Six novel chiral dinuclear Salen complexes[Cu 2 L 1 ·H 2 O(3a),Cu 2 L 2 (3b),Ni 2 L 1 ·2H 2 O(4a),Ni 2 L 2 (4b),Mn 2 Cl 2 L 1 ·H 2 O(5a),Mn 2 Cl 2 L 2 (5b)]have been synthesized(L 1 and L 2 are chiral d...Six novel chiral dinuclear Salen complexes[Cu 2 L 1 ·H 2 O(3a),Cu 2 L 2 (3b),Ni 2 L 1 ·2H 2 O(4a),Ni 2 L 2 (4b),Mn 2 Cl 2 L 1 ·H 2 O(5a),Mn 2 Cl 2 L 2 (5b)]have been synthesized(L 1 and L 2 are chiral dimeric Salen ligands with different chain length which were synthesized from(R,R) - diaminocyclohexane,salicylaldehyde,4,4 ’- (1,10 - decaneoxy)sali - cylaldehyde,4,4 ’- (1,6 - hexyloxy)salicylaldehyde).These compounds were charactered by elemental analysis,1 H NMR,FT - IR,UV - Vis and CD spectra.The FT - IR,UV - Vis and CD spectra were discussed and compared with those of monomeric ligand and complex in detail.It was found that the spectra properties of compounds of differ - ent chain length were almost alike,and the properties of dimeric and monomeric compound were similar too.Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory.It seemed that the direction of Cotton split depend on the configuration of diaminohexane.(R,R) - diaminohexane determine the chirality of Salen compounds as negative,and the positive and negative compo - nent of Cotton split lie at higher and lower energy respectively.展开更多
The binuclear complex [Cu2(TS)(H2O)]·CH3OH , where TS denotes the binucleating ligand derived from the schiff base N,N′ bis(3 carboxylsalidene)trimethylenediamine, was obtained from the self decomposition of mon...The binuclear complex [Cu2(TS)(H2O)]·CH3OH , where TS denotes the binucleating ligand derived from the schiff base N,N′ bis(3 carboxylsalidene)trimethylenediamine, was obtained from the self decomposition of mononuclear complex Na2CuTS·H2O. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.935(2)?,b=15.667(3)?,c=11.621(2)?,β=111.60(3)°,V=2020.2(7)?3, Z=4 with R=0.0467. The structure is made of binuclear units, in which two copper atoms are bridged by two phenolic oxygen atoms. The "inside"copper atom is coordinated by two nitrogens, two phenolic oxygens in a planar coordination site, the copper atom deviates from the mean plane by 0.47?. The "outside"copper atom is five coordinated by two phenolic oxygen atoms?two equatorial carboxyl oxygen atoms and one axial water oxygen atom in a distorted tetragonal cone site, the copper atom is pulled out of the equatorial plane by 0.46?.展开更多
A Series of mono and di-nuclear Zn Ni complexes with 5 - chlorosalicylaldehyde -ethylenediamine Schiff base have been synthesized. Theirs compositions and structures were characterized by the elemental analysis.UV.IR ...A Series of mono and di-nuclear Zn Ni complexes with 5 - chlorosalicylaldehyde -ethylenediamine Schiff base have been synthesized. Theirs compositions and structures were characterized by the elemental analysis.UV.IR spectra and 1H NMR. The Dismutation to O2 free radical has also been investigated.展开更多
The formation of heterobimetallic ruthenium?complex was investigated by absorption and emission spectra. As an intercalator of DNA, the luminescent monometallic ruthenium?complex [Ru(bpy)2tpphz]2+could coordinate with...The formation of heterobimetallic ruthenium?complex was investigated by absorption and emission spectra. As an intercalator of DNA, the luminescent monometallic ruthenium?complex [Ru(bpy)2tpphz]2+could coordinate with Zn2+to form the nonluminescent heterobimetallic complex [Ru(bpy)2(tpphz)Zn]4+. The emission intensity of complex decreased as increasing the amounts of Zn2+and the luminescence was almost lost at the ratio of / of 1. After binding to DNA, the peripheral coordination site on the tpphz ligand remained accessible for Zn2+, the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)2tpphz]2+and the nonluminescent heterobimetallic complex was formed. On the other hand, the [Ru(bpy)2(tpphz)Zn]4+also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)2tpphz]2+between the base pairs of DNA. The complex looked like a molecular nut (the Zn2+) and bolt (the [Ru(bpy)2tpphz]2+).展开更多
