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 Zn(Ⅱ) complex with nitronyl nitroxide radicals [Zn(NIT3Py)2Cl2](1)(NIT3Py=2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction...A Zn(Ⅱ) complex with nitronyl nitroxide radicals [Zn(NIT3Py)2Cl2](1)(NIT3Py=2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction crystal structure determination method.The complex has a mononuclear-metal structure in which each Zn(Ⅱ) ion adopts a distorted tetrahedral geometry and is coordinated by two Cl-anions and two pyridyl-N atoms from two NIT3Py radical ligands.The magnetic measurements show the weak antiferromagnetic interaction between the nitroxide radicals through the diamagnetic Zn(Ⅱ) ion.CCDC:292363.展开更多
A novel heterospin one-dimensional (1-D) chain complex containing both Cu(Ⅱ) and nitroxide radical ligands, {[Cu(tcph)(H2O)4][Cu(tcph)(NIT3Py)2]·2H2O}n (1) (H2tcph = tetrachloro-phthalic acid, NIT3Py = 2-(3′-py...A novel heterospin one-dimensional (1-D) chain complex containing both Cu(Ⅱ) and nitroxide radical ligands, {[Cu(tcph)(H2O)4][Cu(tcph)(NIT3Py)2]·2H2O}n (1) (H2tcph = tetrachloro-phthalic acid, NIT3Py = 2-(3′-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide), has been synthesized and structurally characterized. The structure consists of neutral chains of copper(Ⅱ) ions bridged by tcph and coordinated alternatively by nitroxide radicals as spin branches and solvated water as co-ligand. The magnetic data were fitted using an approximate theoretical model based on population analysis to obtain the coupling parameter values of JCu2-Rad = 22.4 cm-1 and J′Cu1-Cu2 = -2.4 cm-1, indicating the intramolecular ferromagnetic interaction between Cu(Ⅱ) and NIT3Py and weak antiferromagnetic interaction between Cu1 and Cu2 linked by tcph.展开更多
A new one-dimensional （1-D） Zn（Ⅱ） nitronyl nitroxide complex bridged by pyridine-2,4-dicarboxylate anion, [Zn（NIT4Py）（2,4-PDA）（H2O）2], （NIT4Py = 2-（4′-pyridyl）-4,4,5,5- tetramethylimidazoline-1-oxyl-3-o...A new one-dimensional （1-D） Zn（Ⅱ） nitronyl nitroxide complex bridged by pyridine-2,4-dicarboxylate anion, [Zn（NIT4Py）（2,4-PDA）（H2O）2], （NIT4Py = 2-（4′-pyridyl）-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide and 2,4-PDA = pyridine-2,4-dicarboxylate anion）, has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 16.834（2）, b = 7.4376（10）, c = 18.295（3） A, β = 102.848（2）°, V = 2233.2（5） A^3, C19H23N4O3Zn, Mr = 500.78, Dc = 1.489 g/cm^3,μ（MoKa） = 1.152 mm^-1, F（000） = 1036, Z = 4, the final R = 0.0390 and wR = 0.0915 for 3234 observed reflections. In the complex, each zinc（Ⅱ） ion is six-coordinated by one nitrogen atom of the radical ligand （NIT4Py）, one nitrogen atom and two oxygen atoms of two 2,4-PDA anions and two oxygen atoms of two water molecules. Each 2,4-PDA anion bridges two Zn（Ⅱ） ions via a tridentate mode into a 1-D chain, and these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.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 [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
