Cyano-bridged 2D bimetallic 4f-3d arrays with monolayered stair-like, brick-wall-like, or bilayered topologies - rational syntheses and crystal structures

摘要

Three series of fourteen cyano-bridged 2D Ln~(III)-Fe~(III) or Ln~(III)Co~(III) complexes, [Ln(dmso)_2(H _2O)(μ-CN)_4Fe(CN)_2]_n [Ln = Gd (1) and Er (2)], [Ln(dmso)_2(H_2O)_3(μ-CN) _3M(CN)_3]., [La-Fe (3) and Pr-Co (4)], [Ln(dmf) _2(H_2O)_3(μ-CN)3M(CN)_3· nH_2O [NdFe (S), Gd-Fe (6), Dy-Fe (7), Er-Fe (8), Nd-Co (9), and GdCo (10)], [Ln(dmso)_2(H_2O)_3(μ-CN) _3Co(CN)_3]_n ·nH_2O [Ln = Pr (11), Nd (12), and Sm (13)], and [Er(dmf)(H_2O)_3(μ-CN) _4Co(CN)_2]_n·H_2O (14) (dmso = dimethyl sulfoxide; dmf = N,N'-dimethylformamide) were rationally prepared by the ball-milling method, and their structures were characterized. The crystal structures of 1 and 2 reveal a sevenfold coordination environment of the Ln ~(3+) ions and a 2D stair-like structure, while those of 3-13 show an eightfold coordination environment of the Ln~(3+) ions and a 2D monolayered brick-walllike topology and that of 14 exhibits an eightfold coordination environment of the Er~(3+) ions and a 2D bilayered topology. The relationship between the crystal structures and the controllable synthesis was also discussed.