A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structu...A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structure of the palladium complex, PdL2. The geometry of Pd (II) in the complex is close to square planar and in novel cis-configuration with two ferrocene moieties on the same side. Degenerate four-wave mixing (DFWM) measurements show that the complex exhibit obvious nonlinear optical response.展开更多
The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X r...The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X ray diffraction studies have established the structures of PdL 2 (3) and CuL 2 (4). The geometry of Pd(Ⅱ) in (3) is close to a square plane and in the novel cis configuration the two ferrocene moieties are in cis configuration, while that of Cu(Ⅱ) in (4) is close to a tetrahedral configuration. The electrochemical measurements suggested that the square planar configuration of Ni(Ⅱ) and Pd(Ⅱ) moieties can effectively transmit the redox effects of the ferrocene moieties, while the tetrahedral configuration of the Cu(Ⅱ) complex can not transmit the redox effects. The degenerate four wave mixing (DFWM) measurements showed that the complexes exhibit obviously nonlinear optical (NLO) response. The magnitude of their third order NLO susceptibility can be explained by their structure and electrochemical properties.展开更多
The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5...The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.展开更多
MnO_(x)is commonly used as an oxidative cocatalyst to promote charge carrier separation,yet,its underlying mechanism remains incompletely understood.In this study,MnO_(x)nanoparticles were deposited onto the surface o...MnO_(x)is commonly used as an oxidative cocatalyst to promote charge carrier separation,yet,its underlying mechanism remains incompletely understood.In this study,MnO_(x)nanoparticles were deposited onto the surface of BiFeO_(3)nanosheets via a photodeposition method,and their promoting effects in piezocatalytic and piezo-photocatalytic reactions were systematically investigated.The synthesized MnO_(x)/BiFeO_(3)composites exhibited enhanced catalytic performance in RhB degradation.In the piezocatalytic system,the optimized MnO_(x)/BiFeO_(3)catalyst achieved a degradation rate constant of 0.78 h−1,approximately 4.6 times that of pure BiFeO_(3).Under simultaneous ultrasonic vibration and light irradiation,the rate constant further increased to 1.4 h−1,representing 1.8 times and 1.4 times the rates observed under individual piezocatalytic and photocatalytic conditions,respectively.Comprehensive characterization techniques were employed to elucidate the mechanism behind the enhanced performance.The results reveal that MnO_(x)modification induces interfacial stress,enhancing the piezoelectric response of BiFeO_(3).Moreover,an S-scheme heterojunction is formed at the MnO_(x)/BiFeO_(3)interface,wherein holes in the valence band of BiFeO_(3)recombine with electrons from MnO_(x),effectively promoting charge separation and transport while preserving the strong redox capability of both charge carriers.The synergistic piezo-photocatalytic effect of MnO_(x)/BiFeO_(3)is attributed to the global piezoelectric potential of BiFeO_(3),which extends the spatial range of interfacial charge separation within the S-scheme heterojunction.Additionally,the high-density photogenerated electron–hole pairs produced under light irradiation effectively supplement the intrinsic charge carriers.This study not only clarifies the potential mechanism by which MnO_(x)functions as a hole-trapping cocatalyst,but also highlights the unique advantages of S-scheme heterojunctions in the field of piezo-photocatalysis,offering valuable insights for the design of efficient piezocatalytic materials.展开更多
文摘A novel biferocene trinuclear complex for Schiff base ligand S-methyl-N- (ferrocenyl-1-methyl -methylidene) dithiocarbazate thereafter abbreviated as HL) is described. X-ray diffraction studies established the structure of the palladium complex, PdL2. The geometry of Pd (II) in the complex is close to square planar and in novel cis-configuration with two ferrocene moieties on the same side. Degenerate four-wave mixing (DFWM) measurements show that the complex exhibit obvious nonlinear optical response.
文摘The syntheses and characterization of novel biferrocene trinuclear complexes of Schiff base ligand, S methyl N (ferrocenyl 1 methyl methylidene)dithiocarbazate [hereafter abbreviated as HL (1)], are described. The X ray diffraction studies have established the structures of PdL 2 (3) and CuL 2 (4). The geometry of Pd(Ⅱ) in (3) is close to a square plane and in the novel cis configuration the two ferrocene moieties are in cis configuration, while that of Cu(Ⅱ) in (4) is close to a tetrahedral configuration. The electrochemical measurements suggested that the square planar configuration of Ni(Ⅱ) and Pd(Ⅱ) moieties can effectively transmit the redox effects of the ferrocene moieties, while the tetrahedral configuration of the Cu(Ⅱ) complex can not transmit the redox effects. The degenerate four wave mixing (DFWM) measurements showed that the complexes exhibit obviously nonlinear optical (NLO) response. The magnitude of their third order NLO susceptibility can be explained by their structure and electrochemical properties.
文摘The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.
基金supported by the National Natural Science Foundation of China(no.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘MnO_(x)is commonly used as an oxidative cocatalyst to promote charge carrier separation,yet,its underlying mechanism remains incompletely understood.In this study,MnO_(x)nanoparticles were deposited onto the surface of BiFeO_(3)nanosheets via a photodeposition method,and their promoting effects in piezocatalytic and piezo-photocatalytic reactions were systematically investigated.The synthesized MnO_(x)/BiFeO_(3)composites exhibited enhanced catalytic performance in RhB degradation.In the piezocatalytic system,the optimized MnO_(x)/BiFeO_(3)catalyst achieved a degradation rate constant of 0.78 h−1,approximately 4.6 times that of pure BiFeO_(3).Under simultaneous ultrasonic vibration and light irradiation,the rate constant further increased to 1.4 h−1,representing 1.8 times and 1.4 times the rates observed under individual piezocatalytic and photocatalytic conditions,respectively.Comprehensive characterization techniques were employed to elucidate the mechanism behind the enhanced performance.The results reveal that MnO_(x)modification induces interfacial stress,enhancing the piezoelectric response of BiFeO_(3).Moreover,an S-scheme heterojunction is formed at the MnO_(x)/BiFeO_(3)interface,wherein holes in the valence band of BiFeO_(3)recombine with electrons from MnO_(x),effectively promoting charge separation and transport while preserving the strong redox capability of both charge carriers.The synergistic piezo-photocatalytic effect of MnO_(x)/BiFeO_(3)is attributed to the global piezoelectric potential of BiFeO_(3),which extends the spatial range of interfacial charge separation within the S-scheme heterojunction.Additionally,the high-density photogenerated electron–hole pairs produced under light irradiation effectively supplement the intrinsic charge carriers.This study not only clarifies the potential mechanism by which MnO_(x)functions as a hole-trapping cocatalyst,but also highlights the unique advantages of S-scheme heterojunctions in the field of piezo-photocatalysis,offering valuable insights for the design of efficient piezocatalytic materials.
