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（Ⅱ）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）?,α=90.00o,β=96.758（7）o,γ=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）?,α=110.4800（10）o,β=101.1890（10）o,γ=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）?,α=82.562（2）o,β=80.553（2）o,γ=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）?,α=84.531（12）o,β=80.178（12）o,γ=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）?,α=111.202（5）o,β=101.075（5）o,γ=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）?,α=111.422（8）o,β=100.715（7）o,γ=99.989（7）o,Z=2,V=2304.7（4）?3,R1=0.0774,wR2 =0.1638.