Synthesis And Properties Of Urea-containing Complexes

To built a novel structure and functional supramolecular compound via more than two molecules by intermolecular forces is a hot research area in modern chemistry.Urea-based pyridyl ligand could build novel structure complexes by pyridal group with metal ions and bind anions by hydrogen bonding from ureido or protonated pyridal with anions.Based of this information,the paper designed and synthesized six kinds of pyridylurea ligands.And we obtained six transition metal coordination polymer and five oxo-acid product by those pyridylurea ligands.The crystal structure,hydrogen bond pattern and anion selectivity have been discussed in detail.The paper mainly focus on the following aspects:1. Four complexes named{[Cd?L¹??SO₄??H₂O?₃]·H₂O}_n?1?,{[Zn?L¹?I₂]·2C₂H₅OH}_n?2?,{[Hg?L¹?I₂]·C₂H₅OH}_n?3?and[Hg?L¹?Cl₂]·H₂O?4?have been obt ained by the reaction of pyridylurea ligand L¹ with Cd SO₄·8H₂O,Zn I₂,Hg I₂ a nd Hg Cl₂.One complex named{[Hg?L²?]I₂·2DMF}_n?5?have been obtained by the reaction of pyridylurea ligand L² with Hg I₂.One complex named[Cd?L³?I₂]·C₂H₅OH?6?have been obtained by the reaction of pyridylurea ligand L³ wit h Cd I₂.Those complexes were characterized by elemental analysis,FT-IR,X-ra y diffraction analysis,PXRD and TG analysis.Complex 1 form a one-dimensio nal helix chain structure.Complex 2,complex 3 and complex 5 show a one-di mensional zigzag chain structure.Complex 4 show us a 32-membered ring.Co mplex 6 show us a 30-membered ring.2.Two complexes named{[?L⁴H₂??NO₃?₂·2H₂O]}_n?7?,{[?L⁴H₂??SO₄?·H₂O]}_n?8?have been obtained by the reaction of pyridylurea ligand L⁴ with HNO₃ a nd H₂SO₄.Three complexes named{[?L⁵H??NO₃?]}_n?9?,{[?L⁵H??Cl O₄?]}_n?10?,{[?L⁵H?₂?C₄H₅C₂O₄?]}_n?11?.Those complexes were characterized by elemental a nalysis,FT-IR,X-ray diffraction analysis and PXRD.In addition,we have exa med the anion selectivity of L⁴ through powder x-ray diffraction,and found th at showed a remarkable preference for nitrate ion over sulfate ion.Using the s ame procedure to examed the anion selectivity of L⁵ and found that showed ar emarkable preference for nitrate ion over perchlorate ion and adipate ion.3.A anion receptor L⁶ have been designed and synthesized.The structure of L⁶has been determained by X-ray single crystal diffraction.The recognition ability for a series of anions was surveyed,the results showed that L⁶ displayed a obvious recognition for F^-.In addition,the coordination reaction of L⁶ and F^-ion was investigated.The stoichiometric ratio is 1:2 and the association constant of coordination reaction K₁ is 88.78 L·mol^-1,K₂ is 1.65×10⁶ L·mol^-1?...