Syntheses, Crystal Structures, and the Phase Transformation of Octacyanometallate‐Based Ln III –W V Bimetallic Assemblies with Two‐Dimensional Corrugated Layers

The reactions between Ln(NO 3 ) 3 · n H 2 O and (Bu 3 NH) 3 [W(CN) 8 ] · H 2 O have led to two series of octacyanometallate‐based complexes: Ln(H 2 O) 5 [W(CN) 8 ] [Ln = La( 1 ), Pr( 2 ), Nd( 3 ), Eu( 4 ), Gd( 5 )] and Ln(H 2 O) 4 [W(CN) 8 ] [Ln = Ho( 6 ), Er( 7 ), Tm( 8 ), Lu( 9 )]. The crystal structures of 1 – 9 have two‐dimensional corrugated layers in which the Ln III and W V centres are linked in an alternating fashion. Thermogravimetric (TG) and powder XRD results reveal the presence of a phase transformation in the Ln III –W V system with increasing atomic number of the Ln III atoms.