Investigations of the Cobalt Hexamine Uranyl Carbonate System: Understanding the Influence of Charge and Hydrogen Bonding on the Modification of Vibrational Modes in Uranyl Compounds

Hydrogen bonding networks within hexavalent uranium materials are complex and may influence the overall physical and chemical properties of the system. This is particularly true if hydrogen bonding takes places between the donor and the oxo group associated with the uranyl cation (UO22+). In the current study, we evaluate the impact of charge-assisted hydrogen bonding on the vibrational modes of the uranyl cation using uranyl tricarbonate [UO2(CO3)(3)](4- )interactions with [Co(NH3)(6)](3+) as the model system. Herein, we report the synthesis and structural characterization of five novel compounds, [Co(NH3)(6)]Cl(CO3) (Co_Cl_CO3), [Co(NH3)(6)](4)[UO2(CO3)(3)](3)(H2O)(11.67) (Co4U3), [Co(NH3)(6)](3)[UO2(CO3)(3)](2)Cl (H2O)(7.5) (Co3U2_Cl), [Co(NH3)(6)](2)[UO2(CO3)(3)]Cl2 (Co2U_Cl), and [Co(NH3)(6)](2)[UO2(CO3)(3)]CO3 (Co2U_CO3), which contain differences in the crystalline packing and extended hydrogen bonding networks. We show that these slight changes in the supramolecular assembly and hydrogen bonding networks result in the modification of modes as observed by infrared and Raman spectroscopy. We use density functional theory calculations to assign the vibrational modes and provide an understanding about how uranyl bond perturbation and changes in hydrogen bonding interactions can impact the resulting spectroscopic signals.

Automated summary

In this study, the impact of hydrogen bonding networks on the vibrational modes of the uranyl cation in hexavalent uranium materials was investigated. The synthesis and structural characterization of five novel compounds revealed that slight changes in crystalline packing and hydrogen bonding networks result in modifications of the vibrational modes, as observed by infrared and Raman spectroscopy.