Synthesis, Crystal Structures And Properties Of Novel Metal Phosphonate Coordination Polymers With Luminescence

In this work, twenty new phosphonate coordination polymers with novel structures, have been synthesized under hydrothermal conditions by using (2-carboxypiperidyl)-N-methylenephosphonic acid (H3L1), cyclo-hexyl-N(CH2PO3H2)2(H4L),4-phosphono-benzoic acid (H3pbc),(3-ammonium-l-hydroxypropylidene-1,1-bisphosphonate (H4apd),(H2O3PCH2)2N(CH2)2N(CH2PO3H2)2(H8EDTMPA) and H2O3PCH2NCH2(CH2CH2OPO2H)(H3L2) as ligands. The title compounds were structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy and thermogravimetric analysis. Furthermore, the luminescence properties of compounds1-6,10and14-20have been studied. The chemical formulas are listed as follow:(1) Cd2[(O3PCH2NHC5H9COO)(OOCC6H4COO)](2) Cd3.5[((HO3PCH2)(O3PCH2)NC6H11)((O3PCH2)2NC6H11)](3)[Zn(03PC6H4COOH)(H2O)](4)[Pb(O3PC6H4COOH)(H2O)]H2O(5)[Pb0.5Cd(NH3CH2CH2C(OH)(PO3)2)(H2O)](6)[PbZn4(O3PC6H4COOH)2(O3PC6H4COO)2(H2O)](7)[La(H5EDTMPA)(H2O)](8)[Pr(H5EDTMPA)(H2O)](9)[Nd(H5EDTMPA)(H2O)](10)[Sm(H5EDTMPA)(H2O)](11)[Ce(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(12)[Pr(H6EDTMP A)0.5(C2O4)(H2O)]·2H2O(13)[Nd(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(14)[Sm(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(15)[Eu(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(16)[Gd(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(17)[Tb(H6EDTMPA)0.5(C2O4)(H2O)]·2H2O(18)[Tb4{HO3PCH2NHCH2(CH2CH2OPO2)}4(C2O4)4(H2O)4]·8H2O(19)[Dy4{HO3PCH2NHCH2(CH2CH2OPO2)}4(C2O4)4(H2O)4]·8H2O(20)[Sm{HO3PCH2NHCH2(CH2CH2OPO2)}(C2O4)(H2O)]·2H2O Compounds2-4and7-10are prepraed by the dircet reaction. Compound2is synthesized by using cyclo-hexyl-N(CH2PO3H2)2(H4L) as the phosphonate ligand. X-ray diffraction analysis shows that compound2features2D layered structure. Compounds3and4are obtained by using4-phosphono-benzoic acid (H3pbc) as the phosphonate ligand. X-ray diffraction analysis shows that compounds3and4form two-dimensional structures, and the neighboring layers are interdigitated through hydrogen bonding interactions to give rise to a3D supramolecular structure. Compounds7-10are isostructural and show a novel layered structure, which are synthesized by using (H2O3PCH2)2N(CH2)2N(CH2PO3H2)2(H8EDTMPA) as ligand. The poor crystals of compounds8-10were not suitable for single crystals structure analysis, however, X-ray powder diffraction analysis indicates that they are identical to the compound7. Compounds5-6are obtained by introdution of the second metal ion. Compound5is synthesized by using (3-ammonium-l-hydroxypropylidene-1,1-bisphosphonate (H4apd) as the phosphonate ligand, and it features a2D layered structure. Compound6can be described as a3D open-framework, which is prepared by using4-phosphono-benzoic acid (H3pbc) as ligand. Compounds2-4and7-10are synthesized by incorporating a second organic ligands. By introduction of1,4-benzenedicarboxylic acid as a second organic ligand, compound1with (2-carboxypiperidyl)-N-methylenephosphonic acid (H3L1) is synthesized, and it exhibites a novel layered structure. By using (H2O3PCH2)2N(CH2)2N(CH2PO3H2)2(H8EDTMPA) as the phosphonate ligand and oxalate as the second metal linker, compounds11-17are obtained. These compounds are not prepared single crystals, however, X-ray powder diffraction analysis indicates they feature a3D network structure, which is the same as the structure of [La(H6EDTMPA)0.5(C2O4)(H2O)]-2H20prepared by our group. Compounds18-20are synthesized by using H2O3PCH2NCH2(CH2CH2OPO2H)(H3L2)as the phosphonate ligand, and oxalate as the second metal linker. Compounds18-19are isomorphic and feature a2D layered structure. Compound19is not obtained single crystals, however, X-ray powder diffraction analysis indicates that it is identical to the compound18, and compound20exhibites a3D network structure. The luminescence analyses indicate that compounds1-6,10and14-20are good candidate for luminescent material.