Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hy...Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.展开更多
Eight novel binuclear tetradentate Schiff base complexes (M=Cu?,Ni?,Zn?) are synthesized. The structure of complexes is two discrete Schiff base unit bridged. The complexes were condensed from series substituent Keton...Eight novel binuclear tetradentate Schiff base complexes (M=Cu?,Ni?,Zn?) are synthesized. The structure of complexes is two discrete Schiff base unit bridged. The complexes were condensed from series substituent Ketones (5 chloro 2 hydroxybenzophenone, 5 methyl 2 hydroxy benzophenone, 5 Bromo 2 hydroxybenzop henone) and dialdehydes (5,5′ methylene disalicylaldehyde) with the amino group of 1,2 diaminobenzene, and by Metal ion as template. The compounds were characterized by elemental analyses, FT infrared spectra, Raman, 1H NMR, UV vis electronic spectra, EPR spectra. The FT infrared spectra and Raman spectra of complexes were compared and discussed. The UV vis election spectra, 1H NMR and EPR spectra of complexes have also been attributed and minutely analyzed.展开更多
The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density ...The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.展开更多
文摘Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.
文摘Eight novel binuclear tetradentate Schiff base complexes (M=Cu?,Ni?,Zn?) are synthesized. The structure of complexes is two discrete Schiff base unit bridged. The complexes were condensed from series substituent Ketones (5 chloro 2 hydroxybenzophenone, 5 methyl 2 hydroxy benzophenone, 5 Bromo 2 hydroxybenzop henone) and dialdehydes (5,5′ methylene disalicylaldehyde) with the amino group of 1,2 diaminobenzene, and by Metal ion as template. The compounds were characterized by elemental analyses, FT infrared spectra, Raman, 1H NMR, UV vis electronic spectra, EPR spectra. The FT infrared spectra and Raman spectra of complexes were compared and discussed. The UV vis election spectra, 1H NMR and EPR spectra of complexes have also been attributed and minutely analyzed.
文摘The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.
