-5)) whereas for 2 it gave J(1) = 4.48 +/- 2.73 cm(-1), g(1) = 2.20 +/- 0.03, J(2) = -11.26 +/- 2.01 cm(-1), and g(2) = 2.10 +/- 0.03 (R = 1.15 x 10(-4)). The nature of the superexchange pathways in 1 and 2 is discussed on the basis of structural, magnetic, and molecular orbital considerations. Theoretical calculations are performed at the extended Huckel level in order to obtain their molecular orbitals and energies using their crystallographic data.     

含有双螺旋链的配位聚合物[Co(dpa)prz0.5]n的合成、晶体结构及磁性质

A coordination polymer [Co(dpa)prz_0.5]_n(1) with double-helix chains has been constructed hydrothermally using H₂dpa (H₂dpa=diphenic acid), prz (prz=piperazine) and Co(NO₃)₂·6H₂O. The structure and magnetic properties of the complex were investigated. The complex crystallizes in triclinic system and P1 space group. Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry. Two carboxylates of the H₂dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical -C-O-Co- chains. The two types of helical chains are interconnected to each other through the Co(Ⅱ) centers to produce double-helix chains. The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains. The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks. Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions. CCDC: 709275.     

New trinuclear metal string complexes containing rigid Hdzp ligands: synthesis, structure, magnetism and DFT calculation (Hdzp = 1,9-diazaphenoxazine)

The synthesis, crystal structure, magnetic properties, and single-molecule conductance of two new trinuclear metal string complexes, [Ni(3)(dzp)(4)(NCS)(2)] (2) and [Co(3)(dzp)(4)(NCS)(2)] (3), containing the rigid Hdzp ligand (1, 1,9-diazaphenoxazine) are reported. X-ray structural analyses show that compounds 2 and 3 exhibit smaller torsion angles and longer metal-metal distances than those exhibited by the corresponding dpa(-) analogues (dpa(-) = dipyridylamido anion) due to the rigidity of Hdzp ligands. The longer metal-metal distance observed for 2 and 3 results in variations in their magnetic properties. The exchange interaction (J = -160 cm(-1)) between two high spin (HS) Ni(II) ions in 2 decreases slightly in comparison with those of trinickel dpa(-) analogues. The doublet-quartet gap of 3 is smaller than that of [Co(3)(dpa)(4)(NCS)(2)] (4), which causes compound 3 to show spin-crossover behavior even at low temperature.     

Copper(II) azide complexes of aliphatic and aromatic amine based tridentate ligands: novel structure, spectroscopy, and magnetic properties

Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy.     

Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold

Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4'-(NH(2))(2)-6,6'-(NHC(6)H(5))(2)-2,2'-(1,3,5-C(3)N(3))(2), is reported, and its coordination with Co, Ni and Cu is explored. Reactions of metal salts (2 equiv) with Btzn (1 equiv) result in dimeric species [(Btzn)Co(2)(NCS)(4)(EtOH)(2)(DMF)(2)], (2), [(Btzn)Ni(2)(η(1)-ONO(2))(2)(MeOH)(4)(DMF)(2)]·2[NO(3)], (3), [(Btzn)Cu(2)Cl(4)(DMF)(2)], (4), and [(Btzn)Cu(2)(η(2)-O(2)NO)(2)(OH(2))(2)(DMF)(2)]·2[NO(3)], (5). These complexes are the first examples of the coordination of transition metals with bi(1,3,5-triazine) ligands. Their structures display a bridging bis-bidentate coordination mode for Btzn. Variable-temperature magnetic susceptibility of the complexes reveals antiferromagnetic exchange between the spin carriers, with calculated exchange coupling values (J) of -4.7 cm(-1) for 3, -18.2 cm(-1) for 4, and -5.5 cm(-1) for 5. An in-depth evaluation of the metal geometry highlights the inefficient overlap of the magnetic d-orbitals through the bridging ligand, most likely leading to reduced delocalization and coupling.     

Verdazyl radicals as oligopyridine mimics: structures and magnetic properties of M(II) complexes of 1,5-dimethyl-3-(2,2'-bipyridin-6-yl)-6-oxoverdazyl (M = Mn,Ni, Cu,Zn)

