Syntheses, Structures And Property Characterizations Of Novel Open-framework Phosphites

Inorganic open-framework materials have been extensively used in manyindustrial processes, such as catalysis, adsorption and separation. Recently, a newclass of open-framework metal phosphites has been developed by employing thepyramidal phosphite units HPO2-3to replace the tetrahedral phosphate groups PO3-4.Such materials have attracted much attention due to their novel frameworkcompositions and structure features including extra-large pores, chiral and helicalstructures. These materials have potential applications in the areas of optics, magneticchemistry, electrochemistry, catalytic chemistry, etc.In this paper, we have hydrothermally/solvothermally synthesized a series ofmetal phosphites by using different organic amines as the templates. Main resultsinclude:1. Two new indium phosphites [C3H10N2][In2(HPO3)4](InHPO-CJ11) and[C3H12N2][InF(HPO3)2](InHPO-CJ12) have been solvothermally synthesized byusing1,2-propanediamine as the template. InHPO-CJ11displays a novel(3,6)-connected three-dimensional (3D) structure containing multi-directionalintersecting8-ring channels and unique left/right-handed helical chains.InHPO-CJ12has a1D chain-like structure constructed by InO6and HPO3units.Notably, the syntheses of these two compounds are similar except for the use ofhydrofluoric acid. 2. In2(HPO3)3(InHPO-CJ13) and [C4H12N2][In4(HPO3)7(H2O)3](InHPO-CJ14) havebeen solvothermally synthesized in the presence of mixed solvents. InHPO-CJ13possesses a3D inorganic framework with12-ring channels without occludedorganic templates, which is built up by the connection of In2O10face-shareddimers and pseudo pyramidal HPO3units. InHPO-CJ14exhibits a pillar-layeredstructure with intersecting12-ring channels along [100],[010] and [110]directions.3. A three-dimensional (3D) inorganic–organic hybrid zinc phosphite(C6N2H16)0.5ZnHPO3(ZnHPO-CJ15) has been hydrothermally synthesized. It hasa pillar-layered structure, in which1,6-hexamethylenediamine molecules act asthe pillars to link the adjacent4.82zinc phosphite layers to construct the openframework of ZnHPO-CJ15. ZnHPO-CJ15exhibits fluorescence property.4.[C6H9N2][Zn2(PO4)(HPO3)](ZnHPO-CJ16) has been hydrothermally synthesizedby using3-(aminomethyl) pyridine as the organic template. Its frameworkcontains two kinds of anion groups, i.e. phosphate and phosphite. ZnHPO-CJ16possesses a two-dimensional (2D) layer structure, which is constructed by ZnO3Ntetrahedra and HPO3pseudo-pyramids.3-(aminomethyl) pyridine acts as theligands to connect the zinc atoms of inorganic framework. ZnHPO-CJ16possesses fluorescence property due to the existence of3-(aminomethyl) pyridine.5.(C7H18N)2[Zn(HPO3)2](ZnHPO-CJ17) has been hydrothermally synthesized inthe presence of n-heptylamine. Its structure is constructed by ZnO4tetrahedra andHPO3pseudo-pyramids. ZnHPO-CJ17is the first example of1D chain structureof zinc phosphite synthesized by using a single amine as the template.6.(C2H6N)[Co1.5(OH)(HPO3)](CoHPO-CJ10) is a3D inorganic-organic hybridcobalt phosphite. It exhibits a pillar-layered structure with an unusual Co/P ratioof3/2. The1,4-butanediamine molecules act as the pillars to link the adjacentcobalt phosphite layers to form open framework. Interestingly, such structurecontains infinite edge-sharing connected Co–O–Co chains, which is rarely occurred in the structures of cobalt phosphates/phosphites. It exhibitsantiferromagnetic interaction.7. A one-dimensional (1D) galium phosphite [C3H12N2][Ga(HPO3)(OH)2](GaHPO-CJ18) was synthesized by using1,2-propylene amine as the organictemplate. Its inorganic chain is constructed by GaO6octahedra and HPO3pseudo-pyramids. Ga-O-Ga connection mode is found in such structure.