Three new lanthanide-nitronyl nitroxide radical complexes were successfully synthesized with the formula of [Ln（hfac）3（PyNONIT）2]（Ln=Dy（1）, Tm（2）, Ho（3））. All the complexes were isostructural and crystalli...Three new lanthanide-nitronyl nitroxide radical complexes were successfully synthesized with the formula of [Ln（hfac）3（PyNONIT）2]（Ln=Dy（1）, Tm（2）, Ho（3））. All the complexes were isostructural and crystallized in C2/c space group, in which the central metal ions were eight-coordinated in slightly distorted square antiprism coordination geometries（D4d symmetry）. Magnetic studies indicated the existence of antiferromagnetic interaction in complexes 1–3.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＆gt;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 Nd（Ⅲ） nitronyl nitroxide complex [Nd（NIT2Py）2（NO3）3] （NIT2Py = 2-（2＇-pyridyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction. ...A new Nd（Ⅲ） nitronyl nitroxide complex [Nd（NIT2Py）2（NO3）3] （NIT2Py = 2-（2＇-pyridyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.396（4）, b =11.134（4）, c = 23.360（7） A°, β = 98.178（6）°, V= 3191.2（18） A°^3, C24H32N9NdO13, Mr = 798.83, Dc =1.663 g/cm^3, μ（MoKa） = 1.704 mm^-1, F（000） = 1612, Z = 4, the final R = 0.0425 and wR = 0.0957 for 6532 independentreflections with Rint = 0.0642 and 4552 observed reflections （I 〉 2σ（I））. The complex exists as discrete mononuclear molecules and the neodymium（Ⅲ） ion is ten-coordinated with three bidentate nitrate anions and two radical ligands （NIT2Py） via bidentate chelating mode.The optical properties of the complex are discussed.展开更多
A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically c...A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.展开更多
A new complex { [Cu（NIT4py）2（ip）]·6H2O }, （NIT4py=2-（4＂-pyridinyl）-4,4,5,5-tetra methylimidazoline-1-oxyl-3-oxide and ip = isophthalate dianion） has been synthesized and structurally characterized by X-r...A new complex { [Cu（NIT4py）2（ip）]·6H2O }, （NIT4py=2-（4＂-pyridinyl）-4,4,5,5-tetra methylimidazoline-1-oxyl-3-oxide and ip = isophthalate dianion） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in orthorhombic, space group Cmcm with a = 25.161（3）, b =10.045（1）, c = 15.450（2） A°, C32H48N6O14CU, Mr = 804.30, V= 3904.8（8） ,A°^3, Z = 4, De = 1.368 g/cm^3, μ（MoKa） = 0.630 mm^-1, F（000） = 1692, the final R = 0.0326 and wR = 0.0787 for 1843 independent reflections with Rint = 0.0372. Each Cu（Ⅱ） ion is four-coordinated by two carboxylate oxygen atoms and two pyridyl-N atoms from NIT4py radicals to furnish a rhombus geometry. The central Cu（Ⅱ） ion is located at an inversion center and a crystallographic two-fold axis. Each isophthalate dianion binds two Cu（Ⅱ） ions in bis-monodentate mode, leading to a 1-D chain, a＇ these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.展开更多
A new dinuclear copper（Ⅱ） complex with imino nitroxide radicals [Cu2（NO3）2（IM- 1 ′-MeBzIm）2（dca）2] （IM-1 ′-MeBzIm = 2-{2′-[（1′-methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl, dca = dicya...A new dinuclear copper（Ⅱ） complex with imino nitroxide radicals [Cu2（NO3）2（IM- 1 ′-MeBzIm）2（dca）2] （IM-1 ′-MeBzIm = 2-{2′-[（1′-methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl, 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 α = 9.440（5）, b = 10.124（6）, c = 11.603（7） A, α = 102.904（7）, β = 94.033（6）,γ = 104.299（7）°, C34H40Cu2N16O8, Mr = 927.90, V= 1038.2（10） A^3, Z = 1, Dc = 1.484 g/cm^3, μ（MoKα） = 1.093 mm^-1, F（000） = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with Ⅰ 〉 2σ（I）. X-ray analysis reveals that two Cu（Ⅱ） atoms are bridged by two dicyanamides to form a centrosymmetric Cu（Ⅱ）-Cu（Ⅱ） dinuclear entity. Every Cu（Ⅱ） ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1′-MeBzlm ligand coordinates to the metal ion with the k^2 N（1 ′-MeBzlm）, O（IM） mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu（Ⅱ） ion and the IM-1 ′-MeBzIm are ferromagnetic with J = 12.46 cm^-1, where the spin Hamitonian is defined as H^ = -2JS^1S^2 within the complex.展开更多
