The use of trans-4-cotininecarboxylate to construct a polymeric copper(II) azido complex: Hydro(solvo)thermal synthesis, structure and magnetic properties

A new pyridyl-carboxylate ligand, the anion of trans-4-cotininecarboxylic acid, HL, 1, has been used to prepare a new polymeric copper(II) complex, [CuLN₃]_2n, 2, based on a [CuLN₃]₂ dimeric building block. The single crystal structures of both 1 and 2 have been determined and 1 has been found to be in its zwitterionic configuration. The structure of 2 is a one-dimensional tape-like polymeric structure based on an end-on azido-bridged binuclear [Cu₂N₃]₂ backbone moiety. Magnetic studies reveal that 2 is close to paramagnetic from 2 to 300 K with a Curie constant of 1.094 emu K/mol, a Weiss temperature of 0.73 K and a corresponding μ_eff of 2.09 μ_B. A fit of χ_MT for 2 with S₁ = S₂ = ½, yields g = 2.441(6), J = −0.49(3) cm⁻¹, zJ = −0.38(2) cm⁻¹ and N(α) = 0.00053(12) emu/mol, a fit that indicates the presence of both very weak intramolecular intrachain antiferromagnetic exchange coupling within the one-dimensional tape-like chains and very weak interchain antiferromagnetic exchange coupling between these chains.     

Synthesis, structure and property of manganese(II) complexes with mixed tetradentate imidazole-containing ligand and benzenedicarboxylate

Three new coordination complexes [Mn(L)(H₂O)₂](1,4-BDC)·2H₂O (1), [Mn(L)_0.5(1,4-BDC)]CH₃OH·H₂O (2) and [Mn(L)(H₂O)₂](1,2-HBDC)₂·2H₂O (3) were synthesized by solvothermal reactions of 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L) and 1,4-benzenedicarboxylic acid (1,4-H₂BDC) or 1,2-benzenedicarboxylic acid (1,2-H₂BDC) with Mn(II) salt, and characterized by single crystal X-ray diffraction, IR, thermogravimetric and elemental analyses. In complexes 1 and 3, each ligand L links four Mn(II) atoms to form two-dimensional (2D) cationic network with non-coordinated 1,4-BDC²⁻ and 1,2-HBDC⁻ anions lying in the voids between the two adjacent layers, respectively. The 2D layers are further connected together by hydrogen bonds to give three-dimensional (3D) supramolecular structures. However, the 1,4-BDC²⁻ in 2 acts not only as counteranion, but also as bridging ligand leading to the formation of 2-fold interpenetrated 3D framework with pcu (primitive cubic unit) topology. The Mn(II) atoms bridged by carboxylate groups in 2 show antiferromagnetic interactions.     

Three ion-pair complexes containing bis(maleonitriledithiolate)copper(II) anion and substituted 4-dimethylaminopyridinium: Syntheses, crystal structures, and magnetic properties

Three new ion-pair complexes, [4RBzDMAP]₂[Cu(mnt)₂] (mnt²⁻ = maleonitriledithiolate; [4RBzDMAP]⁺ = 1-(4′-R-benzyl)-4-dimethylaminopyridinium, R = F(1), Cl(2) and Br(3)) were synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The [Cu(mnt)₂]²⁻ anions and the cations stack alternately and form a 1D column via C-H···S, C-H···π or C-H···Cu interactions for 1 and 2. While the cations stack into a column though π···π or C-H···π interactions between pyridine and phenyl rings for 1 and 3. The change of the molecular topology of the counteraction when the 4-substituted group in the benzyl ring have been changed from F or Cl to Br atom, results in the difference in the crystal system, space group and the stacking mode of the cations and anions of 1, 2 and 3. Some weak hydrogen bonds between the adjacent columns further generate a 3D network structure. It is interesting that 1 and 2 exhibits antiferromagnetic coupling with θ = −2.372 K and θ = −14.732 K, while 3 shows weak ferromagnetic coupling feature with θ = 0.381 K.     