文摘Six novel chiral dinuclear Salen complexes[Cu 2 L 1 ·H 2 O(3a),Cu 2 L 2 (3b),Ni 2 L 1 ·2H 2 O(4a),Ni 2 L 2 (4b),Mn 2 Cl 2 L 1 ·H 2 O(5a),Mn 2 Cl 2 L 2 (5b)]have been synthesized(L 1 and L 2 are chiral dimeric Salen ligands with different chain length which were synthesized from(R,R) - diaminocyclohexane,salicylaldehyde,4,4 ’- (1,10 - decaneoxy)sali - cylaldehyde,4,4 ’- (1,6 - hexyloxy)salicylaldehyde).These compounds were charactered by elemental analysis,1 H NMR,FT - IR,UV - Vis and CD spectra.The FT - IR,UV - Vis and CD spectra were discussed and compared with those of monomeric ligand and complex in detail.It was found that the spectra properties of compounds of differ - ent chain length were almost alike,and the properties of dimeric and monomeric compound were similar too.Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory.It seemed that the direction of Cotton split depend on the configuration of diaminohexane.(R,R) - diaminohexane determine the chirality of Salen compounds as negative,and the positive and negative compo - nent of Cotton split lie at higher and lower energy respectively.
文摘The binuclear complex [Cu2(TS)(H2O)]·CH3OH , where TS denotes the binucleating ligand derived from the schiff base N,N′ bis(3 carboxylsalidene)trimethylenediamine, was obtained from the self decomposition of mononuclear complex Na2CuTS·H2O. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.935(2)?,b=15.667(3)?,c=11.621(2)?,β=111.60(3)°,V=2020.2(7)?3, Z=4 with R=0.0467. The structure is made of binuclear units, in which two copper atoms are bridged by two phenolic oxygen atoms. The "inside"copper atom is coordinated by two nitrogens, two phenolic oxygens in a planar coordination site, the copper atom deviates from the mean plane by 0.47?. The "outside"copper atom is five coordinated by two phenolic oxygen atoms?two equatorial carboxyl oxygen atoms and one axial water oxygen atom in a distorted tetragonal cone site, the copper atom is pulled out of the equatorial plane by 0.46?.
文摘A Series of mono and di-nuclear Zn Ni complexes with 5 - chlorosalicylaldehyde -ethylenediamine Schiff base have been synthesized. Theirs compositions and structures were characterized by the elemental analysis.UV.IR spectra and 1H NMR. The Dismutation to O2 free radical has also been investigated.
文摘The formation of heterobimetallic ruthenium?complex was investigated by absorption and emission spectra. As an intercalator of DNA, the luminescent monometallic ruthenium?complex [Ru(bpy)2tpphz]2+could coordinate with Zn2+to form the nonluminescent heterobimetallic complex [Ru(bpy)2(tpphz)Zn]4+. The emission intensity of complex decreased as increasing the amounts of Zn2+and the luminescence was almost lost at the ratio of / of 1. After binding to DNA, the peripheral coordination site on the tpphz ligand remained accessible for Zn2+, the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)2tpphz]2+and the nonluminescent heterobimetallic complex was formed. On the other hand, the [Ru(bpy)2(tpphz)Zn]4+also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)2tpphz]2+between the base pairs of DNA. The complex looked like a molecular nut (the Zn2+) and bolt (the [Ru(bpy)2tpphz]2+).