A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized b...A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.展开更多
Two new tri-spin radical-Ln(III)-radical complexes, [Ln(hfac)3(NITPh-Ph)2] (Ln = Dy (1) and Tb (2), NITPh-Ph = 4'-biphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and hfac = hexafluoroacetylacetonat...Two new tri-spin radical-Ln(III)-radical complexes, [Ln(hfac)3(NITPh-Ph)2] (Ln = Dy (1) and Tb (2), NITPh-Ph = 4'-biphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and hfac = hexafluoroacetylacetonate) have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, Uv-visible and magnetic properties. X-ray analysis reveals that the two complexes are isomorphous and crystallize in the triclinic system, space group P1. For complex 1, a = 12.402(3), b = 15.414(3), c = 17.383(3) A, a = 68.61(3), β = 81.97(3), y = 79.40(3)°, V = 3031.7(11) A3, Z = 2, Mr = 1401.86, Dc = 1.536 g/cm^3, kt = 1.344 mm^-1, F(000) = 1398, the final GOF = 1.173, R = 0.0670 and wR = 0.1376 for 9035 observed reflections with 1 〉 2a(/); while for complex 2, a = 12.397(3), b = 15.391(3), c = 17.395(4) A, a = 68.62(3), fl = 81.97(3), ), = 79.60(3)°, V = 3030.0(11) A3, Z = 2, Mr = 1398.29, Dc = 1.537 g/cm^3,μ = 1.344 mm-1, F(000) = 1398, the final GOF = 1.130, R = 0.0644 and wR = 0.1382 for 8989 observed reflections with 1 〉 2a(/). They all consist of the discrete adducts, in which the central Ln(lll) ions are coordinated by six oxygen atoms from three hfacs and two oxygen atoms from nitronyl radicals. The temperature dependency of magnetic susceptibilities for these two complexes is studied, showing that the magnetic interactions are governed by the depopulation of the Ln Stark levels.展开更多
A new complex, [Ni(acac)2(NITQ)2]-2CH2C12 1 (acac = acetylacetone, NITQ = 2-(2"-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide), was synthesized and charac- terized by elemental analysis, IR spec...A new complex, [Ni(acac)2(NITQ)2]-2CH2C12 1 (acac = acetylacetone, NITQ = 2-(2"-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide), was synthesized and charac- terized by elemental analysis, IR spectroscopy, UV-Vis absorption spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 9.6970(19), b = 20.410(4), c = 12.166(2) A, β = 93.89(3)°, Mr = 997.43, V= 2402.3(8) A3, Z = 2, Dc = 1.379 g/cm3, F(000) = 1040,μ = 0.684 mm-1, the final R = 0.0423 and wR = 0.1197 for 2884 observed reflections (1 〉 2σ(I)). Compound 1 is found to assume a mononuclear structure, which is further linked into a three-dimensional (3D) supramolecular network by hydrogen-bonding, C1...O weak contact and π...π stacking interactions. Moreover, the luminescent properties of the ligand and compound 1 were further investigated in detail.展开更多
A new complex of formula [Co(nitmpy)2(tp)(H2O)2]n (nitmpy = 2-(3-pyridyl)- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and tp = terephthalato dianion) has been synthesized and structurally characterized. The complex...A new complex of formula [Co(nitmpy)2(tp)(H2O)2]n (nitmpy = 2-(3-pyridyl)- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and tp = terephthalato dianion) has been synthesized and structurally characterized. The complex crystallizes in monoclinic, space group P21/n with a = 10.647(3), b = 11.093(3), c = 16.647(5) ? b = 106.185(6), V = 1888.2(10) 3, C32H40CoN6O10, Mr = 727.63, Dc = 1.280 g/cm3, m(MoKa) = 0.513 mm-1, F(000) = 762, Z = 2, the final R = 0.0549 and wR = 0.1265 for 1753 observed reflections (I > 2s(I)). The crystal structure consists of neutral infinite chains where the Co(nitmpy)2(H2O)2 units are linked by terephthalate ligands, and the 1-D chains develop into two-dimensional network via the hydrogen bond interactions.展开更多
A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffr...A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13)A, β = 103.904(2)°, V = 1919.6(5)A^3, Dc = 1.528 g/cm^3, μ(MoKα) = 1.579 mm^-1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I〉 2σ(I). X-ray analysis reveals that the Zn(Ⅱ) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.展开更多