Syntheses, structures and properties of copper(II) and cobalt(II) metal-organic frameworks based on R-isophthalate (R = -CH3 or -C(CH3)3) and 1,1′-(1,4-butanediyl)bis(imidazole) ligands

Three new complexes [Cu₂(mip)₂(bbi)]_n (1), {[Cu₂(tbip)₂(bbi)₂(H₂O)]·2H₂O}_n (2) and {[Co₂(tbip)₂(bbi)₂]·2H₂O}_n (3), were prepared through hydrothermal reactions of Cu(II) and Co(II) acetate with H₂mip or H₂tbip (H₂mip = 5-methyl isophthalic acid and H₂tbip = 5-tert-butyl isophthalic acid) and the flexible ligand bbi (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)). All these complexes were structurally characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 exhibits a 3D network, which are constructed from 2D carboxylate layer and bbi pillar. Complex 2 possesses a 2D layer structure, and exists extensive hydrogen-bonding interactions, while complex 3 is constructed from 2D layers which consists of alternating left- and right-handed helical chains, and further assembled to form a 3D framework by hydrogen-bonding interactions. The thermal stabilities of the corresponding complexes have been briefly investigated. In addition, dominant antiferromagnetic coupling was observed in complex 1.     

Long-distance magnetic coupling in dinuclear copper(II) complexes with oligo-para-phenylenediamine bridging ligands

Two novel dinuclear copper(II) complexes of formulae [Cu₂(tren)₂(bpda)](ClO₄)₄ (2) and [Cu₂(tren)₂(tpda)](ClO₄)₄ (3) containing the tripodal tris(2-aminoethyl)amine (tren) terminal ligand and the 4,4′-biphenylenediamine (bpda) and 4,4″-p-terphenylenediamine (tpda) bridging ligands have been synthesized and structurally, spectroscopically, and magnetically characterized. Their experimentally available electronic spectroscopic and magnetic properties have been reasonably reproduced by DFT and TDDFT calculations. Single crystal X-ray diffraction analysis of 2 shows the presence of dicopper(II) cations where the bpda bridging ligand adopts a bismonodentate coordination mode toward two [Cu(tren)]²⁺ units with an overall non-planar, orthogonal anti configuration of the N-Cu-N threefold axis of the trigonal bipyramidal Cu^II ions and the biphenylene group. The electronic absorption spectra of 2 and 3 in acetonitrile reveal the presence of four moderately weak d-d transitions characteristic of a slightly distorted trigonal bipyramid stereochemistry of the Cu^II ions. TDDFT calculations on 2 identify these transitions as those taking place between the four lower-lying, doubly occupied a₂ (d_yz)², b₂ (d_xz)², b₁ (d_xy)², and a₁ (d_x²-y²)² orbitals and the upper, singly occupied a₁ (d_z²)¹ orbital of each trigonal bipyramidal Cu^II ion. Variable-temperature magnetic susceptibility measurements of 2 and 3 show the occurrence of moderate (J = −8.5 cm⁻¹) to weak intramolecular antiferromagnetic couplings (J = −2.0 cm^-1) [H = −JS₁·S₂ with S₁ = S₂ = S_Cu = ½] inspite of the relatively large copper-copper separation across the para-substituted biphenylene- (r = 12.3 Å) and terphenylenediamine (r = 16.4 Å) bridges, respectively. DFT calculations on 2 and 3 support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction between the two unpaired electrons occupying the d_z² orbital of each trigonal bipyramidal Cu^II ion through the predominantly π-type orbital pathway of the oligo-p-phenylenediamine bridges, as reported earlier for the parent compound [Cu₂(tren)₂(ppda)](ClO₄)₄·2H₂O (1) with the 1,4-phenylenediamine (ppda) bridging ligand. Finally, a rather slow exponential decay of the antiferromagnetic coupling (-J) with the number of phenylene repeat units, -(C₆H₄)_n- (n = 1-3), has been found both experimentally and theoretically along this series of oligo-p-phenylenediamine-bridged dicopper(II) complexes. These results further support the ability of linear π-conjugated oligo-p-phenylene spacers to transmit the exchange interaction between the unpaired electrons of the two Cu^II centers with intermetallic distances in the range of 7.5-16.4 Å.     

Structure and properties of two polymorphs of tetra-n-butylammonium bis(maleonitriledithiolato)platinate(1−)

Structural determination of tetra-n-butylammonium bis(maleonitriledithiolato)platinate(1−), a polymorphic compound, revealed that one polymorph consists of a columnar arrangement of dimers of the anion and is isomorphous with a corresponding nickelate complex. In contrast to the nickelate complex, the complex exhibited no spin-Peierls transition; strong antiferromagnetic interactions were observed between the anions due to dimerization in the column. The other polymorph consists of a tetramer unit of the anion.     

