Daopeng Zhang

Diverse Ni(II) MOFs constructed from asymmetric semi-rigid V-shaped multicarboxylate ligands: structures and magnetic properties

Novel nickel(II) coordination polymers have been constructed from asymmetric semi-rigid V-shaped multicarboxylate ligands with the help of 4,4′-bipyridine (4,4′-bpy) ligand. The hydrothermal reaction between 3-(4-carboxy-phenoxy)-phthalic acid (H3L1) and Ni(OAc)2·4H2O led to the formation of [Ni3(L1)2(μ-4,4′-bpy)3(H2O)2]n·(4,4′-bpy)n·(H2O)5n (1). In contrast, the same reaction using 3-(2-carboxy-phenoxy)-phthalic acid (H3L2) as a starting material instead of H3L1 resulted in [Ni3(L2)2(H2O)4(μ-4,4′-bpy)3]n·(H2O)2n (2) and [Ni3(L2)2(H2O)4(μ-4,4′-bpy)4]n·(H2O)2n (3) at 120 and 150 °C, respectively, revealing the effect of reaction temperature on the structure of the coordination polymer formed from the semi-rigid V-shaped ligand of L2. Single-crystal X-ray diffraction analysis reveals that complex 1 shows a 3D framework structure assembled from right- and left-handed helices together with isolated tubes. This compound represents the first metal–organic hybrid tube constructed from an asymmetric semi-rigid V-shaped multicarboxylate ligand. Compound 2 also exhibits a 3D network composed of discontiguous trinuclear Ni(II) clusters, while the 3D architecture of 3 consisting of isolated Ni(II) ions separated in a long distance is constructed by two kinds of 2D (6,3) networks. Magnetic studies reveal the overall antiferromagnetic interaction between the neighbouring Ni(II) ions in 1–3.

Heterobimetallic porphyrin-based single-chain magnet constructed from manganese(III)-porphyrin and trans-dicyanobis(acetylacetonato) ruthenate(III) containing co-crystallized bulk anions and cations

Two cyanide-bridged alternated 1 : 1 Ru(III)/Mn(III) complexes structurally characterized as single-chain containing co-crystallized bulk anions and cations have been successfully assembled from [Mn(TPP)(H(2)O)(2)](+) and [Ru(acac)(2)(CN)(2)](-) blocks. Systematic investigation of their magnetic properties reveals typical single-chain magnet (SCM) behaviors for both of them.

Rational design of cyanide-bridged heterometallic M(I)–Mn(II) (M = Ag, Au) one-dimensional chain complexes: synthesis, crystal structures and magnetic properties

Two mononuclear seven-coordinated macrocycle Mn(II) compounds and four new cyanide-bridged MI–MnII (M = Ag, Au) one-dimensional chain complexes have been synthesized and crystallographically characterized: [Mn(L1)Cl2] · H2O (1), [Mn(L2)Cl2]·H2O (2), [Ag(CN)2Mn(L1)][Ag(CN)2] (3), [Ag(CN)2Mn(L2)][Ag(CN)2] · 1.5H2O (4), [Au(CN)2Mn(L1)][Au(CN)2] (5) and [Au(CN)2Mn(L2)][Au(CN)2] · 1.5H2O (6). The structure of the one-dimensional complexes consists of alternating units of [Mn(L)]2+ and [M(CN)2]−, generating a cyanide-bridged cationic polymeric chain with [M(CN)2]− as the counteranion. In all complexes, the coordination geometry of manganese ion is a slightly distorted pentagonal-bipyrimidal with the cyanide nitrogen atoms at the trans positions and N5 or N3O2 coordinating mode in the equatorial plane from ligand L1 or L2. Investigation over magnetic properties of these four one-dimensional complexes reveals the whole very weak antiferromagnetic interaction between neighbouring Mn(II) ions bridged by the long NC–M–CN unit. A best-fit to the magnetic susceptibility of these complexes leads to the magnetic coupling constant of J = −0.065(2), −0.23(3), −0.15(6) and −0.13(5) cm−1 for complex 3, 4, 5, and 6, respectively.

Dichlorido{μ-6,6′-dimeth­oxy-2,2′-[o-phenyl­enebis(nitrilo­methyl­idyne)]diphenolato}(dimethyl sulfoxide)lead(II)zinc(II) N,N-dimethyl­formamide solvate

In the heterodinuclear complex of the title compound, [PbZn(C22H18N2O4)Cl2(C2H6OS)]·C3H7NO, the ZnII atom is coordinated in a distorted square-pyramidal geometry by two N atoms and two O atoms from the diphenolate ligand, and one Cl atom which occupies the apical position. The PbII atom is coordinated in a distorted octahedral geometry by the four O atoms of the diphenolate ligand, one O atom from the dimethyl sulfoxide molecule and one Cl atom. The dimethyl sulfoxide molecule is disordered over two positions, with site occupancies of 0.576u2005(2) and 0.424u2005(2).

Di-μ-chlorido-dichlorido-bis{μ-6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolato}dilead(II)dizinc(II) N,N′-dimethyl­formamide disolvate

The title compound, [Pb2Zn2(C22H18N2O4)2Cl4]·2C3H7NO, was synthesized using a step-by-step method and has a slipped sandwich configuration. The coordination environment of the Zn2+ ion is distorted square-pyramidal and it is coordinated by N2O2 of the Schiff base ligand and chloride; each Pb2+ ion is coordinated by the four 6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolate (L) O atoms and two chloride ions. The ZnIIPbII dinuclear unit, through an inversion-symmetry operation, forms a tetrameric complex with double chloride bridges.

Bis(isocyanato-κN)bis­(1,10-phenanthroline-κ2N,N′)cobalt(II)

In the title complex, [Co(NCO)2(C12H8N2)2], the CoII atom, lying on a twofold rotation axis, is coordinated in a distorted octahedral environment by four N atoms from two chelating phenanthroline ligands and two N atoms from two isocyanate ligands in cis positions.

Bis(diethyl­enetriamine-κ3N,N′,N′′)nickel(II) bis­(1,2-dicyanoethene-1,2-dithiolato-κ2S,S′)nickel(II)

The title compound, [Ni(C4H13N3)2][Ni(C4N2S2)2], has been synthesized by the reaction of Ni(ClO4)2·6H2O, diethylenetriamine (deta) and Na2[Ni(mnt)2] [mnt = maleonitriledithiolate(2-)] in methanol. The structure is composed of a [Ni(deta)2]2+ cation and a [Ni(mnt)2]2− anion. The coordination geometry of the NiII ion in the cation is slightly distorted octahedral, defined by six N atoms from two deta ligands, while the NiII ion in the anion is four-coordinated by four S atoms from two mnt ligands in a slightly distorted square-planar geometry. The cations and anions are connected by N—H⋯N hydrogen bonds.

3,3'-(m-Phenyl-enedi-oxy)diphthalonitrile.

In the title compound, C(22)H(10)N(4)O(2), the dihedral angles between the mean planes of the central benzene ring and the pendant rings are 79.20u2005(6) and 80.29u2005(6)°. The dihedral angle between the pendant rings is 10.27u2005(7)°.