A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal...A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.展开更多
Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only ...Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.展开更多
The copper( Ⅱ ) complex, [Cu(oxpn)Cu(tmen)2](ClO4)2 was synthesized, where oxpn is N, N' -bis ( 3-aminopropyl) oxamido and tmen is N, N, N' N' -tetram-ethylethylenediamine. The crystal is triclinic, space...The copper( Ⅱ ) complex, [Cu(oxpn)Cu(tmen)2](ClO4)2 was synthesized, where oxpn is N, N' -bis ( 3-aminopropyl) oxamido and tmen is N, N, N' N' -tetram-ethylethylenediamine. The crystal is triclinic, space group P 1, a=1-2349(2), b = 1.3093(2), c=1. 3855(2) nm, α=61-88(1), β=69.49(1), γ=57.91(1)°? V = 1. 6589 nm3, Z = 2. Both copper( Ⅱ ) ions are in a square pyramidal coordination environment , and linked by oxamido bridge. The distance between them is 0. 526 nm. Variable temperature (4. 2-300 K) magnetic susceptibility data for this complex show that there exists a relatively large antiferromagnetic exchange interaction between the two copper( Ⅱ ) ions with a J value of-740. 40 cm-1.展开更多
The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. ...The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure is of monoclinic, space group C2/c with a = 42.587(1), b = 14.1653(4), c = 20.5649(5) ? = 105.945(1)? V =11928.6 3, C57H60.5ClCu2NO5.25P4S2, Mr = 1194.09, Z = 8, Dc = 1.330 g/cm3, (MoK) = 0.98 mm-1 and F(000) = 4948. A total of 15243 reflections were collected, of which 7322 were unique. The structure was refined to R = 0.0739 and wR = 0.1846 for 5135 observed reflections with I > 2(I). The crystal structure consists of the complex cation [Cu2(-dppm)2(-Et2dtc)]+, anion ClO4- and solvate H2O and EtOH, where the dinuclear Cu(Ⅰ) atoms are bridged doubly by two dppm ligands and singly by Et2dtc to give three five-membered rings. The Cu(Ⅰ) atom is in an approxi- mately trigonal-planar environment with the P2S chromophore. The short Cu贩稢u separation (2.7111 ? suggests the presence of metal-metal contact.展开更多
Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPP...Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,with cell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°, V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections. Each copper ion is coordinated by four bridging benzoato ligands and one triphenylphosphine oxide group to form binuclear complexes.展开更多
Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one...Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one hydroxo bridging in one molecule [Cu_2(OH)(C_2H_5COO)(ds-phen)_2]. (NO_3)_2 H_2O(3) and one cononuclear Cu(Ⅱ) complex [Cu(de-phen)(CF_3COO)](NO_3).H_2O(4)(dm-phen= 2,9-dimethyl-1,10-phenanthrolin)were prepared and characterized. The effective magnetic moment, u elf, was measured and their magnetic properties were discussed. The coordination modes of carboxyl moieties in all the title complexes were proposed.展开更多
Dinuclear[Cu(H_(2)pmide)(NO_(3))Cu(Hpmide)](NO_(3))_(2)(1)and trinuclear[(pmide)_(2)Co_(3)(CH_(3)CO_(2))_(2)(NCS)_(2)]·4CH_(3)OH(2)coordination complexes have been prepared by the reaction of the tetradentate H_(...Dinuclear[Cu(H_(2)pmide)(NO_(3))Cu(Hpmide)](NO_(3))_(2)(1)and trinuclear[(pmide)_(2)Co_(3)(CH_(3)CO_(2))_(2)(NCS)_(2)]·4CH_(3)OH(2)coordination complexes have been prepared by the reaction of the tetradentate H_(2)pmide ligand and Cu(NO_(3))_(2)·3H_(2)O or Co(CH_(3)CO_(2))_(2)·4H_(2)O/NaNCS in organic solvent(H_(2)pmide=N-(2-pyridylmethyl)iminodiethanol).In 1,one copper(Ⅱ)ion is bonded with a H_(2)pmide,and the other is coordinated with a mono-deprotonated Hpmide^(-).The copper(Ⅱ)ions are linked through an ethoxo group of the Hpmide-ligand and two oxygen atoms of a nitrate ion,resulting in an asymmetric dinuclear structure.In 2,two terminal cobalt(Ⅲ)units are coordinated with pmide^(2-),NCS^(-),and CH_(3)CO_(2)^(-).The terminal units are each connected to a central cobalt(Ⅱ)cation through the two oxygen atoms of pmide2-and one bridged acetate ion,giving rise to a mixed-valence trinuclear cobalt complex formulated as Co^(Ⅲ)-Co^(Ⅱ)-Co^(Ⅲ).Complex 1 shows a strong antiferromagnetic interaction through the ethoxo and nitrato groups between the copper(Ⅱ)ions[g=2.070,J=-88.1 cm^(-1)(-61.2 K)].However,complex 2 behaves as a paramagnetic cobalt(Ⅱ)monomer,due to the diamagnetic cobalt(Ⅲ)ions in the terminal units[g=2.526,|D|=51.8 cm^(-1)(36.0 K)].展开更多
