Diverse assemblies of the (4,4) grid layers exemplified in Zn(II)/Co(II) coordination polymers with dual linear ligands

Abstract

Diverse (4,4) grid layers are exemplified in five two-dimensional coordination polymers with dual µ{sub 2}-bridged ligands, namely, ([Zn(cbaa)(bpp)]·H{sub 2}O){sub n} (1), [Zn{sub 2}(cbaa){sub 2}(bpy)]{sub n} (2), [Co{sub 2}(cbaa){sub 2}(bpp){sub 2}]{sub n} (3), [Co(cbaa)(bpp)]{sub n} (4), and [Co(bdaa)(bpp)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}cbaa=4-carboxybenzeneacetic acid, bpp=1,3-di(4-pyridyl)propane, bpy=4,4′-bipyridyl, and H{sub 2}bdaa=1,4-benzenediacrylic acid). For 1, two (4,4) grid layers with [ZnN{sub 2}O{sub 2}] tetrahedron as the node are held together by lattice water forming a H-bonding bilayer. Individual (4,4) grid layer in 2 is based on (Zn{sub 2}(OCO){sub 4}) paddlewheel unit as the node. Two (4,4) grid layers with (Co{sub 2}O(OCO){sub 2}) dimer as the node are covalently interconnected by organic ligands affording a thick bilayer of 3 with new framework topology. The different entanglements between two coincident (4,4) grid layers with [CoN{sub 2}O{sub 4}] octahedron as the node leads to two 2D→2D interpenetrated structures for 4 and 5. Furthermore, fluorescent properties of 1 and 2 as well as magnetic properties of 3 are investigated. - Graphical abstract: Diverse assemblies of the (4,4) grid layers with different network nodes forms five coordination polymers that are well characterized by IR, TGA, element analysis, fluorescent and magnetic measurement. - Highlights: • Diverse assemblies of themore » (4,4) grid layers with different structural units as the nodes. • A new topology type with the uninodal 6-connected net of (4{sup 12}.5{sup 2}.6) is found. • Intense fluorescence emissions with a rare blue-shift of 55 nm compared to free carboxylate ligand.« less