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Three novel uranyl selenate and sulfate oxysalts templated by protonated azetidine molecules, [ Az H] + , and its ring-opened counterpart 1-azetidinepropanamine, [ Az H(CH 2 ) 3 NH 3 ] 2+ , have been prepared and studied by X-ray structural analysis. Conformations of azetidinium cations were analysed by means of infrared vibrational assignments supported by the DFT calculations. Crystallization of [ Az H] 2 [(UO 2 ) 2 (SeO 4 ) 3 (H 2 O)] ( I ) from highly acidic solutions suggests that low pH does not necessarily result in the opening of azetidine ring. [ Az H(CH 2 ) 3 NH 3 ][(UO 2 ) 2 (SeO 4 ) 3 (H 2 O)](H 2 O) ( II ) and [ Az H(CH 2 ) 3 NH 3 ](H 5 O 2 )[(UO 2 ) 2 (SO 4 ) 3 (HSO 4 )] ( III ) are the first structurally characterized crystalline compounds bearing isolated ring-opened azetidine moiety. [ABSTRACT FROM AUTHOR]

Cs 2 [(An O 2) 2 (T O 4) 3 ] (where An ​= ​U, Np; T ​= ​S, Se, Cr, Mo) is a remarkable family of actinide-bearing compounds due to the surprising persistence of its structure type despite the substitutions in actinide and oxyanion sites. Cesium uranyl sulfate and selenate compounds have been analysed using high-temperature powder X-ray diffraction, Raman and luminescence spectroscopy techniques; in addition, high-temperature oxide-melt calorimetry studies had been carried out to derive the enthalpies of formation of both compounds. The crystal structures of all six known isotypic compounds have been compared to reveal specific geometric parameters, which results in differences of thermal behavior and spectra. Chemical alteration in the An and T sites results in changes of the Cs+ coordination environment, which in turn leads to an increase of its influence on the layered structural units and the stability of the structure itself. These substitution mechanisms may be regarded as an example of the chemical composition selectivity for the preparation of compounds with the desired properties. The crystal chemistry review and properties of probably the most outstanding family of actinyl-bearing isotypic compounds Cs 2 [(An O 2) 2 (T O 4) 3 ] (where An ​= ​U, Np and T ​= ​S, Se, Cr, Mo), which is the only known to date example of structural type preservation with such a large diversity in chemical composition. Image 1 • Thermal behaviour of Cs uranyl sulfate and selenate was analysed. • Enthalpy of formation and luminescence properties of Cs uranyl sulfate and selenate were determined. • Crystal-chemical review of a family of Cs 2 [(An O 2) 2 (T O 4) 3 ] (An ​= ​U, Np; T ​= ​S, Se, Cr, Mo) compounds was prepared. [ABSTRACT FROM AUTHOR]