Triazolylidenes are an emerging class of mesoionic carbenes with potential as ligands in homogeneous catalysis.In this contribution we present well-defined dicopper(Ⅰ)complexes with di-mesoionic carbenes where the co...Triazolylidenes are an emerging class of mesoionic carbenes with potential as ligands in homogeneous catalysis.In this contribution we present well-defined dicopper(Ⅰ)complexes with di-mesoionic carbenes where the copper centers are held at a distance of about 2.8Å.All complexes display excellent activity as pre-catalysts for the azide–alkyne cycloaddition(click)reaction.Comparisons with analogous mononuclear complexes show the dinuclear pre-catalysts to be twice as active for the same amount of copper used.These results thus point to potentially strong cooperative effects in these dinuclear complexes,and further support the recently established dinuclear reaction pathway for the click reaction.The results presented here provide a synthetic route for generating dinuclear complexes with di-mesoionic carbenes with relatively short metal–metal distances,and opens a general platform for investigating potential cooperative effects in catalysis.展开更多
The oxalato-bridged dicopper(II)complexes[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2](1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2](2)and[Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2](3)[LRR=(8R,10R)-(-)-[...The oxalato-bridged dicopper(II)complexes[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2](1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2](2)and[Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2](3)[LRR=(8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS=(8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2=oxalate]were first prepared.A possible mechanism for the formation of the chial dicopper(II)complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II)ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II)ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be-338.41(4)cm-1,indicating a strong antiferromagnetic interaction between two copper(II)ions.展开更多
The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is u...The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.展开更多
Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). Th...Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). The complexes were characterized by elemental analyses, in fared and electronic spectra, magnetic susceptibilities and ESR spectra, indicating antiferromagnetic spin exchange interactions between metal ions.展开更多
Two new dicopper（II） complexes [Cu2L（OAc）2]（ClO4）·H2O （1） and [Cu2L（BPP）2]-（ClO4） （2） using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate （OAc） and bisphenyl phosphate...Two new dicopper（II） complexes [Cu2L（OAc）2]（ClO4）·H2O （1） and [Cu2L（BPP）2]-（ClO4） （2） using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate （OAc） and bisphenyl phosphate （BPP） have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and Pī space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu（1） and Cu（2） are both distorted square pyramids.展开更多
NbO-type MOFs constructed from dicopper paddlewheel secondary building units and diisophthalate ligands not only exhibit great promise for the separation of environment and energy-related gas pairs but also more impor...NbO-type MOFs constructed from dicopper paddlewheel secondary building units and diisophthalate ligands not only exhibit great promise for the separation of environment and energy-related gas pairs but also more importantly provide an excellent platform for the fundamental investigation of structure–property relationships.In this work,two NbO-type MOFs(ZJNU-91 and ZJNU-92)derived from linear and zigzag-shaped thieno[3,2-b]thiophene-functionalized diisophthalate ligands were solvothermally prepared and structurally characterized.展开更多
基金This work was supported by the National Natural Science Foundation of China (No. 20271029)
文摘A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.