A new one-dimensional dicyanamide bridged zinc(Ⅱ) complex containing nitronyl nitroxide radicals [Zn(NO3)(NIT-1′-MeBzIm)(dca)]n·(H2O)n (NIT-1′-MeBzIm = 2-{2′-[(1′-methyl)benzimidazolyl]}-4,4,5,5...A new one-dimensional dicyanamide bridged zinc(Ⅱ) complex containing nitronyl nitroxide radicals [Zn(NO3)(NIT-1′-MeBzIm)(dca)]n·(H2O)n (NIT-1′-MeBzIm = 2-{2′-[(1′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P^-1, with a = 7.428(3), b = 9.839(3), c = 16.708(6) A^°, α = 93.270(4), β = 101.642(4),γ= 100.632(4)°, C17.5H21N8O5.5Zn, Mr = 496.79, V = 1169.7(7) A^°^3, Dc = 1.411 g/cm^3, μ(MoKα) - 1.096 mm^-1, Z = 2, F(000) = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I 〉 2σ(I). X-ray analysis reveals that the zinc(Ⅱ) ion is six-coordinated with a distorted octahedral geometry. These units develop as 1D species where dicyanamide ligands bridge zine(ID ions. In addition, molecules are linked by π-π piling interactions to form 1-D double-chains. Magnetic investigation indicates that the weak intramolecular interactions are antiferromagnetic with J = -0.27 cm^-1, where the spin Hamitonian is defined as H = -2∑ijJijSiS within the complex.展开更多
A novel azide-bridged copper(Ⅱ) coordination polymer, [Cu3(NITpPy)4(N3)6]n (NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl), was structurally and magnetically characterized. It crystallizes i...A novel azide-bridged copper(Ⅱ) coordination polymer, [Cu3(NITpPy)4(N3)6]n (NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl), was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932(10), b = 14.5556(19), c = 16.122(2) , α = 108.443(2), β = 95.251(2), γ = 104.236(2)°, V = 1631.7(4) 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ(MoKα) = 1.041 mm-1, F(000) = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I 2σ(I). X-ray analysis reveals that the Cu(Ⅱ) ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.展开更多
A new oxalato-bridged dinickel(Ⅱ) complex [Ni2(NIT-MeImz)4(C2O4)](Ac)2·8H2O has been synthesized and characterized structurally as well as magnetically.It crystallizes in monoclinic,space group C2/c with...A new oxalato-bridged dinickel(Ⅱ) complex [Ni2(NIT-MeImz)4(C2O4)](Ac)2·8H2O has been synthesized and characterized structurally as well as magnetically.It crystallizes in monoclinic,space group C2/c with a=24.608(4),b=21.399(3),c=17.992(3),β=131.680(2)°,V=7076(2)3,C50H86N16Ni2O24,Mr=1412.77,Z=4,Dc=1.326 g/cm3,μ(MoKα)=0.614 mm-1,F(000)=2984,R=0.0751 and wR=0.1791 for 2956 observed reflections with Ⅰ>2σ(Ⅰ).X-ray analysis reveals that the crystal structure consists of [Ni2(NIT-MeImz)4(C2O4)]2+ moiety and two Ac^- anions. Each nickel(H) ion is six-coordinated with a distorted octahedral geometry: two nitrogen atoms and two oxygen atoms from NIT-Melmz together with two other oxygen atoms from the oxalato ion. The 2-D net structure is formed and arranged through intermolecular H-bonding interactions. Magnetic measurements show antiferromagnetic interactions for this complex.展开更多
A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2].(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline- 1-oxyl) has been synthesized and characterized structura...A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2].(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline- 1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12)A, β = 105.0290(10)^o, V = 1552.25(19)A3, C24H34CUN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm^3,μ(MoKα) = 0.876 mm^-1, F(000) = 650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a k-2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two 0 and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.展开更多
A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurall...A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurally as well as magnetically in detail. The crystal belongs to the monoclinic system, space group P2_1/c with a = 9.6896(1), b = 20.539(4), c = 12.147(2) ?, β = 93.84(3)°, M_r = 997.65, V = 2412.1(8) ?~3, Z = 2, Dc = 1.374 g/cm, F(000) = 1038, m = 0.635 mm^(-1), the final R = 0.0539 and w R = 0.1289 for 5998 observed reflections(I 〉 2σ(I)). The Co(Ⅱ) ion is coordinated by two nitrogen atoms of quinoxaline rings from two NITQs and four oxygen atoms from two acac ions to complete a distorted octahedral coordination environment. Compound 1 is further linked into a three-dimensional(3D) supramolecular network by hydrogen-bonding, Cl×××O weak contact and π···π stacking interactions. The magnetic measurements show compound 1 exhibits weak ferromagnetic interactions.展开更多
Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n...Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln([Mo]/[M]) vs. time were liner respectively, indicating that was a controlled photopolymerization.展开更多
Compound 1 was first synthesized and characterized. Its crystal structure and magnetic property were determined and investigated. Discussion about the molecule packing in crystal and the macroscopic magnetism was also...Compound 1 was first synthesized and characterized. Its crystal structure and magnetic property were determined and investigated. Discussion about the molecule packing in crystal and the macroscopic magnetism was also presented, in combination with computing study of the spatial distribution over the molecule.展开更多
