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dc.contributor.advisorParsons, Simon
dc.contributor.advisorKamenev, Konstantin
dc.contributor.advisorMoggach, Stephen
dc.contributor.authorCameron, Christopher Alistair
dc.date.accessioned2015-02-23T14:15:46Z
dc.date.available2015-02-23T14:15:46Z
dc.date.issued2015-06-30
dc.identifier.urihttp://hdl.handle.net/1842/9952
dc.description.abstractPressure and temperature are two environmental variables that are increasingly being exploited by solid-state researchers probing structure-property relationships in the crystalline state. Modern high-pressure apparatus is capable of generating many billions of Pascals in the laboratory, and therefore can produce significantly greater alterations to crystalline materials than changes in temperature, which can typically be varied by only a few thousand Kelvin. Many systems such as single-molecule magnets exhibit interesting properties under low-temperature regimes that can be substantially altered with pressure. The desire by investigators to perform analogous single-crystal X-ray diffraction studies has driven the development of new high-pressure apparatus and techniques designed to accommodate low-temperature environments. [Ni(en)3][NO3]2 undergoes a displacive phase transition from P6322 at ambient pressure to a lower symmetry P6122/P6522 structure between 0.82 and 0.87 GPa, which is characterized by a tripling of the unit cell c axis and the number of molecules per unit cell. The same transition has been previously observed at 108 K. The application of pressure leads to a general shortening of O···H hydrogen bonding interactions in the structure, with the greatest contraction (24%) occurring diagonally between stacks of Ni cation moieties and nitrate anions. A novel Turnbuckle Diamond Anvil Cell designed for high-pressure low-temperature single-crystal X-ray experiments on an open-flow cryostat has been calibrated using the previously reported phase transitions of five compounds: NH4H2PO4 (148 K), ferrocene (164 K), barbituric acid dihydrate (216 K), ammonium bromide (235 K), and potassium nitrite (264 K). From the observed thermal differentials between the reported and observed transition temperatures a linear calibration curve has been constructed that is applicable between ambient-temperature and 148 K. Low-temperature measurements using a thermocouple have been shown to vary significantly depending on the experimental setup for the insertion wire, whilst also adding undesirable thermal energy into the sample chamber which was largely independent of attachment configuration. High-pressure low-temperature single-crystal X-ray diffraction data of [Mn12O12(O2CMe)16(H2O)4] (known as Mn12OAc) reveals a pressure-induced expulsion of the crystallized acetic acid from the crystal structure and resolution of the Jahn-Teller axes disorder between ambient pressure and 0.87 GPa. These structural changes have been correlated with high-pressure magnetic data indicating the elimination of a slow-relaxing isomer over this pressure range. Further application of pressure to 2.02 GPa leads to the expansion of these Jahn-Teller axes, resulting in an enhancement of the slow-relaxing magnetic anisotropy as observed in the literature. Relaxation of pressure leads to a resolvation of the crystal structure and re-disordering of the Jahn-Teller axes, demonstrating that this structural-magnetic phenomenon is fully reversible with respect to pressure. The space group of the Prussian blue analogue Mn3[Cr(CN)6].15H2O has been re-evaluated as R-3m between ambient pressure and 2.07 GPa using high-pressure single-crystal X-ray and high-pressure neutron powder data. Reductions in metal-metal distances and gradual distortions of the Mn octahedral geometry have been correlated with previously reported increases in Tc and declines in ferrimagnetic moment in the same pressure range. Increasing the applied pressure to 2.97 GPa leads to partial amorphization and results in a loss of long-range magnetic order as shown by the literature. The application of pressure (1.8 GPa) to the structure of K2[Pt(CN)4]Br0.24.3.24H2O (KCP(Br)) causes a reduction in the Pt intra-chain and inter-chain distances, and results in an enhancement of the overall conductivity under these conditions as demonstrated in the literature. Almost no changes occur to the high-pressure crystal structure upon cooling to 4 K, except in the Pt-Pt intra-chain distances which converge and suppress the Peierls distortion known to occur at 4 K, resulting in a comparatively greater electrical conductivity under these conditions.en
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en
dc.language.isoenen
dc.publisherThe University of Edinburghen
dc.relation.hasversionCameron, C. A., Allan, D. R., Kamenev, K., Moggach, S. A., Murrie, M. & Parsons, S. (2014). Z. Kristallogr. 229, 200-209.en
dc.subjecthigh pressureen
dc.subjectlow temperatureen
dc.subjectsingle-crystal X-ray diffraction studiesen
dc.titleHigh-pressure studies on molecular systems at ambient and low temperaturesen
dc.typeThesis or Dissertationen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD Doctor of Philosophyen


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