A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthe...A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthesized and characterized. X-ray analysis reveals that the compound 1 crystallizes in the monoclinic P21/c (No. 14) space group, and [Cd2(NITpBA)4(H2O)4] units are linked into infinite chains by radical bridging ligands.展开更多
Two novel complexes [Zn（Him-thz）2（NO3）]·NO3 1 and [Ni（Him-thz）2（NO3）]·NO3 2 （Him-thz = 2-（2＇-thiazole）-4,4,5,5-teramethyl-dihydro-1H-imidazolyl-1-hydroxy） have been prepared and structurally cha...Two novel complexes [Zn（Him-thz）2（NO3）]·NO3 1 and [Ni（Him-thz）2（NO3）]·NO3 2 （Him-thz = 2-（2＇-thiazole）-4,4,5,5-teramethyl-dihydro-1H-imidazolyl-1-hydroxy） have been prepared and structurally characterized by X-ray diffraction method. Both complexes crystallize in orthorho- mbic, space group P21 21 2, Z = 2. Crystal data for 1： ZnC20H30N8O8S2, Mr = 640.2, a = 13.1630（14）, b = 10.5149（11）, c = 10.6670（11） A°, V= 1476.4（3）A°^3, Dc = 1.440 g/cm^3, μ（MoKa） = 1.028 mm^-1, F（000） = 664, R = 0.0398 and wR = 0.0901 for 2131 observed reflections with I 〉 2σ（I）. Crystal data for 2： NiC20H30N8O8S2, Mr = 633.36, a = 13.1611（7）, b = 10.4833（6）, c = 10.6928（6） .4,, V = 1475.30（14）A°^3, Dc = 1.426 g/cm^3 ,μ（MoKa） = 0.854 mm^-1, F（000） = 660, R = 0.0281 and wR = 0.0797 for 3099 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the crystal structures consist of [M（Him-thz）2（NO3）]^＋ （M = Zn, Ni） moiety and a NO3^- anion. Both Zinc（Ⅱ） and Nickel（Ⅱ） ions are six-coordinated with distorted octahedral geometries.展开更多
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.
文摘A Zn(Ⅱ) complex with nitronyl nitroxide radicals [Zn(NIT3Py)2Cl2](1)(NIT3Py=2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction crystal structure determination method.The complex has a mononuclear-metal structure in which each Zn(Ⅱ) ion adopts a distorted tetrahedral geometry and is coordinated by two Cl-anions and two pyridyl-N atoms from two NIT3Py radical ligands.The magnetic measurements show the weak antiferromagnetic interaction between the nitroxide radicals through the diamagnetic Zn(Ⅱ) ion.CCDC:292363.
基金Supported by the National Natural Science Foundation of China (Grant No. 20631030)973 Project (Grant No. 2007CB815305)+1 种基金Natural Science Foundation of Tianjin (Grant No. 09JCYBJC05500)100 Projects of Creative Research for the Undergraduates of Nankai University in China (Grant No. BX7-207).
文摘A novel heterospin one-dimensional (1-D) chain complex containing both Cu(Ⅱ) and nitroxide radical ligands, {[Cu(tcph)(H2O)4][Cu(tcph)(NIT3Py)2]·2H2O}n (1) (H2tcph = tetrachloro-phthalic acid, NIT3Py = 2-(3′-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide), has been synthesized and structurally characterized. The structure consists of neutral chains of copper(Ⅱ) ions bridged by tcph and coordinated alternatively by nitroxide radicals as spin branches and solvated water as co-ligand. The magnetic data were fitted using an approximate theoretical model based on population analysis to obtain the coupling parameter values of JCu2-Rad = 22.4 cm-1 and J′Cu1-Cu2 = -2.4 cm-1, indicating the intramolecular ferromagnetic interaction between Cu(Ⅱ) and NIT3Py and weak antiferromagnetic interaction between Cu1 and Cu2 linked by tcph.
