Two Cu coordination polymers [CuCl(pyz)](BF) 1 and [CuBr(pyz)](BF) 2 (pyz = pyrazine) were synthesized in the family of quasi two-dimensional (2D) [Cu(pyz)] magnetic networks. The layer connectivity by monatomic halide ligands results in significantly shorter interlayer distances. Structures were determined by single-crystal X-ray diffraction. Temperature-dependent X-ray diffraction of 1 revealed rigid [Cu(pyz)] layers that do not expand between 5 K and room temperature, whereas the expansion along the c-axis amounts to 2%. The magnetic susceptibility of 1 and 2 shows a broad maximum at ∼8 K, indicating antiferromagnetic interactions within the [Cu(pyz)] layers. 2D Heisenberg model fits result in J = 9.4(1) K for 1 and 8.9(1) K for 2. The interlayer coupling is much weaker with | J| = 0.31(6) K for 1 and 0.52(9) K for 2. The electron density, experimentally determined and calculated by density functional theory, confirms the location of the singly occupied orbital (the magnetic orbital) in the tetragonal plane. The analysis of the spin density reveals a mainly σ-type exchange through pyrazine. Kinks in the magnetic susceptibility indicate the onset of long-range three-dimensional magnetic order below 4 K. The magnetic structures were determined by neutron diffraction. Magnetic Bragg peaks occur below T = 3.9(1) K for 1 and 3.8(1) K for 2. The magnetic unit cell is doubled along the c-axis ( k = 0, 0, 0.5). The ordered magnetic moments are located in the tetragonal plane and amount to 0.76(8) μ/Cu for 1 and 0.6(1) μ/Cu for 2 at 1.5 K. The moments are coupled antiferromagnetically both in the ab plane and along the c-axis. The Cu g-tensor was determined from electron spin resonance spectra as g = 2.060(1), g = 2.275(1) for 1 and g = 2.057(1), g = 2.272(1) for 2 at room temperature.
We report the synthesis of pyrazine-pillared metal-organic frameworks (MOFs) generated through ligand substitution of the Group 6 metal hexacarbonyls. The obtained frameworks exhibit hexagonal pore channels with CO-plastered porewalls. This...
Tessellation of self-assembling molecular building blocks is a promising strategy to design metal-organic materials exhibiting geometrical frustration and ensuing frustrated physical properties. Appearing in two-dimensional quasiperiodic phases, tilings consisting of five-vertex nodes are regarded as approximants for quasicrystals. Unfortunately, these structural motifs are exceedingly rare due to the complications of acquiring five-fold coordination confined to the plane. Lanthanide ions display the sufficient coordinative plasticity, and large ionic radii, to allow their incorporation into irregular molecule-based arrays. We herein present the use of ytterbium(II) as a five-vertex node in a two-dimensional coordination solid, YbI2(4,4′-bipyridine)2.5. The semi-regular Archimedean tessellation structure verges on quasicrystallinity and paves the way for lanthanide-based metal-organic materials with interesting photonic and magnetic properties.
We report an extraordinary pressure dependence of the magnetic interactions in the metal-organic system [CuF_{2}(H_{2}O)_{2}]_{2}pyrazine. At zero pressure, this material realizes a quasi-two-dimensional spin-1/2 square-lattice Heisenberg antiferromagnet. By high-pressure, high-field susceptibility measurements we show that the dominant exchange parameter is reduced continuously by a factor of 2 on compression. Above 18 kbar, a phase transition occurs, inducing an orbital re-ordering that switches the dimensionality, transforming the quasi-two-dimensional lattice into weakly coupled chains. We explain the microscopic mechanisms for both phenomena by combining detailed x-ray and neutron diffraction studies with quantitative modeling using spin-polarized density functional theory.
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