Four cerium compounds - (HPy)2[CeCl6]·2(HPyCl) (Ce1-1), (HPy)2[CeCl6] (Ce1-2), (HPy)m[Ce38O56-x(OH)xCl50(H2O)12]·nH2O (Ce38), and (HPy)m[Ce52O80-x(OH)xCl59(H2O)17]·nH2O (Ce52) - were crystallized from acidic aqueous solutions using pyridinium (HPy) counterions. The latter consists of two unique cerium oxide nanoclusters that are built from 52 metal ions and represents the largest chloride capped {CeIII/IVO} and/or {MIVO} (M = Ce, Th, U, Np, Pu) nanocluster that adopts the fluorite-type structure of MO2 that has been reported.

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear-fuel cycles. Herein, we describe the preparation of (NBu4 )Am[S2 P((t) Bu2 C12 H6 )]4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., Nd(III) ) and an isoelectronic one (Eu(III) ). The results include the first measurement of an Am-S bond length, with a mean value of 2.921(9) Å, by single-crystal X-ray diffraction. Comparison with the Eu(III) and Nd(III) complexes revealed subtle electronic differences between the complexes of Am(III) and the lanthanides.