Syntheses, crystal structures and magnetic properties of 1D and 2D cobaltous coordination polymers with mixed ligands

Two new Co(II) coordination polymers with mixed ligands, {[Co(BTA)_0.5(DBI)₂]·DBI·H₂O}_n (1) and [Co(PDA)(DBI)(H₂O)]_n (2) (H₄BTA = benzene-1,2,4,5-tetracarboxylic acid; H₂PDA = 2,2′-(1,2-phenylene)diacetic acid; DBI = 5,6-dimethyl-1H-benzoimidazole) have been synthesized under hydrothermal conditions, respectively. Both of them are characterized by elemental analyses, powder X-ray diffraction, thermogravimetric analysis, single-crystal X-ray diffraction, and magnetic susceptibilities. In 1, the Co(II) ions are four-coordinated and lie in distorted tetrahedron coordination environment. 1D ladder-like chain structure is formed by the bridging BTA⁴⁻ ligand. In 2, the Co(II) ions are in slightly distorted octahedral coordination geometry, and linked by PDA²⁻ ligand exhibiting a 2D layer structure. Temperature-dependent magnetic susceptibility measurements of 1 and 2 revealed that there are antiferromagnetic interactions between Co(II) ions.     

Frequency domain magnetic resonance and magnetic circular dichroism studies on Ni4 cubane molecular nanomagnets: A magnetic anisotropy investigation

A study of the magnetic anisotropies of three Ni cubane single-molecule magnets (SMM), [Ni(hmp)(MeOH)Cl]₄·H₂O (1·H₂O) (hmpH = (2-hydroxymethyl)pyridine) [Ni(hmp)(dmb)Cl]₄ (2) (dmb = 3,3-dimethylbutanol) and [Ni(hmp)(dmp)Cl]₄ (3) (dmp = 2,2-dimethylpropanol) is reported. Frequency domain magnetic resonance spectroscopic (FDMRS) studies on 1, 2 and 3 as powder pellets reveal zero-field splitting (ZFS) for the spin ground states of these compounds in the solid state. The ZFS of the complexes 1 and 2 were determined and the presence of different molecular species was found in both complexes while only one species was found in 3. The nesting of the variable temperature variable field (VTVH) curves observed from magnetic circular dichroism (MCD) measurements on 1 in solution confirms the presence of ZFS. Virtually all the bands observed in the magnetic circular dichroism spectra possess the same sign, which may be related to the ferromagnetic exchange coupling. In addition, MCD measurements of a dilute solution demonstrate the molecular origin of the magnetic anisotropy in 1.     

Efficient biosynthesis of uridine diphosphate glucose from maltodextrin by multiple enzymes immobilized on magnetic nanoparticles

Uridine diphosphate glucose (UDP-Glc) serves as a glucosyl donor in many enzymatic glycosylation processes. This paper describes a multiple enzyme, one-pot, biocatalytic system for the synthesis of UDP-Glc from low cost raw materials: maltodextrin and uridine triphosphate. Three enzymes needed for the synthesis of UDP-Glc (maltodextrin phosphorylase, glucose-1-phosphate thymidylytransferase, and pyrophosphatase) were expressed in Escherichia coli and then immobilized individually on amino-functionalized magnetic nanoparticles. The conditions for biocatalysis were optimized and the immobilized multiple-enzyme biocatalyst could be easily recovered and reused up to five times in repeated syntheses of UDP-Glc. After a simple purification, approximately 630 mg of crystallized UDP-Glc was obtained from 1 l of reaction mixture, for a moderate yield of around 50% (UTP conversion) at very low cost.     

Cryopreservation of periodontal ligament cells with magnetic field for tooth banking

The purpose of this study was to establish a long-term tooth cryopreservation method that can be used for tooth autotransplantation. Human periodontal ligament (PDL) cells were frozen in 10% dimethyl sulfoxide (Me₂SO) using a programmed freezer with a magnetic field. Cells were cryopreserved for 7 days at −150 °C. Immediately after thawing, the number of surviving cells was counted and the cells were cultured; cultured cells were examined after 48 h. Results indicated that a 0.01 mT of a magnetic field, a 15-min hold-time, and a plunging temperature of −30 °C led to the greatest survival rate of PDL cells. Based on these findings, whole teeth were cryopreserved under the same conditions for 1 year. The organ culture revealed that the PDL cells of cryopreserved tooth with a magnetic field could proliferate as much as a fresh tooth, although the cells did not appear in the cryopreserved tooth without a magnetic field. Histological examination and the transmission electron microscopic image of cryopreserved tooth with a magnetic field did not show any destruction of cryopreserved cells. In contrast, severe cell damage was seen in cells frozen without a magnetic field. These results indicated that a magnetic field programmed freezer is available for tooth cryopreservation.