Paul Goddard

Abstract:

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.

Abstract:

The magnetic ground state of two isostructural coordination polymers (i) the quasi two-dimensional S = 1/2 square-lattice antiferromagnet [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$; and (ii) a new compound [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, were examined with neutron powder diffraction measurements. We find the ordered moments of the Heisenberg S = 1/2 Cu(II) ions in [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ are 0.6(1)$\mu_{B}$, whilst the ordered moments for the Co(II) ions in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ are 3.02(6)$\mu_{B}$. For Cu(II), this reduced moment indicates the presence of quantum fluctuations below the ordering temperature. We show from heat capacity and electron spin resonance measurements, that due to the crystal electric field splitting of the S = 3/2 Co(II) ions in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, this isostructual polymer also behaves as an effective spin-half magnet at low temperatures. The Co moments in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ show strong easy-axis anisotropy, neutron diffraction data which do not support the presence of quantum fluctuations in the ground state and heat capacity data which are consistent with 2D or close to 3D spatial exchange anisotropy.

Abstract:

We report a Co(III) 2 Dy(III) complex, which shows single-ion-magnet behaviour. AC susceptibility data of this compound reveals the presence of slow relaxation of the magnetization in zero-field below 15 K. The relaxation barrier is 88 K.