Preparation And Properties Of CPs Based On Aromatic Acylhydrazidate Ligands

Coordination polymers(CPs),as a new kind of organic-inorganic hybrid materials,have shown good application prospects in the fields of energy storage,gas separation,catalysis,fluorescence,and magnetic materials.It has become one of the hot topics to design and synthesize new inorganic functional coordination compound materials in the field of inorganic chemistry.This paper is mainly based on the design,syntheses,crystal structure and properties of new coordination polymers constructed from aromatic acylhydrazidate ligands.Due to aromatic acylhydrazidate ligands have abundant coordination modes,which contain many O/N atoms and can form many coordination modes with metal ions.And the O/N atoms are easy to form hydrogen bonds,which is more helpful for the high-dimensional supramolecular networks.According to the above,we have successfully synthesized 3 series of 11 novel coordination polymer materials with novel structure through in situ acylation reaction between different organic ortho-carboxylic acids and hydrazine hydrate using different design concepts.We also discussed the influencing factors of the final structure of the compounds are introduced in detail Meanwhile,the synthesized coordination polymers materials were characterized by X-ray single-crystal diffraction analysis,elemental analysis,infrared spectroscopy(IR),powder X-ray diffraction and thermogravimetric analysis(TGA).The fluorescence and magnetic properties of the partially regulated compounds were also studied,and the structure and properties of the coordination polymers based on aromatic acylhydrazidate ligands were further discussed.1.We synthesized three 2,3-quinoline dihydrazide ligands coordination compounds constructed from selecting 2,3-quinolinedicarboxylic acid and hydrazine hydrate as ligand precursors in situ acylation reaction under water(solvent)thermal conditions.molecular formula:[Fe(QLH)2(H2O)2]·4H2O(1),[Co(QLH)2(H2O)2]·4H2O(2)and[Ni(QLH)2(H2O)2]·4H2O(3)Compounds 1-3 are isomorphic.X-ray single-crystal diffraction results show that compounds 1 and 2 are zero-dimensional compounds,and adjacent coordination units are linked into a three-dimensional supramolecular network by intermolecular hydrogen bonding and π…π stacking,respectively.We expected to synthesize low-dimensional coordination polymers based on Fe(Ⅱ),Co(Ⅱ),Ni(Ⅱ)ions were achieved,provided the basis for the later study of magnetic properties.The structure of compound 3 was obtained by infrared spectroscopy and X-ray powder diffraction data analysis that compound 3 is isomorphic to compounds 1 and 2.Through the study of magnetic properties,compound 1 has weak ferromagnetic behavior,compounds 2 and 3 have weak antiferromagnetic behavior.compound 2 exhibits AC susceptibility to magnetic relaxation,and the presence of field-induced single ions magnet behavior.2.We synthesized 5 cases coordination polymers constructed from selecting 5.6-bcnzimidazole dicarboxylic acid and hydrazine hydrate as ligand precursors in situ acylation reaction under water(solvent)thermal conditions.[Zn(BMTH)]n·0.5nH2O(4)、[Zn2(BMTH)2]n(5)、[Zn(BMTH)(H2O)]n(6)、[Co(BMTH)]n·0.5nH2O(7)and[Co(HBMTH)(SDH)]n(8).The fluorescence properties of compound 4-6 were studied,and the results showed that both compounds 4-6 emitted blue light.The ability of compounds 4-6 to detect metal ions as a fluorescent probe was explored,because compounds 4-6 has high stability and excellent luminescence properties in water.The results of compounds 4-6 to detect metal ions as a fluorescent probe illustrated that compounds 4 and 6 can exhibit high selectivity to Fe3+by fluorescence quenching,and compound 5 can exhibit high selectivity to Hg2+ by fluorescence enhancement.The magnetic properties of compounds 7 and 8 shovv that there is a weak anti ferromagnetic effect between the metal centers of the compounds.3.We selected 4-(3,4-dicarboxyphenyl)phthalic acid and hydrazine hydrate as the ligand precursor.and successfully synthesized 2 cases coordination pompounds 9 and 10 in-situ acylation reaction and 1 case of coordination pompound 11 constructed with 4-(3,4-dicarboxyphenyl)phthalic acid as ligands under water(solvent)heat conditions.Molecular formula:[Mn(BPTH)(H2O)2]n(9)、[Co(BPTH)(phen)]n(10)and[Co2(BPTA)(phen)(H2O)2]n·nH2O(11).X-ray sihgle crystal diffraction results show that compound 9 has the 3D network structure,compound 10 had a one-dimensional double-stranded structure,and compound 11 had a two-dimensional layered structure.Through the study of magnetic properties of compound 9-11,compound 9 has weak ferromagnetic action,and compounds 10 and 11 have weak antiferromagnetic action.