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

Three octacyanometallate‐based hetero‐bimetallic complexes, [ Ln (H 2 O) 4 (CH 3 CN) 2 ][ M (CN) 8 ] · CH 3 CN [ 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 Ln 2 M 2 (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.