[Ni(4,4‘-bpy)₂(H₂PO₄)₂]·C₄H₉OH·H₂O:  a Novel Metal Phosphate That Exhibits Interpenetration of 2D Net into 3D Framework

Abstract

The construction of coordination polymers based on metalbridging ligand building blocks is an area of great activity because of their fascinating structural diversity and potential applications as function materials. 1,2 A study of the literature about transition metal supramolecular architectures shows that the most extensively studied bridging ligand is 4,4′-bipyridine (4,4′-bpy), and a wide range of infinite frameworks including diamondoid, grid, ladder, brick, railroad, and octahedral building blocks have been generated with 4,4′-bpy or its extended analogues. 1 In some cases, the frameworks generate spacious voids, cavities, and channels, which are usually occupied by solvent molecules. In other cases, interpenetrating structures are formed in which the voids associated with one framework are occupied by one or more independent infinite substructures of the same chemical composition and with the same topology. 3 Examples of interpenetrating 3D frameworks

Hydrothermal synthesis and characterization of a new three-dimensional hybrid zinc phosphate [Zn2(HPO4)2(4,4′-bipy)]·3H2O with neutral porous framework

“…Each structure is constructed from four-ring secondary building units that consist of two tetrahedral zinc atoms and two tetrahedral phosphate groups. A study of the literature about inorganic-organic hybrid compounds shows that 4,4 0 -bipyridine (4,4 0 -bipy) is a good candidate for assembly these compounds, therefore we extended our research into the zinc/4,4 0 -bipy/H 3 PO 4 system [12][13][14][15][16][17][18][19]. In previous work, a novel 3-D zinc fluorophosphates: Zn 2 (4,4 0 -bipy)(PO 3 F) 2 synthesized under the presence of the fluoride ion has been reported [20].…”

Controlled assembly of an unprecedented 2D + 3D interpenetrated array of (4,4)-connected and pcu topologies

“…24 The 'classical' interpenetrations involving n-fold interpenetrating 2D layers or 3D nets are now extensively studied, unusual interpenetration topologies including interpenetration of nets of different dimensions, such as 0D + 1D, 1D + 2D, 1D + 3D, and 2D + 3D, are still very rare. [25][26][27][28][29] In a 2001 review article, Batten made the prediction of several unusual interpenetration topologies, 12 one of which was the 3D 6-connected (4 12 .6 3 ) pcu or a-Po net with interpenetrating 2D (4,4)-connected nets. However, such fascinating interpenetrated array has been remaining theoretical for 10 years.…”

Co3(PO4)2·4H2O

“…For example, microporous nickel phosphates incorporating 24-membered rings such as VSB-5 (Versailles/Santa have been demonstrated to exhibit hydrogen uptake at low temperatures (Forster et al, 2003). Over the past couple of decades, a considerable number of metal phosphates/phosphites with open molecular architectures have also been synthesized incorporating organic units (see, for example: Jiang et al, 2001) and ionic liquids (Cooper et al, 2004) as structure-directing agents, often under hydrothermal or solvothermal conditions. One of the best known families of this type consists of zinc phosphate structures; individual materials of this type can exist as one dimensional (chain and ladder), two dimensional (layer) and three dimensional framework arrangements (Choudhury et al, 2000).…”