基金This work was supported by the National Natural Science Foundation of China (No. 20331010 and 20571045)
文摘A new one-dimensional （1-D） Zn（Ⅱ） nitronyl nitroxide complex bridged by pyridine-2,4-dicarboxylate anion, [Zn（NIT4Py）（2,4-PDA）（H2O）2], （NIT4Py = 2-（4′-pyridyl）-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide and 2,4-PDA = pyridine-2,4-dicarboxylate anion）, has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 16.834（2）, b = 7.4376（10）, c = 18.295（3） A, β = 102.848（2）°, V = 2233.2（5） A^3, C19H23N4O3Zn, Mr = 500.78, Dc = 1.489 g/cm^3,μ（MoKa） = 1.152 mm^-1, F（000） = 1036, Z = 4, the final R = 0.0390 and wR = 0.0915 for 3234 observed reflections. In the complex, each zinc（Ⅱ） ion is six-coordinated by one nitrogen atom of the radical ligand （NIT4Py）, one nitrogen atom and two oxygen atoms of two 2,4-PDA anions and two oxygen atoms of two water molecules. Each 2,4-PDA anion bridges two Zn（Ⅱ） ions via a tridentate mode into a 1-D chain, and these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.
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 (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Project supported by the National Natural Science Foundation of China(21421001)the Ministry of Education of China(ITR13022,13R30)
文摘Three new lanthanide-nitronyl nitroxide radical complexes were successfully synthesized with the formula of [Ln（hfac）3（PyNONIT）2]（Ln=Dy（1）, Tm（2）, Ho（3））. All the complexes were isostructural and crystallized in C2/c space group, in which the central metal ions were eight-coordinated in slightly distorted square antiprism coordination geometries（D4d symmetry）. Magnetic studies indicated the existence of antiferromagnetic interaction in complexes 1–3.
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＆gt;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 National Natural Science Foundation of China (No. 20331010) and Natural Science Foundation of Tianjin (No. 033602011)
文摘A new Nd（Ⅲ） nitronyl nitroxide complex [Nd（NIT2Py）2（NO3）3] （NIT2Py = 2-（2＇-pyridyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.396（4）, b =11.134（4）, c = 23.360（7） A°, β = 98.178（6）°, V= 3191.2（18） A°^3, C24H32N9NdO13, Mr = 798.83, Dc =1.663 g/cm^3, μ（MoKa） = 1.704 mm^-1, F（000） = 1612, Z = 4, the final R = 0.0425 and wR = 0.0957 for 6532 independentreflections with Rint = 0.0642 and 4552 observed reflections （I 〉 2σ（I））. The complex exists as discrete mononuclear molecules and the neodymium（Ⅲ） ion is ten-coordinated with three bidentate nitrate anions and two radical ligands （NIT2Py） via bidentate chelating mode.The optical properties of the complex are discussed.
基金the National Natural Science Foundation of China (No. 20471026)Natural Science Foundation of Henan Province (No. 0311021200) the Foundation of Education Committee of Henan Province (2006150017)
文摘A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.
