Study On Syntheses,Structures,Fluorescences And Catalytic Activities Of Naphthalenediol-based Bis (Salamo-type) Metal Complexes

In this paper,a novel bis?Salamo-type?tetraoxime ligand?H4L?was designed and synthesized.A series of characterization experiments were carried out by means of elemental analyses,IR spectra,UV-Vis spectra,1H NMR,and so on.The target product?H4L?was reacted with different transition and alkaline earth metal salts?Co?OAc?2·4H₂O;Zn?OAc?2·2H₂O;Ba?OAc?2;Sr?OAc?2;Ca?OAc?2?,and finally obtained the six new complexes: [Co₃?L??OAc?2?CH₃CH₂OH??H₂O?]?1?,[Co₂Ba?L??OAc?2]?2?,[Co₂Ca?L??OAc?2]·CHCl₃?3?,[Zn₂Ca?L??OAc?2]·CHCl₃?4?,[Zn₂Sr?L??OAc?2]?5?,[Zn₂Ba?L??OAc?2]?6?.Those complexes were also analyzed by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction determinations,respectively.The catecholase activities of homo-and hetero-trinuclear cobalt???complexes[Co₃?L??OAc?2?CH₃CH₂OH??H₂O?]?1?,[Co₂Ba?L??OAc?2]?2?and [Co₂Ca?L??OAc?2]·CHCl₃?3?were studied.The results showed that complexes 1,2 and 3 exhibited good catecholase activities in acetonitrile solution.Using UV–vis spectra,we monitored the aerial oxidation of3,5-di-tert-butylcatechol?3,5-DTBCH₂?to 3,5-di-tert-butylquinone?3,5-DTBQ?,which confirms the essential role of these complexes in enhancing the catalytic reaction.Since the reaction law of complex 1 was consistent with the kinetic equation of the enzyme?Michaelis-Menten equation?,the catalytic kinetics of complex 1 were further studied,and then the relationship between the parameters of the catalytic reaction was fitted by the double reciprocal method.Finally,the catalytic constant of the complex 1 was calculated.Complex 1?[Co₃?L??OAc?2?CH₃CH₂OH??H₂O?]?: Empirical formula,C₄₀H₄₅Co₃N₄O₁₆,Formula weight,1014.60,monoclinic,P2/n,Unit cell parameters: a=11.1657?8??,b=13.5989?9??,c=28.9628?17??,?=90.00o,?=96.758?7?o,?=90.00o,Z=4,V=4367.2?5??3,R1=0.0553,wR2 =0.1192.Complex 2?[Co₂Ba?L??OAc?2]?: Empirical formula,C₃₈H₃₈Co₂ Ba N₄O₁₄,Formula weight,1029.92,triclinic,P-1,Unit cell parameters: a=12.6248?5??,b=13.3958?6??,c=15.2840?6??,?=110.4800?10?o,?=101.1890?10?o,?=99.6460?10?o,Z=2,V=2296.13?17??3,R1=0.0306,w R2 =0.0751.Complex 3?[Co₂Ca?L??OAc?2]·CHCl₃?: Empirical formula,C₃₉H₃₉Co₂CaN₄O₁₄Cl₃,Formula weight,1052.05,triclinic,P-1,Unit cell parameters: a=12.5212?8??,b=13.1612?10??,c=13.3725?8??,?=82.562?2?o,?=80.553?2?o,?=86.513?2?o,Z=2,V=2153.8?3??3,R1=0.0530,wR2 =0.1438.Complex 4?[Zn₂Ca?L??OAc?2]·CHCl₃?: Empirical formula,C₃₉H₃₉Zn₂CaN₄O₁₄Cl₃,Formula weight,1064.94,triclinic,P-1,Unit cell parameters: a=12.4374?17??,b=12.9596?18??,c=13.3757?19??,?=84.531?12?o,?=80.178?12?o,?=86.928?11?o,Z=2,V=2113.1?5??3,R1=0.0617,wR2 =0.1279.Complex 5?[Zn₂Sr?L??OAc?2]?: Empirical formula,C₃₈H₃₈Zn₂SrN₄O₁₄,Formula weight,993.11,triclinic,P-1,Unit cell parameters: a=12.5470?19??,b=13.3336?19??,c=15.453?2??,?=111.202?5?o,?=101.075?5?o,?=100.367?5?o,Z=2,V=2275.7?6??3,R1=0.0644,wR2=0.1073.Complex 6?[Zn₂Ba?L??OAc?2]?: Empirical formula,C₃₈H₃₈Zn₂BaN₄O₁₄,Formula weight,1042.81,triclinic,P-1,Unit cell parameters: a=12.6093?11??,b=13.4496?12??,c=15.4036?14??,?=111.422?8?o,?=100.715?7?o,?=99.989?7?o,Z=2,V=2304.7?4??3,R1=0.0774,wR2 =0.1638.