Four new compounds, [Cd(5-aip)(bpy)]·1.5DMA (1), [Cu(5-aip)(bpy)]·1.3DMA (2), [Co(5-aip)(bpy)]·1.6DMA (3), and [Cd(5-aip)(bpy)0.5(H2O)]·1.3DMA (4), based on 5-aminoisophthalic acid and 4,4′-bipyridine, have been synthesized by the solvothermal method and structurally determined using single crystal X-ray diffraction. Compounds 1–3 are structurally similar and show non-interpenetrating three-dimensional (3D) pillar-layer frameworks, while compound 4 displays a two-dimensional (2D) (3,4)-connected parallel non-interpenetrating architecture. In all these compounds, 1D rectangular channels are observed and the ligand 5-aminoisophthalic acid exhibits three kinds of coordination modes. Furthermore, 1 displays a single-crystal-to-single-crystal transformation when immersed in a methanol solution. More significantly, 1 can absorb and deliver I2 molecules by means of its channels, and could induce a reversible luminescent transformation from quenching to the initial state. The luminescent properties of 1 and 4 have also been studied.
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