PMBP-Based N₂O₂-type Ligands And Their Co???,Ni???,Cu???and Zn??? Complexes:Synthesis,Structure,Hirshfeld Analyses And Fluorescent Properties

Salamo-type compounds,as a novel derivative in the field of modern coordination chemistry,have attracted more and more attention and research.It is derived from the Salen compounds.Compared with Salen compounds,it has better stability,flexibility and more diverse coordination modes.Transition metal salts,rare earth metal salts and Salamo-type ligands were mixed to obtain metal complexes with various structures.There are many hydrogen bonds in these complexes,such as C-H���? and ?���?,which self-assemble to form supramolecular structures through hydrogen bondings.They have wide applications,especially in the fields of optical properties,magnetic materials,cell imagings,catalysis and so on.Therefore,the design and synthesis of Salamo-type ligands and their derivatives has important significance.Firstly,1,2-bis?aminooxy?ethane and 1,3-bis?aminooxy?propane were successfully prepared.Using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone?PMBP?as raw material,the best reaction temperature and solvent ratio were selected for condensation reaction of the above two diamines with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone?PMBP?,respectively.N₂O₂-type ligands H₂L¹ and H₂L² containing PMBP group were prepared and purified.Two mononuclear metal complexes were prepared by the reactions of ligand H₂L¹ with transition metal salts?nickel acetate and cobalt acetate?,[Ni?L¹??MeOH?₂]�MeOH?1?and[Co?L¹??MeOH?₂]?2?.The structures of the above-referenced complexes were determined by X-ray single crystal diffraction analyses.The complexes were characterized by elemental analyses,IR,UV-Vis spectra and Hirshfeld surfaces analyses.In addition,the supramolecular structures and fluorescence properties of the complexes were studied in detail.Secondly,four metal complexes were prepared by the reactions of ligand H₂L² with transition metal salts?nickel acetate,copper acetate and zinc nitrate?.[Ni₃?L²?₃?EtOH?₆]?3?,[Ni₃?L²?₃?H₂O?₆]?4?,[Cu₄?L²?₄]�2CHCl₃?5?and[Zn₃?L²?₃?H₂O?₃?MeOH?₃]?6?.Similarly,the structures of these metal complexes was determined by X-ray single crystal diffractometer,and their physical and chemical properties were characterized by conventional methods.The synthesis methods,crystal structures,supramolecular interactions,solvent effects and fluorescence properties of complexes 3-6 were systematically and thoroughly discussed.