The verdazyl radical 1,5-dimethyl-3-(2,2'-bipyridin-6-yl)-6-oxoverdazyl (3) was prepared, and its homoleptic metal complexes M(3)(2)(2+).2X(-) (5, M = Mn(II); 6, M = Ni(II); 7, M = Cu(II); 8, M = Zn(II); X = ClO(4), PF(6)) were characterized by single-crystal X-ray diffraction and variable-temperature magnetic susceptibility measurements. Relevant crystallographic parameters are as follows: 5, monoclinic space group Pna2(1), a = 18.755(4) A, b = 11.154(3) A, c = 16.594(4) A, alpha = 90.00 degrees, beta = 90.00 degrees, gamma = 90.00 degrees, V = 3471.4(13) A(3), and Z = 4; 7, triclinic space group Ponedblac;, a = 9.4638(18) A, b = 9.8442(19) A, c = 18.769(4) A, alpha = 103.746(3) degrees, beta = 92.925(3) degrees, gamma = 94.869(3) degrees, V = 1687.8(6) A(3), and Z = 2; 8, triclinic space group Ponedblac;, a = 9.4858(14) A, b = 9.7919(14) A, c = 18.889(3) A, alpha = 104.196(3) degrees, beta = 92.855(3) degrees, gamma = 94.216(3) degrees, V = 1692.1(4) A(3), and Z = 2. In all cases, the two verdazyl-based ligands bind almost perpendicular to each other in meridional positions, yielding pseudooctahedral metal complexes whose general structural features are strongly reminiscent of metal bis(terpyridine) complexes. The intramolecular metal-verdazyl magnetic exchange coupling is strongly ferromagnetic in 6 (J(Ni-vd) = +240 cm(-1)), and strongly antiferromagnetic in 5 (J(Mn-vd) = -93 cm(-1)). Complex 7 exhibits weak ferromagnetic coupling (J(Cu-vd) = -4.5 cm(-1)). Intramolecular radical-radical coupling in the zinc complex 8 was found to be weakly antiferromagnetic (J(vd-vd) = -8 cm(-1)). Intramolecular radical-radical exchange was generally weak in the four metal complexes, ranging from -10 cm(-1) (for 5) to +2 cm(-1) (for 7). The low-temperature magnetic behavior of 7 and 8 is complex, possibly arising from a combination of intra- and intermolecular interactions.     

1-D polymers with alternate Cu2 and Ln2 units (Ln = Gd, Er, Y) and carboxylate linkages

Three isostructural Cu 2Ln 2 1-D polymers [Cu 2Ln 2L 10(H 2O) 4.3H 2O] n where Ln = Gd ( 1), Er ( 2), and Y ( 3) and HL= trans-2-butenoic acid, were synthesized and characterized by X-ray crystallography, electron paramagnetic resonance, and magnetic measurements. Pairs of alternate Cu 2 and Ln 2 dinuclear units are combined into a linear array by a set of one covalent eta (2):eta (1):mu 2 carboxylate oxygen and two H bonds, at Cu...Ln distances of ca. 4.5 A. These units exhibit four eta (1):eta (1):mu 2 and two eta (2):eta (1):mu 2 carboxylate bridges, respectively. Magnetic measurements between 2 and 300 K, fields B 0 = mu 0 H between 0 and 9 T, and electron paramagnetic resonance (EPR) measurements at the X-band and room temperature are reported. The magnetic susceptibilities indicate bulk antiferromagnetic behavior of the three compounds at low temperatures. Magnetization and EPR data for 1 and 3 allowed evaluation of the exchange couplings between both Cu and Gd ions in their dinuclear units and between Cu and Gd neighbor ions in the spin chains. The data for the isolated Cu 2 units in 3 yield g || = 2.350 and g [symbol: see text] = 2.054, J Cu-Cu = -338 (3) cm (-1) for the exchange coupling [ H ex(1,2) = - J 1-2 S1 x S2], and D 0 = -0.342 (0.003) cm (-1) and E 0 = 0.003 (0.001) cm (-1) for the zero-field-splitting parameters of the triplet state arising from anisotropic spin-spin interactions. Considering tetranuclear blocks Gd-Cu-Cu-Gd in 1, with the parameters for the Cu 2 unit obtained for 3, we evaluated ferromagnetic interactions between Cu and Gd neighbors, J Cu-Gd = 13.0 (0.1) cm (-1), and between Gd ions in the Gd 2 units, J Gd-Gd = 0.25 (0.02) cm (-1), with g Gd = 1.991. The bulk antiferromagnetic behavior of 1 is a consequence of the antiferromagnetic coupling between Cu ions and of the magnitude, |J Cu-Gd|, of the Cu-Gd exchange coupling. Compound 2 displays a susceptibility peak at 15 K that may be interpreted as the combined result from antiferromagnetic couplings between Er (III) ions in Er 2 units and their coupling with the Cu 2 units.     

