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 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 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 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 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
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
A new Zn（Ⅱ） nitronyl nitroxide complex [Zn（NIT4Py）（PDA）（HzO）3] （NIT4Py = 2-（4＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, H2PDA = pyridine-2,5-dicarboxylic acid） has been synthesized and str...A new Zn（Ⅱ） nitronyl nitroxide complex [Zn（NIT4Py）（PDA）（HzO）3] （NIT4Py = 2-（4＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, H2PDA = pyridine-2,5-dicarboxylic acid） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P2 1/c with a = 16.881（8）, b = 7.356（4）, c = 18.857（9） A°,β = 108.616（6）°, V = 2219.1 （19）A°^3 ,C 19H25N4O9Zn, Mr = 518.80, Dc = 1.553 g/cm^3, μ（MoKa） = 1.165 mm^-1, F（000） = 1076, Z = 4, the final R = 0.0269 and wR = 0.0715 for 3193 observed reflections with I 〉 2σ（I）. The complex exists as discrete mononuclear molecules and the zinc（Ⅱ） ion is six-coordinated with one radical ligand （NIT4Py）, one bidentate pyridine-2,5-dicarboxylate anion and three water molecules. A three-dimensional network structure is formed through the intermolecular interactions.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 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 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
The mono-α-nitronyl nitroxide substituted diacetylene was synthesized and its structure was established by EA,FAB-MS,IR,ESR and x-ray diffraction analysis.Using the Extracting Sample Magnetometer,its magnetic propert...The mono-α-nitronyl nitroxide substituted diacetylene was synthesized and its structure was established by EA,FAB-MS,IR,ESR and x-ray diffraction analysis.Using the Extracting Sample Magnetometer,its magnetic properties was investigated,and the results indicate that this compound possesses antiferromagnetic properties.展开更多
The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b...The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) ? b = 101.700(5), V = 1711.9(9) ?, Z = 2, Dc = 1.485 g/cm3, m(MoKa) = 1.456 mm～1, F(000) = 792, the final R = 0.0401 and wR = 0.0861 for 2054 observed reflections with I>2s(I). The imino nitroxide 2-(3- methyl-2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl (im2Py) was reduced to obtain 2-(3-methyl -2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-ydroxy (Him2Py) coordinating to the zinc (II) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two m1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py. The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.展开更多
A novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental anal...A novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction methods. The title complex crystallizes in trigonal, space group P3 and Z = 2. Crystal data： C45H57ClN12NaO10, Mr = 984.47, a = 13.9411（8）, b = 13.9411（8）, c = 14.8622（16） A, γ= 120°, V= 2501.5（3） A^3, Dc = 1.307 g/cm^3, μ（MoKα） = 0.152 mm^-1, F（000） = 1038, R = 0.0637 and wR = 0.1813 for 1957 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Na（I） ion is six-coordinated with three NIT-1＇-MeBzlm radicals. As we know, three radicals coordinating to the Na（I） ion in the main group by a chelate way is the first example. The Na（I） ion resides in a distorted octahedron with a facial configuration. Meanwhile, the intermolecular weak interactions result in a 2-D double layer conformation where the uncoordinated perchlorate anions are inserted in the packing space and take part in the H-bond interactions, and each complex is connected with six neighboring complexes and three perchlorate anions.展开更多
A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction ...A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data：C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074（3）,b = 21.350（3）,c = 11.6962（19）,β = 108.879（2）°,V = 4034.3（11）3,Dc = 1.160 g/cm3,μ（MoKα） = 0.597 mm-1,F（000） = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I 2σ（I）.X-ray analysis reveals that the Co（Ⅱ） ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co（Ⅱ） ion and the radicals（J =-52.88 cm-1）.展开更多
A new Cd（Ⅱ） complex with four nitronyl nitroxide radicals [Cd（NIT4Py）4Cl2]（NIT4Py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ra...A new Cd（Ⅱ） complex with four nitronyl nitroxide radicals [Cd（NIT4Py）4Cl2]（NIT4Py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441（4）,b = 13.6964（8）,c = 13.7354（8） ,α = 89.8610（10）,β = 77.9180（10）,γ = 87.2250（10）°,V = 1331.01（13） 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ（MoKα） = 0.573 mm-1,F（000） = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections（I 〉2σ（I））.The title complex exists in the mononuclear-metal structures,in which each Cd（Ⅱ） ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.展开更多
Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln（hfac）3（NITmNO2）2] （Ln = Sm（Ⅲ） （1）, Tb（Ⅲ） （2）, hfac = hexafluoroacetylacet...Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln（hfac）3（NITmNO2）2] （Ln = Sm（Ⅲ） （1）, Tb（Ⅲ） （2）, hfac = hexafluoroacetylacetonate, NITmNO2 = 2-（3-nitrophenyl）-4,4,5,5-tetramethyl-imidazo- line-1-oxyl-3-oxide） have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln（Ⅲ）-radical structures, in which the central Ln（Ⅲ） ions are all eight coordinated in D2d dodecahedral （DD） geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm（Ⅲ） ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb（Ⅲ） ion and NITmNO2 in complex 2.展开更多
