Structure and properties of cobalt ortho-phenylenediacetate coordination polymers with rigid dipyridyl ligands

Divalent cobalt coordination polymers containing both ortho-phenylenediacetate (ophda) and rigid dipyridyl ligands 4,4′-bipyridine (bpy) or 1,2-bis(4-pyridyl)ethylene (dpee) display different topologies depending on carboxylate binding mode, tether length, and inclusion of charged species. [Co(ophda)(H₂O)(dpee)]_n (1) displays a common (4,4) grid layer motif. Use of the shorter bpy tether afforded {[Co₂(ophda)₂(bpy)₃(H₂O)₂][Co(bpy)₂(H₂O)₄](NO₃)₂·2bpy·7H₂O}_n (2) or [Co(ophda)(bpy)]_n (3) depending on cobalt precursor. Compound 2 manifests 5-connected [Co₂(ophda)₂(bpy)₃(H₂O)₂]_n pillared bilayer slabs with rare 4⁸6² SnS topology and entrained [Co(bpy)₂(H₂O)₄]²⁺ complex cations. The 3-D coordination polymer 3 has an uncommon 4,6-connected binodal (4⁴6²)(4⁴6¹⁰8) fsc topology, and shows ferromagnetic coupling (J = +1.5(2) cm⁻¹) along 1-D spiro-fused [Co(OCO)₂]_n chain submotifs.     

Crystal structures and magnetic properties of Ni-bisdithiolene complexes with decamethylmetallocenium cations

Three new compounds of formula (1), (2), and (3) have been synthesised, and structurally and magnetically characterised (dmit²⁻ = 1,3-dithiol-2-thione-4,5-dithiolato; dmid²⁻ = 1,3-dithiol-2-one-4,5-dithiolato). Their structural features and magnetic behaviours are compared with those of and . The result of this is that the interactions between the Ni(dmit)₂ units in 1 are of ferromagnetic-type, as suggested previously for . The change from acetonitrile to acetone when going from to 2 results in stronger ferromagnetic intermolecular interactions. This better cooperativity is due to a significant increase of the number of contacts between the various moieties within the . On the contrary, the inclusion of larger solvents such as benzonitrile in this type of complexes results in a totally different structural arrangement, which leads to an antiferromagnetic behaviour for 3.     

A ferromagnetically coupled copper(II) trinuclear secondary building unit as precursor for the preparation of molecule-based magnets

The compounds 3D-{(Ph₄P)₂[ZnCu₃(Hmesox)₃Cl]·2.5H₂O} (1) and 3D-{(Ph₄P)₂[NiCu₃(Hmesox)₃Cl]·2.5H₂O} (2) have been prepared and their structure and magnetic properties investigated (H₄mesox = mesoxalic acid, 2-dihydroxymalonic acid). The compounds are obtained by means of the same procedure followed to prepare 3D-{(Ph₄P)₂[MnCu₃(Hmesox)₃Cl]·3.5H₂O}and 3D-{(Ph₄P)₂[CoCu₃(Hmesox)₃Cl]}, to which 1 and 2 are isostructural as deducted from the X-ray powder diffraction patterns and IR spectra. During the synthesis the {Cu₃(Hmesox)₃Cl}⁴⁻ unit is generated which acts as ferromagnetically coupled secondary building unit (SBU) to give 3D chiral networks with (10,3)-a topology, the [Zn{Cu₃(C₃HO₆)₃Cl}]²ⁿ⁻ and [Ni{Cu₃(C₃HO₆)₃Cl}]²ⁿ⁻, in 1 and 2, respectively. The tetraphenylphosphonium cations are located in the voids of the 3D anion framework giving a supramolecular 3D cation net with the same (10,3)-a topology as the anion framework and both can be thought of forming interpenetrating supramolecular and covalent (10,3)-a nets. Because of the different nature of the interpenetrated 3D (10,3)-a frameworks a single crystal of 1 and 2 is chiral and enantiopure. The analysis of the magnetic properties in 1 by means of the isotropic spin Hamiltonian, H = −J(S₁S₂ + S₂S₃ + S₁S₃), reveal a ferromagnetic coupling with J = +11.2 cm⁻¹ in the copper(II) trinuclear unit of 1. Compound 2 exhibits long-range magnetic ordering with a T_c of 7.0 K due to a ferrimagnetic coupling between the ferromagnetically coupled copper(II) ions of the trinuclear unit, antiferromagnetically coupled to the Ni(II) ions.     