基金This work was supported by the National Natural Science Foundation of China (No. 20331010 ) and Natural Science Foundation of Tianjin (No. 033602011)
文摘A new complex { [Cu（NIT4py）2（ip）]·6H2O }, （NIT4py=2-（4＂-pyridinyl）-4,4,5,5-tetra methylimidazoline-1-oxyl-3-oxide and ip = isophthalate dianion） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in orthorhombic, space group Cmcm with a = 25.161（3）, b =10.045（1）, c = 15.450（2） A°, C32H48N6O14CU, Mr = 804.30, V= 3904.8（8） ,A°^3, Z = 4, De = 1.368 g/cm^3, μ（MoKa） = 0.630 mm^-1, F（000） = 1692, the final R = 0.0326 and wR = 0.0787 for 1843 independent reflections with Rint = 0.0372. Each Cu（Ⅱ） ion is four-coordinated by two carboxylate oxygen atoms and two pyridyl-N atoms from NIT4py radicals to furnish a rhombus geometry. The central Cu（Ⅱ） ion is located at an inversion center and a crystallographic two-fold axis. Each isophthalate dianion binds two Cu（Ⅱ） ions in bis-monodentate mode, leading to a 1-D chain, a＇ these 1-D chains are further linked into a 2-D network via hydrogen-bonding 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 dinuclear copper（Ⅱ） complex with imino nitroxide radicals [Cu2（NO3）2（IM- 1 ′-MeBzIm）2（dca）2] （IM-1 ′-MeBzIm = 2-{2′-[（1′-methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl, 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 α = 9.440（5）, b = 10.124（6）, c = 11.603（7） A, α = 102.904（7）, β = 94.033（6）,γ = 104.299（7）°, C34H40Cu2N16O8, Mr = 927.90, V= 1038.2（10） A^3, Z = 1, Dc = 1.484 g/cm^3, μ（MoKα） = 1.093 mm^-1, F（000） = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with Ⅰ 〉 2σ（I）. X-ray analysis reveals that two Cu（Ⅱ） atoms are bridged by two dicyanamides to form a centrosymmetric Cu（Ⅱ）-Cu（Ⅱ） dinuclear entity. Every Cu（Ⅱ） ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1′-MeBzlm ligand coordinates to the metal ion with the k^2 N（1 ′-MeBzlm）, O（IM） mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu（Ⅱ） ion and the IM-1 ′-MeBzIm are ferromagnetic with J = 12.46 cm^-1, where the spin Hamitonian is defined as H^ = -2JS^1S^2 within the complex.
文摘A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthesized and characterized. X-ray analysis reveals that the compound 1 crystallizes in the monoclinic P21/c (No. 14) space group, and [Cd2(NITpBA)4(H2O)4] units are linked into infinite chains by radical bridging ligands.
基金This work was supported by the National Natural Science Foundation of China (No. 20471026) and the Natural Science Foundation of Henan province (No. 0311021200)
文摘Two novel complexes [Zn（Him-thz）2（NO3）]·NO3 1 and [Ni（Him-thz）2（NO3）]·NO3 2 （Him-thz = 2-（2＇-thiazole）-4,4,5,5-teramethyl-dihydro-1H-imidazolyl-1-hydroxy） have been prepared and structurally characterized by X-ray diffraction method. Both complexes crystallize in orthorho- mbic, space group P21 21 2, Z = 2. Crystal data for 1： ZnC20H30N8O8S2, Mr = 640.2, a = 13.1630（14）, b = 10.5149（11）, c = 10.6670（11） A°, V= 1476.4（3）A°^3, Dc = 1.440 g/cm^3, μ（MoKa） = 1.028 mm^-1, F（000） = 664, R = 0.0398 and wR = 0.0901 for 2131 observed reflections with I 〉 2σ（I）. Crystal data for 2： NiC20H30N8O8S2, Mr = 633.36, a = 13.1611（7）, b = 10.4833（6）, c = 10.6928（6） .4,, V = 1475.30（14）A°^3, Dc = 1.426 g/cm^3 ,μ（MoKa） = 0.854 mm^-1, F（000） = 660, R = 0.0281 and wR = 0.0797 for 3099 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the crystal structures consist of [M（Him-thz）2（NO3）]^＋ （M = Zn, Ni） moiety and a NO3^- anion. Both Zinc（Ⅱ） and Nickel（Ⅱ） ions are six-coordinated with distorted octahedral geometries.