The title compound {[Zn（NIT4Py）（fum）（HEO）2]·H2O}n, where NIT4Py = 2-（4＇- pyridinyl）-4,4,5,5-tetra-methylimidazoline-looxyl-3-oxide and fum = fumarate, has been prepared and structurally characterized by ...The title compound {[Zn（NIT4Py）（fum）（HEO）2]·H2O}n, where NIT4Py = 2-（4＇- pyridinyl）-4,4,5,5-tetra-methylimidazoline-looxyl-3-oxide and fum = fumarate, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1^- with a = 6.9533（9）, b = 9.805（1）, c = 15.248（2） A, α= 94.608（2）, β = 92.328（2）, γ = 105.840（2）°, C16H24N3O9Zn, Mr = 467.75, V = 994.8（2） A^3, Z = 2, Dc = 1.562 g/cm^3,μ（MoKα） = 1.289 mm^-1, F（000） = 486, the final R = 0.0243 and wR = 0.0622 for 3505 independent reflections with Rint = 0.0125. The Zn（II） adopts a distorted five-coordinate triangle bipyramidal geometry. The basic framework structure of the complex is a 1-D chain. The intrachain hydrogen bonds are helpful to stabilize the 1-D chain structure. Furthermore, the chains are connected by O-H…O hydrogen bonds to give a 2-D double-layer network.展开更多
Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n...Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> (1) and [Cu(hfac)<sub>2</sub><sub> </sub>(NIToPhO3Py)]<sub>2</sub> (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NITmPhO3- Py)<sub>2</sub>} via the bridging unit [Cu(hfac)<sub>2</sub>];complex 2 presented a binuclear cyclic structure [Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIToPhO3Py)<sub>2</sub>. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.展开更多
Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3...Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3PyPh)<sub>2</sub>](<strong>2</strong>)(NIT-4PyPh=2-[4-(4-pyridinylmethoxy) phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-3PyPh=2-[4-(3-pyridinylmethoxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,hfac=hexafluoroacetylacetone), have been synthesized and characterized. The X-ray crystal structure analyses show that structures of the two complexes are different. Complex <strong>1</strong> crystallizes in cyclic metal-radical dimer consisting of four Cu(hfac)<sub>2</sub> and two NIT-4PyPh ligands;four Cu(II) atoms adopt two coordinated modes. In the ring, each Cu(II) ion is hexa-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) and one nitrogen atom of the pyridinyl group from two different radicals. Outside the ring, each Cu(II) is penta-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) from the radical ligand. Complex <strong>2</strong> crystallizes in discrete molecule, while the Cu(II) atom is hexa-coordinated by four oxygen atoms of two hfac molecules and two nitrogen atoms of the pyridinyl group from two radical ligands.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
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 (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 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 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.
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.
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 Zn（Ⅱ） nitronyl nitroxide complex [Zn（NIT4Py）（PDA）（HzO）3] （NIT4Py = 2-（4＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, H2PDA = pyridine-2,5-dicarboxylic acid） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P2 1/c with a = 16.881（8）, b = 7.356（4）, c = 18.857（9） A°,β = 108.616（6）°, V = 2219.1 （19）A°^3 ,C 19H25N4O9Zn, Mr = 518.80, Dc = 1.553 g/cm^3, μ（MoKa） = 1.165 mm^-1, F（000） = 1076, Z = 4, the final R = 0.0269 and wR = 0.0715 for 3193 observed reflections with I 〉 2σ（I）. The complex exists as discrete mononuclear molecules and the zinc（Ⅱ） ion is six-coordinated with one radical ligand （NIT4Py）, one bidentate pyridine-2,5-dicarboxylate anion and three water molecules. A three-dimensional network structure is formed through the intermolecular interactions.
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.
文摘The mono-α-nitronyl nitroxide substituted diacetylene was synthesized and its structure was established by EA,FAB-MS,IR,ESR and x-ray diffraction analysis.Using the Extracting Sample Magnetometer,its magnetic properties was investigated,and the results indicate that this compound possesses antiferromagnetic properties.
基金This work was supported by the National Natural Science Foundation of China (No. 20171025 and No. 90101028)
文摘The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) ? b = 101.700(5), V = 1711.9(9) ?, Z = 2, Dc = 1.485 g/cm3, m(MoKa) = 1.456 mm～1, F(000) = 792, the final R = 0.0401 and wR = 0.0861 for 2054 observed reflections with I>2s(I). The imino nitroxide 2-(3- methyl-2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl (im2Py) was reduced to obtain 2-(3-methyl -2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-ydroxy (Him2Py) coordinating to the zinc (II) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two m1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py. The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.