EPR and magnetic properties of [Mn(μ-Cl)2(bpy)]n: An unusual ferromagnetic interaction in a Mn(II) chloro-bridged polymer

The study of the magnetic properties and EPR spectra of the one-dimensional bis(μ-chloro) Mn(II) polymer [Mn(μ-Cl)₂(bpy)]_n (1) (bpy = 2,2′-bipyridine) is reported. Magnetic susceptibility measurements reveal a weak ferromagnetic interaction between the Mn(II) ions (J = +0.19 cm⁻¹). This is the first polymer of six-coordinated Mn(II) ions with a [Mn₂(μ-Cl)₂]²⁺ magnetic repeating unit, showing a ferromagnetic interaction. The coordination octahedra are elongated in the Cl?Cl direction and the elongation axes are parallel along the chain. Extended Hückel calculations show that the octahedra share an equatorial-apical edge, with the equatorial plane being parallel, and perpendicular to the Mn₂(μ-Cl)₂. Due to this disposition, the overlap through the chloride bridges is small, so the antiferromagnetic contribution must also be small and, therefore, a ferromagnetic behaviour is observed. The EPR spectra of a polycrystalline sample of 1 at different temperatures are also reported. A variation of the bandwidth with temperature is observed, which could be because this ferromagnetic interaction is weak: above 150 K the dipolar interaction is the predominant effect, while below 150 K the magnetic exchange interaction dominates.     

Ferromagnetic trinuclear carbonato-bridged and tetranuclear hydroxo-bridged Cu(II) compounds with 4,4′-dimethyl-2,2′-bipyridine as ligand. X-ray structure, spectroscopy and magnetism

A controlled synthesis, characterisation and single-crystal X-ray analysis of two novel copper(II) compounds with the ligand 4,4′-dimethyl-2,2′-bipyridine (abbreviated dmbipy) is described. In a CO₂ atmosphere, with sodium hydroxide added, the carbonato-bridged triangular trinuclear compound [Cu₃(dmbipy)₆(μ₃-CO₃)](BF₄)₄(C₂H₅OH)(H₂O) (1) is obtained. Compound 1 crystallises in the monoclinic space group P2₁/n with a=16.169(6), b=23.351(11), c=21.312(7) Å, β=91.26(3), Z=4. The three copper ions are connected via the oxygen atoms from the symmetrically bridging carbonato group, resulting in a triangular array of copper atoms. Each copper has a distorted square-pyramidal environment with a basal plane formed by three nitrogen atoms of the two chelating bipyridine groups and the oxygen atom of the bridging carbonato group (Cu-N/O distances about 2.0 Å). The apical position at each copper is occupied by the fourth nitrogen atom of the bipyridines with distances varying from 2.100(11) to 2.146(11) Å. In all other experimental conditions the tetranuclear hydroxo-bridged compound [Cu₄(dmbipy)₄(μ₃-OH)₂(μ-OH)₂(H₂O)₂](BF₄)₄(H₂O)₄ (2) is obtained. Compound 2 crystallises in the monoclinic space group P2₁/c with a=13.274(8), b=21.685(7), c=11.266(7) Å, β=107.71(4), Z=2. The structure consists of two bis(hydroxo)-bridged dinuclear planar units which are connected with long Cu-O bonds to form a tetranuclear unit. Each Cu ion has a similar square-pyramidal coordination geometry: the equatorial plane of each Cu ion consists of two nitrogen atoms of the dmbipy ligand (Cu-N distances 1.945-2.003 Å), and two bridging hydroxo oxygen atoms (Cu-O distances 1.945-1.973 Å). The apical position of Cu1 is occupied by an oxygen atom of a water molecule with a distance of 2.262 Å. The second copper atom, Cu2, has the apical position occupied by an oxygen atom of a bridging hydroxo group at a distance of 2.349 Å; this bond is responsible for the formation of the tetranuclear unity. Compound 1 exhibits a ferromagnetic interaction between the copper ions with a J=29.3 cm⁻¹ and a very weak ferromagnetic intercluster interaction with zj′=2.4 cm⁻¹. Compound 2 also exhibits a ferromagnetic interaction between the copper ions with a J=31.1 cm⁻¹ and an overall magnetic interaction between the two dimeric units J′=8.76 cm⁻¹     

