Synthesis And Structural Characterization Of Multi-functional Ferrocenyl-containing Schiff Base Ligands And Preparation Of Their Coordination Complexes

With the development of industrialization,traditional single metal catalysts with low catalytic efficiency can not meet the needs of large-scale production.In order to improve the production efficiency and reduce the cost,heteronuclear polymetallic catalysts have attracted much attention.Compared with the single metal catalysts,heteronuclear polymetallic catalysts have higher catalytic efficiency and shorter reaction time due to the synergistic effect between metals.Treatment of ferrocene?-diketone with alkyl or aryl diamine(ethylenediamine,1,3-diaminopropane,cyclohexane-1,4-diamine,1,2-diaminobenzene,1,4-phenylenediamine)afforded four novel biferrocenyl tetradentate Schiff base(Fc–C(O)CH=C(CH₃)N(H)RN(H)(CH₃)C=CHC(O)–Fc)(HL1:R=CH₂CH₂;HL8:R=CH₂CH₂CH₂;HL6:R=C₆H₁₀;HL4:R=C₆H₄(Fc=Ferrocene)),three half-unit Schiff base(Fc–C(O)CH=C(CH₃)N(H)R₁)(HL2:R₁=CH₂CH₂NH₂;HL5:R₁=p-C₆H₁₀NH₂;HL3:R₁=1,4-C₆H₄NH₂)and a seven-membered ring compound(HL7)2-ferrocenyl-4-methyl-1,5-benzodiazepine.Interaction of“half-unit”Schiff base HL3 and salicylaldehydes with different substituents gave five tetradentate asymmetric ferrocenyl Schiff base ligands(HL9,HL10 HL11,HL12,HL13),Interaction of“half-unit”Schiff base HL2 and salicylaldehyde gave a tetradentate asymmetric ferrocenyl Schiff base(HL14),all of the synthesized ferrocenyl Schiff base compounds can be used as the potential ligands for heteronuclear polymetallic complexes.Reaction of HL1 with Cu(CH₃COO)₂ and Ni(CH₃COO)₂gave tetradentate N₂O₂complexes[Cu(L1)](1)and[Ni(L1)](2),respectively.Treatment of HL2 with cis-[Ru(dmso)₄Cl₂]gave a tridentate N₂O complex[(Fc-C(O)CHC(O)CH₃)Ru(dmso)(L2)](3).The structures of nine compounds have been established by single-crystal X-ray crystallography,and all ligands were characterized by ¹H NMR,FT-IR,and elemental analysis.Besides,UV-vis spectroscopies,fluorescence and electrochemical properties were also investigated,and according to the photochemical property of ruthenium complexes,the photocatalytic properties for hydrogen production from water hydrolysis were explored.