High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Critical Analysis on the Structural and Magnetic Properties of Bulk and Nanocrystalline Cu-Fe-O

Nanocrystalline and bulk samples of “Fe”-doped CuO were prepared by coprecipitation and ceramic methods. Structural and compositional analyses were performed using X-ray diffraction, SEM, and EDAX. Traces of secondary phases such as CuFe2O4, Fe3O4, and α-Fe2O3 having peaks very close to that of the host CuO were identified from the Rietveld profile analysis and the SAED pattern of bulk and nanocrystalline Cu0.98Fe0.02O samples. Vibrating Sample Magnetometer (VSM) measurements show hysteresis at 300 K for all the samples. The ferrimagnetic Neel transition temperature () was found to be around 465°C irrespective of the content of “Fe”, which is close to the value of cubic CuFe2O4. High-pressure X-Ray diffraction studies were performed on 2% “Fe”-doped bulk CuO using synchrotron radiation. From the absence of any strong new peaks at high pressure, it is evident that the secondary phases if present could be less than the level of detection. Cu2O, which is diamagnetic by nature, was also doped with 1% of “Fe” and was found to show paramagnetic behavior in contrast to the “Fe” doped CuO. Hence the possibility of intrinsic magnetization of “Fe”-doped CuO apart from the secondary phases is discussed based on the magnetization and charge state of “Fe” and the host into which it is substituted.