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
Five novel chiral dinuclear Salen complexes M2L (M = Fe3+Cl-, Mn3+Cl-, Co2+, Ni2+, Cu2+) and Ba2+-crown ether complex H4BaL(ClO4)2 were synthesized. The complexes were synthesized by reaction between ligand 3 (H4L) an...Five novel chiral dinuclear Salen complexes M2L (M = Fe3+Cl-, Mn3+Cl-, Co2+, Ni2+, Cu2+) and Ba2+-crown ether complex H4BaL(ClO4)2 were synthesized. The complexes were synthesized by reaction between ligand 3 (H4L) and corresponding metal salts (FeCl3, Mn(OAc)2·4H2O, Co(OAc)2·4H2O, Ni(OAc)2·4H2O, Cu(OAc)2·H2O, Ba(ClO4)2·2H2O). The chiral two discrete Salen ligand 3 was condensed from 3,3′-[Oxybis(2,l-ethanediyloxy)]bis(2-hydroxybenzaldehyde) and (R,R)-1,2-diamino-cyclohexane. The structure of complexes is two discrete Salen unit bridged with crown ether from two sides. We found that ligand 3 had three complex cites. The two N2O2 cavities can found complexes with d-metals (compound 4), while the O10 cavity can found complex with alkali metals and alkaline-earth metals (compound 5). The compounds were characterized by elemental analyses, 1H NMR, Mass-spectra, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra property of complexes were minutely analyzed.展开更多
The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffractio...The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffraction method at room temperature. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.855(2)?, b=14.722(3)?, c=12.080(2)?, β=117.32(3)°, V=1879.4(7)?3 , Z=4 with R1=0.0330. The structure is made of heterobinuclear units . The copper atom is coordinated by two nitrogens, two phenolic oxygens, in a square planar manner. And the cobalt atom is coordinated by two phenolic oxygen atoms, two equatorial carboxyl oxygen atoms and one axial water oxygen atom, in a distorted square pyramid. Two metal atoms are bridged by two phenolic oxygens. In the crystal packing, the neutral molecules built layers. Within these layers the molecules are connected through hydrogen bonds. And the thermal property of the complex according to crystal structure is also investigated.展开更多
A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-5-(3-tert-butyl-2-hydroxy benzaldehyde) -α-D-glucofuranose with (1R,2R)-1,2-diamino...A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-5-(3-tert-butyl-2-hydroxy benzaldehyde) -α-D-glucofuranose with (1R,2R)-1,2-diaminocyclohexane. Several chiral complexes of Mn3+, Fe3+, Co2+ and Cu2+ were prepared from this ligand. Both the ligand and the complexes were characterized by elemental analysis, NMR, IR, MS, and UV-Vis.展开更多
Binuclear mixed valent manganese complex [(Phen) 2Mn( μ O) 2Mn(Phen) 2] (ClO 4) 3·CH 2ClCOOH·2H 2O was synthesized by the reaction of [Mn 3O(O 2CCH 2Cl) 6(C 5H 5N) 2(H 2O)] ·CH 2ClCOO·H 2O with Ph...Binuclear mixed valent manganese complex [(Phen) 2Mn( μ O) 2Mn(Phen) 2] (ClO 4) 3·CH 2ClCOOH·2H 2O was synthesized by the reaction of [Mn 3O(O 2CCH 2Cl) 6(C 5H 5N) 2(H 2O)] ·CH 2ClCOO·H 2O with Phen and NaClO 4 in the CH 2ClCOOH CH 2ClCOONa buffer (pH=4.0). X ray diffraction result for the single crystal shows that the crystal is triclinic, space group P 1, with a =\{1.182 64(7)\} nm, b =1.449 32(8) nm, c =1.664 99(9) nm, α =104.585 0(10)°, β =97.123 0(10)°, \{ γ =\}106.921 0(10)°, V =2.581 6(3) nm 3, Z =2, D c=1.660 g·cm -3 , R =0.052 2. A peak at 640 nm in UV Vis spectrum is designed to the electronic transition of bridge legend O 2- to Mn(Ⅲ). Cyclic voltammogram shows that the complex in CH 3CN undergoes two quasi reversible one electron redox reactions at E 1/2 =1.25 V and E 1/2 =0.33 V, respectively.展开更多
The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction....The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.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Five novel chiral dinuclear Salen complexes M2L (M = Fe3+Cl-, Mn3+Cl-, Co2+, Ni2+, Cu2+) and Ba2+-crown ether complex H4BaL(ClO4)2 were synthesized. The complexes were synthesized by reaction between ligand 3 (H4L) and corresponding metal salts (FeCl3, Mn(OAc)2·4H2O, Co(OAc)2·4H2O, Ni(OAc)2·4H2O, Cu(OAc)2·H2O, Ba(ClO4)2·2H2O). The chiral two discrete Salen ligand 3 was condensed from 3,3′-[Oxybis(2,l-ethanediyloxy)]bis(2-hydroxybenzaldehyde) and (R,R)-1,2-diamino-cyclohexane. The structure of complexes is two discrete Salen unit bridged with crown ether from two sides. We found that ligand 3 had three complex cites. The two N2O2 cavities can found complexes with d-metals (compound 4), while the O10 cavity can found complex with alkali metals and alkaline-earth metals (compound 5). The compounds were characterized by elemental analyses, 1H NMR, Mass-spectra, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra property of complexes were minutely analyzed.
文摘The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffraction method at room temperature. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.855(2)?, b=14.722(3)?, c=12.080(2)?, β=117.32(3)°, V=1879.4(7)?3 , Z=4 with R1=0.0330. The structure is made of heterobinuclear units . The copper atom is coordinated by two nitrogens, two phenolic oxygens, in a square planar manner. And the cobalt atom is coordinated by two phenolic oxygen atoms, two equatorial carboxyl oxygen atoms and one axial water oxygen atom, in a distorted square pyramid. Two metal atoms are bridged by two phenolic oxygens. In the crystal packing, the neutral molecules built layers. Within these layers the molecules are connected through hydrogen bonds. And the thermal property of the complex according to crystal structure is also investigated.
文摘A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-5-(3-tert-butyl-2-hydroxy benzaldehyde) -α-D-glucofuranose with (1R,2R)-1,2-diaminocyclohexane. Several chiral complexes of Mn3+, Fe3+, Co2+ and Cu2+ were prepared from this ligand. Both the ligand and the complexes were characterized by elemental analysis, NMR, IR, MS, and UV-Vis.
文摘Binuclear mixed valent manganese complex [(Phen) 2Mn( μ O) 2Mn(Phen) 2] (ClO 4) 3·CH 2ClCOOH·2H 2O was synthesized by the reaction of [Mn 3O(O 2CCH 2Cl) 6(C 5H 5N) 2(H 2O)] ·CH 2ClCOO·H 2O with Phen and NaClO 4 in the CH 2ClCOOH CH 2ClCOONa buffer (pH=4.0). X ray diffraction result for the single crystal shows that the crystal is triclinic, space group P 1, with a =\{1.182 64(7)\} nm, b =1.449 32(8) nm, c =1.664 99(9) nm, α =104.585 0(10)°, β =97.123 0(10)°, \{ γ =\}106.921 0(10)°, V =2.581 6(3) nm 3, Z =2, D c=1.660 g·cm -3 , R =0.052 2. A peak at 640 nm in UV Vis spectrum is designed to the electronic transition of bridge legend O 2- to Mn(Ⅲ). Cyclic voltammogram shows that the complex in CH 3CN undergoes two quasi reversible one electron redox reactions at E 1/2 =1.25 V and E 1/2 =0.33 V, respectively.
文摘The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.
