Photoluminescent Lanthanide(III) Single-Molecule Magnets in Three-Dimensional Polycyanidocuprate(I)-Based Frameworks.

Three-dimensional bimetallic cyanido-bridged frameworks, [LnIII (2,2'-bipyridine N,N'-dioxide)2 (H2 O)][CuI 2 (CN)5 ]⋅5 H2 O (Ln=Dy, 1; Yb, 2), are reported. They exhibit the effect of slow relaxation of magnetization, leading to a magnetic hysteresis loop, and sensitized visible-to-near-infrared photoluminescence. Both physical properties are related to the eight-coordinated lanthanide(III) complexes embedded in the unprecedented coordination skeleton composed of symmetry-breaking polycyanidocuprate linkers. The three-dimensional d-f cyanido-bridged network was shown to serve as an efficient coordination scaffold to achieve emissive lanthanide single-molecule magnets.