Stable s-butyl n-heptafluorobutyryl nitroxide 3 has been generated in an electron transfer reaction in F113 ( CFCl2CF2Cl ) solution at r.t. The aN values for 3 in 11 aprotic solvents show a linear correlation with cy...Stable s-butyl n-heptafluorobutyryl nitroxide 3 has been generated in an electron transfer reaction in F113 ( CFCl2CF2Cl ) solution at r.t. The aN values for 3 in 11 aprotic solvents show a linear correlation with cybotactic solvent parameters ET and Z. The physical significance for slopes, slope×ET or slope×Z, and the extrapolated intercepts on the aN axis are well established. The plots of aN versus noncybotactic solvent parameters, such as dipolar moment and dielectric constant, are badly behaved.展开更多
Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl (TIPNO) and α, ω-alkyl bromide by atom transfer radical addition(ATRA) was employed as “biradical initiator” for nitr...Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl (TIPNO) and α, ω-alkyl bromide by atom transfer radical addition(ATRA) was employed as “biradical initiator” for nitroxide-mediated radical polymerization(NMRP) of isoprene and styrene. The kinetics study for the polymerization of styrene at different time showed living features. The poly(styrene-b-isoprene-b-styrene) (SIS) copolymers have two glass transition temperatures, indicating the immiscibility of the corresponding blocks.展开更多
Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]....Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]. Organic materials, such as conducting polymers (polyacetylene, polypyrrole, polyaniline, etc.)[5], conjugated carbonyl compounds (quinone compounds, imides, etc.)[6–9] and nitroxide radical (N-O.)[10,11] compounds have been attempted as cathode materials in lithium-ion batteries (LIBs).展开更多
The electron spin resonance spectra of N-carbamoyl-N-(l-oxyl-2,2,5,5-tetramethyl-pyrrolin-3-yl) urea compounds in ten solvents with different polarities were determined. It was found that the hyperfine splitting const...The electron spin resonance spectra of N-carbamoyl-N-(l-oxyl-2,2,5,5-tetramethyl-pyrrolin-3-yl) urea compounds in ten solvents with different polarities were determined. It was found that the hyperfine splitting constant AN and spin density pN. as well as the energy difference between two adjacent energy levels E of different pyrroline nitroxides in the same solvent increase with the increase of electron-withdrawing α-bility of the substituted groups on the aromatic ring. There was a linear correlation between AN and Reichardt ET value, and between AN and Z value as well. Such a linear correlation was also found between solvent viscosity n and ESR rotational correlation time r. On the other hand, the correlation between T and the relative height hr of peak on high field was reverse. The results are discussed in the paper.展开更多
The titled compound 1 as well as compounds 2 and 3 with similar chemical structures were prepared and characterized. The magnetic properties of 1 were investigated with SQUID (MPMS, quantum design) magnetometer. Studi...The titled compound 1 as well as compounds 2 and 3 with similar chemical structures were prepared and characterized. The magnetic properties of 1 were investigated with SQUID (MPMS, quantum design) magnetometer. Studies with Langmuir-Blodgett (LB) technique indicated that stable condensed film of 1 could be formed at air-water interface and could be transferred onto various solid substrate under suitable conditions.展开更多
Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room ...Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room temperature in CFCl2-CF2Cl.展开更多
4-oxo-2, 2, 6, 6-tetramethylpiperidinyl-1-oxy radical (TEMPO), a nitroxide, oxidized 4-substituted Hantzsch 1,4-dihydropyridines (DHP) under UV irradiation in CH3CN to give aromatic products in good yields. A possible...4-oxo-2, 2, 6, 6-tetramethylpiperidinyl-1-oxy radical (TEMPO), a nitroxide, oxidized 4-substituted Hantzsch 1,4-dihydropyridines (DHP) under UV irradiation in CH3CN to give aromatic products in good yields. A possible mechanism for the oxidation was suggested.展开更多
基金supported by the National Natural Science Foundation of China (No. 20901059)the Technological Development Foundation Project of Tianjin Educational Committee (No. 20080503)
文摘A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.