文摘Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.
基金Supported by the National Natural Science Foundation of China
文摘The copper( Ⅱ ) complex, [Cu(oxpn)Cu(tmen)2](ClO4)2 was synthesized, where oxpn is N, N' -bis ( 3-aminopropyl) oxamido and tmen is N, N, N' N' -tetram-ethylethylenediamine. The crystal is triclinic, space group P 1, a=1-2349(2), b = 1.3093(2), c=1. 3855(2) nm, α=61-88(1), β=69.49(1), γ=57.91(1)°? V = 1. 6589 nm3, Z = 2. Both copper( Ⅱ ) ions are in a square pyramidal coordination environment , and linked by oxamido bridge. The distance between them is 0. 526 nm. Variable temperature (4. 2-300 K) magnetic susceptibility data for this complex show that there exists a relatively large antiferromagnetic exchange interaction between the two copper( Ⅱ ) ions with a J value of-740. 40 cm-1.
基金Supported by the Government of Guangdong province
文摘The title complex [Cu2(-dppm)2(-Et2dtc)](ClO4)EtOH0.25H2O (dppm = bis- (diphenylphosphino)methane, Et2dtc = diethyldithiocarbamate) has been synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure is of monoclinic, space group C2/c with a = 42.587(1), b = 14.1653(4), c = 20.5649(5) ? = 105.945(1)? V =11928.6 3, C57H60.5ClCu2NO5.25P4S2, Mr = 1194.09, Z = 8, Dc = 1.330 g/cm3, (MoK) = 0.98 mm-1 and F(000) = 4948. A total of 15243 reflections were collected, of which 7322 were unique. The structure was refined to R = 0.0739 and wR = 0.1846 for 5135 observed reflections with I > 2(I). The crystal structure consists of the complex cation [Cu2(-dppm)2(-Et2dtc)]+, anion ClO4- and solvate H2O and EtOH, where the dinuclear Cu(Ⅰ) atoms are bridged doubly by two dppm ligands and singly by Et2dtc to give three five-membered rings. The Cu(Ⅰ) atom is in an approxi- mately trigonal-planar environment with the P2S chromophore. The short Cu贩稢u separation (2.7111 ? suggests the presence of metal-metal contact.
文摘Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,with cell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°, V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections. Each copper ion is coordinated by four bridging benzoato ligands and one triphenylphosphine oxide group to form binuclear complexes.
基金This work was supported by Henan Natural Science Foundation.
文摘Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one hydroxo bridging in one molecule [Cu_2(OH)(C_2H_5COO)(ds-phen)_2]. (NO_3)_2 H_2O(3) and one cononuclear Cu(Ⅱ) complex [Cu(de-phen)(CF_3COO)](NO_3).H_2O(4)(dm-phen= 2,9-dimethyl-1,10-phenanthrolin)were prepared and characterized. The effective magnetic moment, u elf, was measured and their magnetic properties were discussed. The coordination modes of carboxyl moieties in all the title complexes were proposed.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education,Science and Technology(2013R1A1A2007314 and 2014R1A1A2058815).