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 novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction methods. The title complex crystallizes in trigonal, space group P3 and Z = 2. Crystal data： C45H57ClN12NaO10, Mr = 984.47, a = 13.9411（8）, b = 13.9411（8）, c = 14.8622（16） A, γ= 120°, V= 2501.5（3） A^3, Dc = 1.307 g/cm^3, μ（MoKα） = 0.152 mm^-1, F（000） = 1038, R = 0.0637 and wR = 0.1813 for 1957 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Na（I） ion is six-coordinated with three NIT-1＇-MeBzlm radicals. As we know, three radicals coordinating to the Na（I） ion in the main group by a chelate way is the first example. The Na（I） ion resides in a distorted octahedron with a facial configuration. Meanwhile, the intermolecular weak interactions result in a 2-D double layer conformation where the uncoordinated perchlorate anions are inserted in the packing space and take part in the H-bond interactions, and each complex is connected with six neighboring complexes and three perchlorate anions.
基金supported by the National Natural Science Foundation of China (Nos.20771054 and 21071074)the Henan Tackle Key Problem of Science and Technology(No.0524220001)
文摘A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data：C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074（3）,b = 21.350（3）,c = 11.6962（19）,β = 108.879（2）°,V = 4034.3（11）3,Dc = 1.160 g/cm3,μ（MoKα） = 0.597 mm-1,F（000） = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I 2σ（I）.X-ray analysis reveals that the Co（Ⅱ） ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co（Ⅱ） ion and the radicals（J =-52.88 cm-1）.
基金supported by the National Natural Science Foundation of China (No. 20901059 and 20771083)the Technological Development Foundation Project of Tianjin Educational Committee (No. 20080503)
文摘A new Cd（Ⅱ） complex with four nitronyl nitroxide radicals [Cd（NIT4Py）4Cl2]（NIT4Py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441（4）,b = 13.6964（8）,c = 13.7354（8） ,α = 89.8610（10）,β = 77.9180（10）,γ = 87.2250（10）°,V = 1331.01（13） 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ（MoKα） = 0.573 mm-1,F（000） = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections（I 〉2σ（I））.The title complex exists in the mononuclear-metal structures,in which each Cd（Ⅱ） ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.
基金Supported by the National Natural Science Foundation of China(21471084,21101096,21471083,21371104)National Innovating Experimentation Project 201410055097100 Projects of Creative Research for the Undergraduates of Nankai University in China(No.BX13165)
文摘Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln（hfac）3（NITmNO2）2] （Ln = Sm（Ⅲ） （1）, Tb（Ⅲ） （2）, hfac = hexafluoroacetylacetonate, NITmNO2 = 2-（3-nitrophenyl）-4,4,5,5-tetramethyl-imidazo- line-1-oxyl-3-oxide） have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln（Ⅲ）-radical structures, in which the central Ln（Ⅲ） ions are all eight coordinated in D2d dodecahedral （DD） geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm（Ⅲ） ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb（Ⅲ） ion and NITmNO2 in complex 2.
基金supported by the Natural Science Foundation of Hebei Normal University (L2007Z05, L2006Q09)
文摘The title compound {[Zn（NIT4Py）（fum）（HEO）2]·H2O}n, where NIT4Py = 2-（4＇- pyridinyl）-4,4,5,5-tetra-methylimidazoline-looxyl-3-oxide and fum = fumarate, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1^- with a = 6.9533（9）, b = 9.805（1）, c = 15.248（2） A, α= 94.608（2）, β = 92.328（2）, γ = 105.840（2）°, C16H24N3O9Zn, Mr = 467.75, V = 994.8（2） A^3, Z = 2, Dc = 1.562 g/cm^3,μ（MoKα） = 1.289 mm^-1, F（000） = 486, the final R = 0.0243 and wR = 0.0622 for 3505 independent reflections with Rint = 0.0125. The Zn（II） adopts a distorted five-coordinate triangle bipyramidal geometry. The basic framework structure of the complex is a 1-D chain. The intrachain hydrogen bonds are helpful to stabilize the 1-D chain structure. Furthermore, the chains are connected by O-H…O hydrogen bonds to give a 2-D double-layer network.
文摘Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> (1) and [Cu(hfac)<sub>2</sub><sub> </sub>(NIToPhO3Py)]<sub>2</sub> (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NITmPhO3- Py)<sub>2</sub>} via the bridging unit [Cu(hfac)<sub>2</sub>];complex 2 presented a binuclear cyclic structure [Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIToPhO3Py)<sub>2</sub>. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.
文摘Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3PyPh)<sub>2</sub>](<strong>2</strong>)(NIT-4PyPh=2-[4-(4-pyridinylmethoxy) phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-3PyPh=2-[4-(3-pyridinylmethoxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,hfac=hexafluoroacetylacetone), have been synthesized and characterized. The X-ray crystal structure analyses show that structures of the two complexes are different. Complex <strong>1</strong> crystallizes in cyclic metal-radical dimer consisting of four Cu(hfac)<sub>2</sub> and two NIT-4PyPh ligands;four Cu(II) atoms adopt two coordinated modes. In the ring, each Cu(II) ion is hexa-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) and one nitrogen atom of the pyridinyl group from two different radicals. Outside the ring, each Cu(II) is penta-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) from the radical ligand. Complex <strong>2</strong> crystallizes in discrete molecule, while the Cu(II) atom is hexa-coordinated by four oxygen atoms of two hfac molecules and two nitrogen atoms of the pyridinyl group from two radical ligands.
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.
