A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
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
A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in...A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.展开更多
Reactions of CuBr with equimolar PyHBr orγMePyHBr afforded two novel one dimensional bromocuprate?polymers{(PyH)_(3)[Cu_(3)Br_(6)]}_(∞)(1)and{(γMePyH)_(2)[Cu_(2)Br_(4)]}_(∞)(2),respectively.Both 1 and 2 were chara...Reactions of CuBr with equimolar PyHBr orγMePyHBr afforded two novel one dimensional bromocuprate?polymers{(PyH)_(3)[Cu_(3)Br_(6)]}_(∞)(1)and{(γMePyH)_(2)[Cu_(2)Br_(4)]}_(∞)(2),respectively.Both 1 and 2 were characterized by IR,elemental analysis,and X ray crystallography.Crystal data for 1:monoclinic,space group P2_(1)/n,a=0.93262(12)nm,b=1.3497(2)nm,c=1.9149(2)nm,β=93.465(7)°,V=2.4060(5)nm^(3),Z=4.Crystal data for 2:orthorhombic,space group Pbcm,a=0.8659(4)nm,b=1.5669(6)nm,c=1.2849(5)nm,V=1.7432(2)nm^(3),Z=4.The structure of 1 has a unique helical chain composed of units andμbromide anions while that of 2 shows a linear chain consisted of[Cu_(2)(μBr)_(2)]units bridged by pairs ofμBr atoms.CCDC:1,208412;2,208413.展开更多
A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-r...A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P21/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm3, Dc=1.769 Mg·m-3, Z=2, F(000)=744, R1=0.025 4, wR2=0.069 5, Gof=1.077, Δρ=328^-455 e·nm-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO3- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO3- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.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 aminocarboxylic acid, phenyliminodiacetic acid [C 6H 5N(CH 2COOH) 2, H 2L] , was synthesized by the reaction between phenylid and chloroacetic acid. The copper complex with the acid [CuL(H 2O)] was obtained in aqu...The aminocarboxylic acid, phenyliminodiacetic acid [C 6H 5N(CH 2COOH) 2, H 2L] , was synthesized by the reaction between phenylid and chloroacetic acid. The copper complex with the acid [CuL(H 2O)] was obtained in aquo solution and its crystal structure was determined by X ray diffraction with a final R 1 value of 0.024 4 and a wR 2 value of 0.066 0. The crystal is of monoclinic system with a space group P2 1/C . The unit cell parameters are as follows: a =1.218 3(2) nm, b =0.868 31(10) nm, c= 0.979 40 nm , β =96.100(10)°, V =1.032 2(2) nm 3, Z =4, D c=1.862 g/cm 3, F (000)=588, μ =2.129 mm -1 . In crystal, each copper ion is coordinated with three oxygen atoms and one nitrogen atom from H 2L and an oxygen atom from water; the coordination polyhedron around Cu 2+ is a distorted tetragonal pyramid. Cu 2+ are linked by anti anti carboxyl bridges to form endless zigzag chain, a two dimensional network is obtained through the hydrogen bonds between the adjacent chains.展开更多
The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space...The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space group of P2 1 /c.The cell parameters are a=1.42231(2)nm,b=2.53181(3)nm,c=1.43392(2)nm,β=102.0518(5)°,Z =4,F(000)=2360,D c =1.508g·cm -3 ,The final R=0.0788,w R 2 =0.232,The catalytic rate constant of the dismutation of superoxide radic als has been obtained by means of photo reduction of nitroblue tetrazoliu m(NBT),and it is 1.875×10 6 mol -1 ·L·s -1 .展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
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A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.
文摘Reactions of CuBr with equimolar PyHBr orγMePyHBr afforded two novel one dimensional bromocuprate?polymers{(PyH)_(3)[Cu_(3)Br_(6)]}_(∞)(1)and{(γMePyH)_(2)[Cu_(2)Br_(4)]}_(∞)(2),respectively.Both 1 and 2 were characterized by IR,elemental analysis,and X ray crystallography.Crystal data for 1:monoclinic,space group P2_(1)/n,a=0.93262(12)nm,b=1.3497(2)nm,c=1.9149(2)nm,β=93.465(7)°,V=2.4060(5)nm^(3),Z=4.Crystal data for 2:orthorhombic,space group Pbcm,a=0.8659(4)nm,b=1.5669(6)nm,c=1.2849(5)nm,V=1.7432(2)nm^(3),Z=4.The structure of 1 has a unique helical chain composed of units andμbromide anions while that of 2 shows a linear chain consisted of[Cu_(2)(μBr)_(2)]units bridged by pairs ofμBr atoms.CCDC:1,208412;2,208413.
文摘A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P21/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm3, Dc=1.769 Mg·m-3, Z=2, F(000)=744, R1=0.025 4, wR2=0.069 5, Gof=1.077, Δρ=328^-455 e·nm-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO3- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO3- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.
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 aminocarboxylic acid, phenyliminodiacetic acid [C 6H 5N(CH 2COOH) 2, H 2L] , was synthesized by the reaction between phenylid and chloroacetic acid. The copper complex with the acid [CuL(H 2O)] was obtained in aquo solution and its crystal structure was determined by X ray diffraction with a final R 1 value of 0.024 4 and a wR 2 value of 0.066 0. The crystal is of monoclinic system with a space group P2 1/C . The unit cell parameters are as follows: a =1.218 3(2) nm, b =0.868 31(10) nm, c= 0.979 40 nm , β =96.100(10)°, V =1.032 2(2) nm 3, Z =4, D c=1.862 g/cm 3, F (000)=588, μ =2.129 mm -1 . In crystal, each copper ion is coordinated with three oxygen atoms and one nitrogen atom from H 2L and an oxygen atom from water; the coordination polyhedron around Cu 2+ is a distorted tetragonal pyramid. Cu 2+ are linked by anti anti carboxyl bridges to form endless zigzag chain, a two dimensional network is obtained through the hydrogen bonds between the adjacent chains.
文摘The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space group of P2 1 /c.The cell parameters are a=1.42231(2)nm,b=2.53181(3)nm,c=1.43392(2)nm,β=102.0518(5)°,Z =4,F(000)=2360,D c =1.508g·cm -3 ,The final R=0.0788,w R 2 =0.232,The catalytic rate constant of the dismutation of superoxide radic als has been obtained by means of photo reduction of nitroblue tetrazoliu m(NBT),and it is 1.875×10 6 mol -1 ·L·s -1 .