基金Supported by the Natural Science Foundation of Anhui Province (KJ2012B174)the Doctoral Start-up Fund of Huainan Normal University
文摘Two new tri-spin radical-Ln(III)-radical complexes, [Ln(hfac)3(NITPh-Ph)2] (Ln = Dy (1) and Tb (2), NITPh-Ph = 4'-biphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and hfac = hexafluoroacetylacetonate) have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, Uv-visible and magnetic properties. X-ray analysis reveals that the two complexes are isomorphous and crystallize in the triclinic system, space group P1. For complex 1, a = 12.402(3), b = 15.414(3), c = 17.383(3) A, a = 68.61(3), β = 81.97(3), y = 79.40(3)°, V = 3031.7(11) A3, Z = 2, Mr = 1401.86, Dc = 1.536 g/cm^3, kt = 1.344 mm^-1, F(000) = 1398, the final GOF = 1.173, R = 0.0670 and wR = 0.1376 for 9035 observed reflections with 1 〉 2a(/); while for complex 2, a = 12.397(3), b = 15.391(3), c = 17.395(4) A, a = 68.62(3), fl = 81.97(3), ), = 79.60(3)°, V = 3030.0(11) A3, Z = 2, Mr = 1398.29, Dc = 1.537 g/cm^3,μ = 1.344 mm-1, F(000) = 1398, the final GOF = 1.130, R = 0.0644 and wR = 0.1382 for 8989 observed reflections with 1 〉 2a(/). They all consist of the discrete adducts, in which the central Ln(lll) ions are coordinated by six oxygen atoms from three hfacs and two oxygen atoms from nitronyl radicals. The temperature dependency of magnetic susceptibilities for these two complexes is studied, showing that the magnetic interactions are governed by the depopulation of the Ln Stark levels.
基金Supported by the National Natural Science Foundation of China(No.21071006)the Natural Science Foundation of Henan Province(No.102102210457)the Natural Science Foundation of the Henan Higher Education Institutions of China(No.2010B150001)
文摘A new complex, [Ni(acac)2(NITQ)2]-2CH2C12 1 (acac = acetylacetone, NITQ = 2-(2"-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide), was synthesized and charac- terized by elemental analysis, IR spectroscopy, UV-Vis absorption spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 9.6970(19), b = 20.410(4), c = 12.166(2) A, β = 93.89(3)°, Mr = 997.43, V= 2402.3(8) A3, Z = 2, Dc = 1.379 g/cm3, F(000) = 1040,μ = 0.684 mm-1, the final R = 0.0423 and wR = 0.1197 for 2884 observed reflections (1 〉 2σ(I)). Compound 1 is found to assume a mononuclear structure, which is further linked into a three-dimensional (3D) supramolecular network by hydrogen-bonding, C1...O weak contact and π...π stacking interactions. Moreover, the luminescent properties of the ligand and compound 1 were further investigated in detail.
基金the National Natural Science Foundation of China (No. 20271029)
文摘A new complex of formula [Co(nitmpy)2(tp)(H2O)2]n (nitmpy = 2-(3-pyridyl)- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and tp = terephthalato dianion) has been synthesized and structurally characterized. The complex crystallizes in monoclinic, space group P21/n with a = 10.647(3), b = 11.093(3), c = 16.647(5) ? b = 106.185(6), V = 1888.2(10) 3, C32H40CoN6O10, Mr = 727.63, Dc = 1.280 g/cm3, m(MoKa) = 0.513 mm-1, F(000) = 762, Z = 2, the final R = 0.0549 and wR = 0.1265 for 1753 observed reflections (I > 2s(I)). The crystal structure consists of neutral infinite chains where the Co(nitmpy)2(H2O)2 units are linked by terephthalate ligands, and the 1-D chains develop into two-dimensional network via the hydrogen bond interactions.