Chiral and achiral layered divalent metal aromatic ortho-dicarboxylate coordination polymers with bis(4-pyridylmethyl)piperazine ligands: Luminescent behavior and magnetic properties

Four divalent metal coordination polymers containing bis(4-pyridylmethyl)piperazine (4-bpmp) and the ortho-dicarboxylate ligands phthalate (pht) or 4-methylphthalate (mpht) have been prepared by solvent diffusion or hydrothermal methods. {[Cu₂(pht)₂(H4-bpmp)₂(H₂O)₂](NO₃)₂·H₂O}_n (1) and {[Cu₂(pht)₂(H4-bpmp)₂(H₂O)₂](SO₄)·2H₂O}_n (2) possess chiral cationic layer motifs formed by the junction of [Cu(H₂O)(pht)]_n chains by tethering curled-conformation H4-bpmp⁺ ligands. {[Co(pht)(H₂O)(4-bpmp)]·5.5H₂O}_n (3) displays a (4,4) grid constructed from anti-syn carboxylate-bridged {Co₂(H₂O)₂(pht)₂} dimeric clusters linked by open-conformation 4-bpmp ligands. {[Cd₂(mpht)₂(H₂O)₂(4-bpmp)(H4-bpmp)]ClO₄·4H₂O}_n (4) manifests cationic layered motifs based on neutral [Cd₂(H₂O)₂(mpht)₂] dinuclear units with {CdOC₄O}₂ 12-membered circuits, linked by open-conformation 4-bpmp and H4-bpmp⁺ ligands. Variable-temperature magnetic data indicate likely concomitant zero-field splitting and ferromagnetic coupling in 3. Violet light emission is observed when 4 is subjected to ultraviolet irradiation.     

Ferromagnetic Cu8 pinwheel clusters as building blocks for larger magnetic networks: Long-range structural and magnetic ordering

The structural and magnetic properties of a series of Cu₈ pinwheel clusters with the tritopic ligands 2POMP, 2POPP, Cl2POMP and SEt2POMP are described. Two different ligand binding modes lead to two different arrangements of Cu-Cu bridge connections within the pinwheel. In one case, all the Cu(II) centers are bridged by hydrazone oxygen atoms, and the Cu-Cu distances are all similar (∼4 Å). In the other case, the central Cu(II) centers are bridged by hydrazone oxygen atoms, while the peripheral Cu²⁺ cations are bridged to the core by diazine (N-N) groups. In both cases, the bridges are orbitally strictly orthogonal and so ferromagnetic exchange dominates. In the complex [(2POMP-2H)₄Cu₈Br₆](CuBr₄)(H₂O)₁₁ (1) bromide ions bridge the peripheral Cu(II) centers of adjacent Cu₈ pinwheel cluster molecules forming a 2D network with additional ions occupying cavities in the lattice. In [(Cl2POMP-2H)₄Cu₈(N(CN)₂)₈](H₂O)₉(CH₃CN) (3), nitrogen atoms of the coordinated dicyanamide (dca) ions bound to the peripheral Cu(II) centers interact with ligand bound chlorine atoms of adjacent molecules to form stacks of pinwheels. In [(Set2POMP-2H)₄Cu₈(H₂O)₈](PF₆) ₈(CH₃OH)₆(CH₃CN)_1.5 (4) relatively short S?S contacts exist between pinwheels and cause stacking in the extended structure. Surprisingly, there is evidence for long-range magnetic interactions in 3 via the intermolecular contacts, but not in 1, which has direct bonding between pinwheel subunits. Exchange integrals within the pinwheel clusters fall in the rangeJ = 4-7 cm⁻¹.