| In recent years,more and more scholars have been engaged in the research of transition metal complexes containing disulfines and halogens because of their diversified structures and good potential application prospects in fields such as magnetic,optics and catalysis,etc.In this paper,a transition metal complex with two kinds of ligands is combied with substituted benzylpyridine,benzyltriphenylphosphonium,substituted benzyltris(4-methoxy)phenylphosphonium,1,1'-ethyl-2,2'-duplex pyridine,benzyl-4-aminopyridine cation to synthesize a total of 14 kinds of complexes,of which 7 kinds of known structures were synthesized and characterized by using IR,UV-Vis spectra,Electron Spray Mass Spectrometry,X-ray single crystal diffraction,X-ray powder diffraction,Thermogravimetry-Differential Thermal Analysis(TG-DTA)and other methods.The catalytic or fluorescence properties were investigated.1.In order to investigate the effect of substituents on the phenyl ring on the structures and electrocatalytic properties of the dithione cobalt ligand,4-substituted benzylpyridine was used as the counter cation([4-RBz Py]+)and bis(maleonitriledithiolate)Cobalt(III)anion.[Co(mnt)2]-as a building unit,three new dithione cobalt complexes,[4FBz Py][Co(mnt)2](1),[4IBz Py][Co(mnt)2](2),[4NO2Bz Py][Co(mnt)2](3),were designed and synthesized.All complexes 1?3 crystallized in triclinic,P-1 space group.The electrocatalytic test shows that the TOF values for 1?3 are 520.8,536.6,and 344.7 h-1 in the neutral phosphate buffer solution with a voltage of-1.45 V,respectively.The electrolysis power was linearly related to the time by electrolysis in the mixed solution for 72 h,indicating that the complexes 1?3 were stable in electrolysis water catalysis.2.To investigate the effect of different dithione ligands on the electrocatalytic properties of nickel complexes,three known structures of dithione nickel(II)complexes,[Bz TPP]2[Ni(mnt)2](4),[Bz TPP]2[Ni(i-mnt)2](5),[Bz TPP]2[Ni(tdas)2](6),were synthesized by the literature method.Their existential states in the solution were confirmed by ESI-MS,and it was determined to be stable at different p H by UV-Vis spectroscopy.The electrocatalytic test showed that the TOF values which in a neutral phosphate buffer solution at a voltage of-1.45 V were 504.76,591.52,and 1022.93 h-1,respectively.The long-term electrolytic test found that the three of complex catalysts were relatively stable.3.To explore the effect of different transition metals on the electrocatalytic properties of the same ligands,three different known structures of dithione nickel(III)complexes,[Bz TPP][Co(mnt)2](7),[Bz TPP][Ni(mnt)2](8),[Bz TPP]2[Cu(mnt)2](9),were synthesized by the literature method.Their existential states in the solution were confirmed by ESI-MS.The electrocatalytic performance test showed that the electrolysis was carried out in a neutral phosphate buffer solution at a voltage of-1.45 V,and the TOF values were 674.95,634.25,and 690.68 h-1,respectively.Through the long-term electrolysis test,the electrocatalytic activity of the complexes 7?9 were no greatly lost,indicating that the catalysts of these were relatively stable.4.In order to explore the effect of quaternary phosphonium cations on the structure and fluorescence properties of containing complexes tetrachloromanganese anion,[Bz TPP]2[Mn Cl4](10)was synthesized by the literature method,and[Bz T(4-Me O)PP]2[Mn Cl4](11),[4FBz T(4-Me O)PP]2[Mn Cl4](12),[Et Bi Py][Cu Cl4](13),[Bz-4-NH2Py]2[Cd Br4](14)were designed and synthesized.The crystal structures of complexes 11?14 were measured,and the thermal stability as well as fluorescence properties of these complexes were investigated.It was found that complexes have good heat resistance,and the complexes 10 and 11 excited strongly green light under at ultraviolet light(360 nm).The IR,Raman,nonlinear optical effects of 14 by DFT calculation is basically consistent with experimental values.The calculated first hyperpolarizability(?tot)is about 14.3 times that of the reference crystal monopotassium phosphate(KDP). |
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