Allopurinol- and Hypoxanthine-Copper(II) Compounds. Spectral and Magnetic Studies of Novel Dinuclear Coordination Compounds with Bridging Hypoxanthine

The synthesis in aqueous solution and pH = 1.0 of several novel Cu(II) compounds with allopurinol and hypoxanthine as heterocyclic ligands and X = Cl(-), Br(-), NO(3)(-), SO(4)(2-), and ClO(4)(-) as anions, together with their spectral and magnetic characterization, is reported. The studies of the Cu(II) systems with these heterocycles and Cl(-) or Br(-) support their Cu(II)(L)(2)(X)(2) character and their interactions through halogen atoms as bridging ligands, leading to a very weak antiferromagnetic coupling. For the Cu(II) compounds with hypoxanthine and X = NO(3)(-), SO(4)(-), or ClO(4)(-), new examples of the cupric acetate type are obtained, showing in all cases similar strong antiferromagnetic coupling. These three cases are new examples of the scarce Cu(II) dinuclear compounds with bridging hypoxanthine which have been reported up to now.     

Metal complexes formed by metal-assisted solvolysis of di-pyridylketone azine: structures and magnetic properties

A series of metal complexes were achieved from the metal-assisted solvolysis reaction of di-pyridylketone azine (dpka). The tetranuclear nickel cluster , [Ni(2)[dpk(O)(OH)][dpk(O)(OCH(3))](N(3))(2)](2), is centrosymmetric with a central core described as an edge-shared triangle core. Neighboring Ni(II) ions are alternately bridged by (micro(2)-N(3), micro(3)-O) and (micro(2)-O, micro(3)-O) double bridges. Complex , [Cu(4)[dpk(O)(OCH(3))](4)(N(3))(2)](CuCl(2))(2) contains a tetranuclear cluster and two identical [CuCl(2)]M(-) anions. The tetranuclear structure has two crystallographically imposed twofold axes, in which the four copper ions are arranged to be rhombic shape. The neighboring copper(ii) ions along the lateral are bridged by single micro(2)-O from the ligand dpk(O)(OCH(3)) and the short diagonal copper ions are bridged by two symmetric end-on azides. In dinuclear Cu(ii) complex [Cu(2)[dpka(OCH(2)CH(3))]Cl(2)](ClO(4)) (3), the metal centers are coordinated in a planar configuration and bridged by a -N-N- bridge. It is also observed that the Cl atom coordinated to one Cu(II) center is also weakly coordinated to another inversion related Cu(II) to generate a centrosymmetric dimer. The metal centers in one-dimensional polymeric Cu(ii) complex [Cu(2)[dpka(OCH(3))](N(3))(2)(ClO(4))](n) (4), however, are bridged by a -N-N- bridge and an end-to-end azide bridge, alternately. Magnetic susceptibility measurements indicate that shows ferromagnetic interaction within the tetranuclear cluster, and that displays moderately strong antiferromagnetic interaction (J = -56.7 cm(-1)) for the bis(micro-N(3)) bridge. For compound , it shows strong antiferromagnetic coupling (J = -286 cm(-1)) between the intradinuclear Cu(II) ions mediated by the single N-N bridge and negligible magnetic interactions between the adjacent dinuclear Cu(II) ions mediated by the single end-to-end azide bridge. The mechanism of the metal-assisted solvolysis reaction was also discussed.     

Intermolecular magnetic couplings in the dinuclear copper(II) complex mu-chloro-mu-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] aqua chlorocopper(II) dichlorocopper(II): synthesis, crystal structure, and EPR and magnetic characterization

Mu-chloro-mu-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] aqua chlorocopper(II) dichlorocopper(II) is the first characterized dimeric complex of a transition metal and this hetero ligand [C(12)H(10)Cl(4)Cu(2)N(4)OS; triclinic; space group P; a = 9.296(3) A, b = 9.933(3) A, c = 10.412(3) A; alpha = 79.054(5) degrees, beta = 82.478(6) degrees, gamma = 67.099(5) degrees; Z = 2 at room temperature]. The Cu(II) ions are bridged by the N-N thiadiazole bond and a chloride ion [Cu1-Cu2 = 3.7800(8) A]. Thermogravimetric analysis shows this structure to be stable at temperatures up to 348 K. At higher temperatures, the successive loss of a water molecule and one chloride of the dimeric unit is identified. From room temperature to 125 K, half of the Cu(2+) ions are progressively engaged in intermolecular dinuclear antiferromagnetic exchanges, while the other half remain paramagnetic. At lower temperatures, both susceptibility and electron paramagnetic resonance measurements show the paramagnetic-only couplings of this half of the Cu(2+) ions, involving a singlet ground state for interacting Cu(2+). This unusual behavior has been satisfactorily explained on the basis of intermolecular Cu-Cu interactions (J = -180 cm(-1)), involving the magnetic d(z)2 orbital perpendicular to the molecular plane, on which are seen the conjugate effects of the bridging chloride and the planar thiadiazole. It is noteworthy that the behavior of the title compound is original, compared to the systematic in-plane intramolecular antiferromagnetic coupling of other thiadiazole-containing binuclear complexes.