Showing papers by "Cameron J. Kepert published in 2001"

Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni2(4,4'-bipyridine)3(NO3)4: guest modification of host sorption behavior.

Abstract: This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a compensation effect. The results are discussed in terms of reversible adsorbate/adsorbent (guest/host) structural changes and interactions and the adsorption mechanism. The paper contains the first evidence of specific interactions between guests and functional groups leading to structural change in flexible porous coordination polymer frameworks.

Layered Cobalt Hydroxysulfates with Both Rigid and Flexible Organic Pillars: Synthesis, Structure, Porosity, and Cooperative Magnetism

Abstract: The synthesis and characterization of two members of a family of porous magnetic materials is described. The structures of Co4(SO4)(OH)6(C2N2H8)0.5*3H2O and Co4(SO4)(OH)6(C6N2H12)0.5*H2O and their thermal stability can be tailored via the choice of organic pillar. The interactions between the pillaring agent and the compositionally complex inorganic layer are discussed. The influences of two pillaring agents i.e., the flexible ethylenediamine and the relatively rigid 1,4-diazabicyclo[2,2,2]octane, on thermal stability, rigidity upon guest loss, and magnetic behavior of the pillared solids are compared. The magnetism of the pillared layered cobalt hydroxides is complex due to the influences of multiple metal sites, inter- and intralayer exchange, spin-orbit coupling, and geometrical frustration. The wide variety of potential pillars, oxyanions, and possible metal substitutions at the octahedral and tetrahedral sites offers the possibility of tailoring the magnetic and porous properties of these materials.

Muon-spin-rotation and magnetization study of metal-organic magnets based on the dicyanamide anion

Abstract: We report the results of a study of the metal-organic magnets MII[N(CN)2]2, where MII = Ni, Co and Mn, using bulk magnetization and muon-spin relaxation (µSR). Implanted muons are sensitive to the onset of long-range magnetic order in each of these materials and strong muon-spin relaxation is observed in the paramagnetic state due to low-frequency fluctuations of the electronic moments in the 109-1010 Hz range. The size of the muon-spin relaxation in the paramagnetic state can be related to the magnitude of the transition-metal-ion moment. Very strongly damped oscillations are observed below the magnetic transition temperature in Co[N(CN)2]2.

MEM(TCNQ)2 at room temperature and 10 K, and the absence of a spin-Peierls transition.

Abstract: Precise X-ray determinations of the crystal structure of the 1:2 complex of N-ethyl-N-methyl­morpholinium and 7,7,8,8-tetra­cyano-p-quinodi­methanide, abbreviated as MEM–TCNQ or MEM(TCNQ)2 (C7H16NO+·2C12H4N40.5−), have been performed at 293 and at 10 K. Evidence for the expected spin-Peierls transition at 19 K is not found, and this may follow from radiation damage to the crystal or from insufficient equipment sensitivity.