Syntheses, Characterizations And Properties Of Metal Aminodiphosphonate Coordination Polymers

Metal phosphonates have received a great deal of attention in recent years due to the possibility to form interesting structures with potential applications in the areas of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry and materials chemistry.In this work, we have devoted effort toward hydrothermal synthesis of metal phosphonate coordination polymers by using three aminodiphosphonic acid, RN(CH2PO3H2)2 (R=-C3H7, -C6H11, -CH2C5H4N) as building units to obtain possible new types of materials with potential applications. Twenty-one novel metal phosphonate coordination polymers are hydrothermally synthesized by using direct reaction or oxalic acid as the second ligand, and structurally characterized by using X?ray single crystal diffraction, X–ray powder diffraction, IR spectroscopy and thermogravimetric analysis.Ten kinds of metal including transition metal (Zn, Cd, Mn), main group metal (Sn, Pb) and rare earth metal (La, Ce, Pr, Nd, Sm) were used in the synthesis of metal phosphonate coordination polymers. In the structure of these compounds, the MOn (M = metal, n = the number of oxygen atoms) polyhedral are bridged and chelated by the oxygen atoms from the functional groups of the ligands, resulting in the formation of two?dimensional layer and three?dimensional open?framework. The chemical constitution formulas are listed as follow:(1) Zn[(HO3PCH2)(O3PCH2)NHC3H7](2) Cd2[(O3PCH2)2NC3H7](3) Cd3.5[(O3PCH2)2NC3H7][(O3PCH2)(HO3PCH2)NC3H7](4) Mn2[((O3PCH2)2NHC3H7)(H2O)F]·H2O(5) Zn6[(O3PCH2)2NHC6H11]4·6H2O(6) Mn2[((O3PCH2)2NHC6H11)(H2O)F]·H2O(7) Cd2.5[((O3PCH2)2NC6H11)(H2O)2F]·H2O(8) Pb2[(O3PCH2)2NC6H11]·H2O(9) Sn3O[(O3PCH2)2NC6H11] (10) La[((O3PCH2)(HO3PCH2)NHC6H11)Cl](11)-(15) Ln[((O3PCH2)2NHC6H11)(H2O)]·H2O (Ln = La, Ce, Pr, Nd, Sm)(16) Mn2[((O3PCH2)2NHCH2C5H4N)(H2O)F]·H2O(17)-(21) Ln2[((HO3PCH2)2NHCH2C5H4NH)(C2O4)3(H2O)]·3H2O (Ln = La, Ce, Pr, Nd, Sm)Compounds 1–4 are prepared under hydrothermal reaction conditions by the combination of Zn, Cd and Mn cation with CH3CH2CH2N(CH2PO3H2)2. X?ray single?crystal diffraction analysis shows that compounds 1–4 are two?dimensional layered structures. Compounds 5–15 are synthesized by using the aminodiphosphonic acid, C6H11N(CH2PO3H2)2 as ligand. Ten kinds of metal, including transition metal (Zn, Cd, Mn), main group metal (Sn, Pb) and rare earth metal (La, Ce, Pr, Nd, Sm), were used in the synthesis. X?ray diffraction analysis shows that the compounds 6–15 are a two?dimensional layered structure, and compound 5 features a three?dimensional open?framework structure. Notably, compound 5 can be described as a 3D open–framework with two large channel systems in different directions. Additionally, using the aminodiphosphonic acid, C5H4NCH2N(CH2PO3H2)2, compound 16 is obtained by the direct reaction, and compounds 17–21 are obtained by using oxalic acid as the second ligand. X?ray single?crystal diffraction analysis shows that compound 16 features a two?dimensional layered structure, and compounds 17–21 can be described as a 3D open–framework structure.