Design, Synthesis, Crystal Structures And Properties Of Conjugate-Type Metal Phosphonate Materials With Photoelectrical Functionalities

In this work, we have successfully obtained egiht new metal diphosphonates coordination polymers by using4-HOOCC6H4CH2N(CH2PO3H2)2and1-hydroxyethylidenediphosphonate as ligands under hydrothermal conditions. All compounds were structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, IR spectroscopy and thermogravimetric analysis. Meanwhile, the luminescent properties of compounds1and2have been studied. The surface photovoltage properties of compounds5-8have also been investigated. The chemical formulas are listed as follow:(1)[Sn2{HOOCC6H4CH2N(CH2PO3)2}]·2H2O(2)Pb2Cl[HOOCC6H4CH2NH(CH2PO3)2](3)Zn[HOOCC6H4CH2NH(CH2PO3)(CH2PO3H)](4) Ni1.5(4,4’-bipy)0.5[{HOOCC6H4CH2N(CH2PO3)(CH2P03H)}(HZO)2](5)[Co(2,2’-bipy)(hedpH3)2]·H2O(6)[Ni(2,2’-bipy)(hedpH3)2]·H2O(7)[Co(1,10-phen)(hedpH3)2]·H2O(8)[Ni(1,10-phen)(hedpH3)2]·H2OBy using4-HOOCC6H4CH2N(CH2PO3H2)2as the phosphonate ligand, compounds1-4are synthesized. Compounds1-3are prepraed by the dircet reaction and compound4is synthesized by using4,4’-bipy as the second metal linker. X-ray diffraction analysis exhibits that compounds1and3feature2D structures, compounds2and4feature3D framework structures. Compounds5-8are synthesized by using1-hydroxyethylidenediphosphonate as the phosphonate ligand and2,2’-bipy or1,10-phen as the second metal linker. X-ray diffraction analysis shows that compounds5and6are isomorphous forming two-dimensional structures. Compounds7and8are also isostructural and show a novel1D double chains structure by π-π stacking interactions and hydrogen bonds. Luminescence analyses show that compounds1and2will be candidate for luminescent materials. The SPS and FISPS of compounds5-8indicate that they show p-type semiconductor characteristic.