Three Octacyanometallate‐Based LnIII–MV (Ln = La,Ce; M = Mo,W) Bimetallic Assemblies with a One‐Dimensional Rope‐Ladder Chain Structure

Three octacyanometallate‐based hetero‐bimetallic complexes, [Ln(H₂O)₄(CH₃CN)₂][M(CN)₈] · CH₃CN [Ln = La, M = Mo( 1 ), W( 2 ); Ln = Ce, M = W( 3 )], were synthesized and characterized structurally. Single‐crystal X‐ray analysis reveals that 1 – 3 are isomorphous and consist of infinite one‐dimensional (1D) 3,3 rope‐ladder chains, in which the 12‐membered puckered square Ln₂M₂(CN)₄ is the basic building unit. The 1D chains are further linked through interchain hydrogen bonds, resulting in a three‐dimensional (3D) supramolecular network.