基金supported by the National Natural Science Foundation of China (Nos. 20471026 and 20771054)the Henan Tackle Key Problem of Science and Technology (No. 0524220001)
文摘A new complex [Zn(NIT-1′-MeBzlm)Cl2(H2O)] (NIT-1′-MeBzlm = 2-{2′-[(1′- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13)A, β = 103.904(2)°, V = 1919.6(5)A^3, Dc = 1.528 g/cm^3, μ(MoKα) = 1.579 mm^-1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I〉 2σ(I). X-ray analysis reveals that the Zn(Ⅱ) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.
基金Supported by the National Natural Science Foundation of China (Nos. 20471026 and 20771054)the Henan Tackle Key Problem of Science and Technology (No. 0524220001)
文摘A new one-dimensional dicyanamide bridged zinc(Ⅱ) complex containing nitronyl nitroxide radicals [Zn(NO3)(NIT-1′-MeBzIm)(dca)]n·(H2O)n (NIT-1′-MeBzIm = 2-{2′-[(1′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P^-1, with a = 7.428(3), b = 9.839(3), c = 16.708(6) A^°, α = 93.270(4), β = 101.642(4),γ= 100.632(4)°, C17.5H21N8O5.5Zn, Mr = 496.79, V = 1169.7(7) A^°^3, Dc = 1.411 g/cm^3, μ(MoKα) - 1.096 mm^-1, Z = 2, F(000) = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I 〉 2σ(I). X-ray analysis reveals that the zinc(Ⅱ) ion is six-coordinated with a distorted octahedral geometry. These units develop as 1D species where dicyanamide ligands bridge zine(ID ions. In addition, molecules are linked by π-π piling interactions to form 1-D double-chains. Magnetic investigation indicates that the weak intramolecular interactions are antiferromagnetic with J = -0.27 cm^-1, where the spin Hamitonian is defined as H = -2∑ijJijSiS within the complex.
基金supported by the National Natural Science Foundations of China (Nos. 20771054 and 21071074)
文摘A novel azide-bridged copper(Ⅱ) coordination polymer, [Cu3(NITpPy)4(N3)6]n (NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl), was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932(10), b = 14.5556(19), c = 16.122(2) , α = 108.443(2), β = 95.251(2), γ = 104.236(2)°, V = 1631.7(4) 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ(MoKα) = 1.041 mm-1, F(000) = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I 2σ(I). X-ray analysis reveals that the Cu(Ⅱ) ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.
基金supported by the National Natural Science Foundation of China (Nos 20471026 and 20771054)the Natural Science Foundation of Henan Province (No 0311021200)
文摘A new oxalato-bridged dinickel(Ⅱ) complex [Ni2(NIT-MeImz)4(C2O4)](Ac)2·8H2O has been synthesized and characterized structurally as well as magnetically.It crystallizes in monoclinic,space group C2/c with a=24.608(4),b=21.399(3),c=17.992(3),β=131.680(2)°,V=7076(2)3,C50H86N16Ni2O24,Mr=1412.77,Z=4,Dc=1.326 g/cm3,μ(MoKα)=0.614 mm-1,F(000)=2984,R=0.0751 and wR=0.1791 for 2956 observed reflections with Ⅰ>2σ(Ⅰ).X-ray analysis reveals that the crystal structure consists of [Ni2(NIT-MeImz)4(C2O4)]2+ moiety and two Ac^- anions. Each nickel(H) ion is six-coordinated with a distorted octahedral geometry: two nitrogen atoms and two oxygen atoms from NIT-Melmz together with two other oxygen atoms from the oxalato ion. The 2-D net structure is formed and arranged through intermolecular H-bonding interactions. Magnetic measurements show antiferromagnetic interactions for this complex.
基金This work was supported by the N N S F of China (No. 20471026)the Natural Science Foundation of Henan Province (No. 0311021200)
文摘A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2].(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline- 1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12)A, β = 105.0290(10)^o, V = 1552.25(19)A3, C24H34CUN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm^3,μ(MoKα) = 0.876 mm^-1, F(000) = 650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a k-2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two 0 and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.
