[H4Ni10(H2O)8Nb32O102]20−, representing the first high-nuclear nickel-cation-bridged polyoxoniobate, has been synthesized. It incorporates two [{Ni2O4}(H2O)2(Nb6O19)]12− and two [Ni3(H2O)2Nb10O34]12− subunits exhibiting a rhombus-like architecture. Furthermore, the solution behaviour was examined by electrospray ionization mass spectrometry and the magnetic properties in the low temperature range indicate the presence of ferromagnetic interactions.
