Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as guest molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