文摘Dinuclear[Cu(H_(2)pmide)(NO_(3))Cu(Hpmide)](NO_(3))_(2)(1)and trinuclear[(pmide)_(2)Co_(3)(CH_(3)CO_(2))_(2)(NCS)_(2)]·4CH_(3)OH(2)coordination complexes have been prepared by the reaction of the tetradentate H_(2)pmide ligand and Cu(NO_(3))_(2)·3H_(2)O or Co(CH_(3)CO_(2))_(2)·4H_(2)O/NaNCS in organic solvent(H_(2)pmide=N-(2-pyridylmethyl)iminodiethanol).In 1,one copper(Ⅱ)ion is bonded with a H_(2)pmide,and the other is coordinated with a mono-deprotonated Hpmide^(-).The copper(Ⅱ)ions are linked through an ethoxo group of the Hpmide-ligand and two oxygen atoms of a nitrate ion,resulting in an asymmetric dinuclear structure.In 2,two terminal cobalt(Ⅲ)units are coordinated with pmide^(2-),NCS^(-),and CH_(3)CO_(2)^(-).The terminal units are each connected to a central cobalt(Ⅱ)cation through the two oxygen atoms of pmide2-and one bridged acetate ion,giving rise to a mixed-valence trinuclear cobalt complex formulated as Co^(Ⅲ)-Co^(Ⅱ)-Co^(Ⅲ).Complex 1 shows a strong antiferromagnetic interaction through the ethoxo and nitrato groups between the copper(Ⅱ)ions[g=2.070,J=-88.1 cm^(-1)(-61.2 K)].However,complex 2 behaves as a paramagnetic cobalt(Ⅱ)monomer,due to the diamagnetic cobalt(Ⅲ)ions in the terminal units[g=2.526,|D|=51.8 cm^(-1)(36.0 K)].
文摘Triazolylidenes are an emerging class of mesoionic carbenes with potential as ligands in homogeneous catalysis.In this contribution we present well-defined dicopper(Ⅰ)complexes with di-mesoionic carbenes where the copper centers are held at a distance of about 2.8Å.All complexes display excellent activity as pre-catalysts for the azide–alkyne cycloaddition(click)reaction.Comparisons with analogous mononuclear complexes show the dinuclear pre-catalysts to be twice as active for the same amount of copper used.These results thus point to potentially strong cooperative effects in these dinuclear complexes,and further support the recently established dinuclear reaction pathway for the click reaction.The results presented here provide a synthetic route for generating dinuclear complexes with di-mesoionic carbenes with relatively short metal–metal distances,and opens a general platform for investigating potential cooperative effects in catalysis.
基金supported by the National Natural Science Foundation of China(20773098&20973136)the Innovation Foundation of Xiamen University(Series 2)(XDKJCX20061027)
文摘The oxalato-bridged dicopper(II)complexes[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2](1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2](2)and[Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2](3)[LRR=(8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS=(8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2=oxalate]were first prepared.A possible mechanism for the formation of the chial dicopper(II)complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II)ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II)ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be-338.41(4)cm-1,indicating a strong antiferromagnetic interaction between two copper(II)ions.
基金the support from the National Natural Science Foundation of China(No.20172038).
文摘The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.
基金Supported by the National Natural Science Foundation of China
文摘Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). The complexes were characterized by elemental analyses, in fared and electronic spectra, magnetic susceptibilities and ESR spectra, indicating antiferromagnetic spin exchange interactions between metal ions.
文摘Two new dicopper（II） complexes [Cu2L（OAc）2]（ClO4）·H2O （1） and [Cu2L（BPP）2]-（ClO4） （2） using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate （OAc） and bisphenyl phosphate （BPP） have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and Pī space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu（1） and Cu（2） are both distorted square pyramids.
基金the Natural Science Foundation of China(No.21771162)the Natural Science Foundation of Zhejiang Province,China(LR16B010001)the Qianjiang Talents Project in Zhejiang Province(ZC304015017)for financial support.
文摘NbO-type MOFs constructed from dicopper paddlewheel secondary building units and diisophthalate ligands not only exhibit great promise for the separation of environment and energy-related gas pairs but also more importantly provide an excellent platform for the fundamental investigation of structure–property relationships.In this work,two NbO-type MOFs(ZJNU-91 and ZJNU-92)derived from linear and zigzag-shaped thieno[3,2-b]thiophene-functionalized diisophthalate ligands were solvothermally prepared and structurally characterized.