基金supported by the National Natural Science Foundation of China(No.21071006)the Natural Science Foundation of Henan Province(No.102102210457)the Natural Science Foundation of the Henan Higher Education Institutions of China(No.2010B150001)
文摘A new complex with the formula [Co(acac)_2(NITQ)_2]×2CH_2Cl_2 1(acac = acetylacetone, NITQ = 2-(2′-quinoxalinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), was synthesized and elucidated structurally as well as magnetically in detail. The crystal belongs to the monoclinic system, space group P2_1/c with a = 9.6896(1), b = 20.539(4), c = 12.147(2) ?, β = 93.84(3)°, M_r = 997.65, V = 2412.1(8) ?~3, Z = 2, Dc = 1.374 g/cm, F(000) = 1038, m = 0.635 mm^(-1), the final R = 0.0539 and w R = 0.1289 for 5998 observed reflections(I 〉 2σ(I)). The Co(Ⅱ) ion is coordinated by two nitrogen atoms of quinoxaline rings from two NITQs and four oxygen atoms from two acac ions to complete a distorted octahedral coordination environment. Compound 1 is further linked into a three-dimensional(3D) supramolecular network by hydrogen-bonding, Cl×××O weak contact and π···π stacking interactions. The magnetic measurements show compound 1 exhibits weak ferromagnetic interactions.
基金Financially supports from the National Natural Science Foundation of China(No.20274023 and 20474036)Guangdong Province Natural Science Foundation(No.021241)are gratefully acknowledged.
文摘Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln([Mo]/[M]) vs. time were liner respectively, indicating that was a controlled photopolymerization.
文摘Compound 1 was first synthesized and characterized. Its crystal structure and magnetic property were determined and investigated. Discussion about the molecule packing in crystal and the macroscopic magnetism was also presented, in combination with computing study of the spatial distribution over the molecule.
文摘Stable s-butyl n-heptafluorobutyryl nitroxide 3 has been generated in an electron transfer reaction in F113 ( CFCl2CF2Cl ) solution at r.t. The aN values for 3 in 11 aprotic solvents show a linear correlation with cybotactic solvent parameters ET and Z. The physical significance for slopes, slope×ET or slope×Z, and the extrapolated intercepts on the aN axis are well established. The plots of aN versus noncybotactic solvent parameters, such as dipolar moment and dielectric constant, are badly behaved.
基金Supported by the National Natural Science Foundation of China(No. 20134010) the Science Research Fund of the Minis-try of Education of P. R. China(No. 104005).
文摘Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl (TIPNO) and α, ω-alkyl bromide by atom transfer radical addition(ATRA) was employed as “biradical initiator” for nitroxide-mediated radical polymerization(NMRP) of isoprene and styrene. The kinetics study for the polymerization of styrene at different time showed living features. The poly(styrene-b-isoprene-b-styrene) (SIS) copolymers have two glass transition temperatures, indicating the immiscibility of the corresponding blocks.
基金financially supported by the National Key R&D Program of China(2017YFA0206700)the National Natural Science Foundation of China(grant No.21822506&51671107)+1 种基金the 111 project of B12015the Natural Science Foundation of Tianjin(grant No.19JCJQJC62400)。
文摘Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]. Organic materials, such as conducting polymers (polyacetylene, polypyrrole, polyaniline, etc.)[5], conjugated carbonyl compounds (quinone compounds, imides, etc.)[6–9] and nitroxide radical (N-O.)[10,11] compounds have been attempted as cathode materials in lithium-ion batteries (LIBs).
文摘The electron spin resonance spectra of N-carbamoyl-N-(l-oxyl-2,2,5,5-tetramethyl-pyrrolin-3-yl) urea compounds in ten solvents with different polarities were determined. It was found that the hyperfine splitting constant AN and spin density pN. as well as the energy difference between two adjacent energy levels E of different pyrroline nitroxides in the same solvent increase with the increase of electron-withdrawing α-bility of the substituted groups on the aromatic ring. There was a linear correlation between AN and Reichardt ET value, and between AN and Z value as well. Such a linear correlation was also found between solvent viscosity n and ESR rotational correlation time r. On the other hand, the correlation between T and the relative height hr of peak on high field was reverse. The results are discussed in the paper.
文摘The titled compound 1 as well as compounds 2 and 3 with similar chemical structures were prepared and characterized. The magnetic properties of 1 were investigated with SQUID (MPMS, quantum design) magnetometer. Studies with Langmuir-Blodgett (LB) technique indicated that stable condensed film of 1 could be formed at air-water interface and could be transferred onto various solid substrate under suitable conditions.
文摘Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room temperature in CFCl2-CF2Cl.
基金the National Natural Science Foundation of China for the financial support (The grant No. 20072013)
文摘4-oxo-2, 2, 6, 6-tetramethylpiperidinyl-1-oxy radical (TEMPO), a nitroxide, oxidized 4-substituted Hantzsch 1,4-dihydropyridines (DHP) under UV irradiation in CH3CN to give aromatic products in good yields. A possible mechanism for the oxidation was suggested.