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Two poly-oxo cluster complexes of tetravalent neptunium (Np(iv)), Np38O56Cl18(bz)24(THF)8·nTHF and Np38O56Cl42(ipa)20·mipa (bz = benzoate, THF = tetrahydrofuran, and ipa = isopropanol), were obtained via solvothermal synthesis and structurally characterised by single-crystal X-ray diffraction. The {Np38} clusters are comparable to the analogous {U38} and {Pu38} motifs, filling the gap in this largest poly-oxo cluster series of tetravalent actinides.

{Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

{Np₃₈} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides