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1.
Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties
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Mei Zhu Peng Hu Yungai Li Xiufeng Wang Prof. Licun Li Prof. Daizheng Liao V. M. L. Durga Prasad Goli Prof. S. Ramasesha Dr. Jean‐Pascal Sutter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13356-13365
Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd , Tb 2Tb , Dy 2Dy , Ho 2Ho , Yb 2Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd , Tb 3Tb , Dy 3Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior. 相似文献
2.
Lili Zhu Xiaodan Chen Qihua Zhao Zhongshu Li Xiangyang Zhang Baiwang Sun Prof. Dr. 《无机化学与普通化学杂志》2010,636(8):1441-1443
The novel heterospin complex [Ni2(PhCOO)4(NITpPy)2]·2CH3CN ( 1 ) was synthesized by the reaction of nickel benzoate and 2‐(4‐pyridyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide (NITpPy) in acetonitrile and dichloromethane solutions. The X‐ray structure determination shows that complex 1 consists of a symmetrical dimeric NiII benzoate paddle‐wheel core and pyridyl nitrogen atoms of radical ligands at the apical position, in addition, the temperature (2–300K) dependent magnetic susceptibility measurements indicate that 1 has antiferromagnetic behavior. 相似文献
3.
A series of heterometallic LnIII–SbIII edta‐containing compounds with the formulas [Sb2(edta)2Ln]NO3 · nH2O [edta = ethylenediaminetetraacetate; Ln = Eu, n = 7 ( 1 ); Gd, n = 7.5 ( 2 ) and Tb, n = 8 ( 3 )] were synthesized and characterized by elemental analyses (EA), powder X‐ray diffraction (PXDP), Fourier transform infrared spectroscopy (FT‐IR), and thermogravimetric analyses (TGA). Their fluorescence and magnetic properties were also studied. The thermal analysis demonstrates the compounds formation of the antimony, lanthanide ions, and edta4– ligands. FT‐IR spectra reveal that the antimony and lanthanide ions are connected through the carboxylate bridges. The studies of luminescence properties show that compounds 1 and 3 exhibit typical luminescence in the visible region. Furthermore, magnetic properties reveal compounds 2 and 3 have weak ferromagnetic behavior. 相似文献
4.
Structural and Magnetic Properties of 2p‐3d‐4f Hetero‐Tri‐Spin Chains Comprising [{Cu(hfac)2‐Radical}2] Dimers and Ln(hfac)3 (hfac=hexafluoroacetylacetonate)
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A new family of 2p‐3d‐4f hetero‐tri‐spin complexes [Ln(hfac)3{Cu(hfac)2(NIT‐3 PyPh)}2] (Ln=Gd ( 1 ), Tb ( 2 ), Dy ( 3 ), Ho ( 4 ); NIT‐3 PyPh=2‐[4‐(3‐pyridinylmethoxy)phenyl]‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide; hfac=hexafluoroacetylacetonate) have been synthesized. Four complexes possess a 1D chain structure in which two radical ligands join two Cu(hfac)2 molecules to form a [{Cu(hfac)2‐rad)}2] dimer cycle and the dimer rings are linked by Ln(hfac)3 units. Magnetic studies show that ferromagnetic exchange couplings exist between the coordinated NO groups of radical ligands and metal ions. Field‐induced slow relaxation of the magnetization was observed in the Tb and Dy compounds. 相似文献
5.
ZnCl2(NIT‐pPy) 1 , (NIT‐pPy = 2‐(4‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐oxyl‐3‐oxide) crystallizes in the orthorhombic space group Pnn2 with the cell parameters a = 9.4083(9), b = 39.686(3), c = 7.4417(14) Å. ZnCl2(NIT‐6M‐oPy) 2 , (NIT‐6M‐oPy = 2‐(6‐methyl‐2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐oxyl‐3‐oxide) crystallizes in the monoclinic space group Pn with a = 7.377(2), b = 19.096(4), c = 11.853(2) Å, β = 95.65(3)°. The temperature dependence magnetic susceptibility of complex 1 revealed an intermolecular ferromagnetic exchange interaction. A simple spin‐polarization model has been used to justify the observed ferromagnetic exchange interaction between the spins of the radical NO group in complex 2 . 相似文献
6.
A new Nd(Ⅲ) nitronyl nitroxide complex [Nd(NIT2Py)2(NO3)3] (NIT2Py = 2-(2'-pyridyl)-4,4,5,5-tetramethylimidazoline-1-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, C24H32NgNdO13, Mr = 798.83, Dc =1.663 g/cm3, μ(MoKα) = 1.704 mm-1, F(000) = 1612, Z = 4, the final R = 0.0425 and wR = 0.0957for 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. 相似文献
7.
Xiaoling Wang Panpan Xu Xia Bao Fengwu Wang Yonghong Chen Yijun Wei 《无机化学与普通化学杂志》2013,639(1):176-180
Abstract. Two radical–LnIII–radical complexes, [Ln(hfac)3(NITPh‐Ph)2] [Ln = Gd ( 1 ) and Ho ( 2 ), hfac = hexafluoroacetylacetonate; and NITPh‐Ph = 4′‐biphenyl‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide] were synthesized and characterized by X‐ray diffraction, elemental analysis, magnetic measurements, as well as IR and UV/Vis spectroscopy. X‐ray crystal structure analysis revealed that the structures of both complexes are isomorphous, the central LnIII ions are coordinated by six oxygen atoms from three hfac ligand molecules and two oxygen atoms from nitronyl radicals. The temperature dependencies of the magnetic susceptibilities were studied. They showed that in the GdIII complex, ferromagnetic interactions between GdIII and the radicals and antiferromagnetic interactions between the radicals coexist in this system (with JRad–Gd = 0.1 cm–1, JRad–Rad = –0.309 cm–1). 相似文献
8.
Two 3d‐4f Heterometallic Coordination Polymers of Macrocyclic Oxamide with Benzotriazole‐5‐carboxylate Co‐ligand: Syntheses,Crystal Structures and Magnetic Properties
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Two heterometallic 3d–4f coordination polymers, [Gd(CuL)2(Hbtca)(btca)(H2O)] · 2H2O ( 1 ) and [Er(CuL)2(Hbtca)(btca)(H2O)] · H2O · CH3OH ( 2 ) (CuL, H2L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H2btca = benzotriazole‐5‐carboxylic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit a double‐strand meso‐helical chain structures formed by [LnIIICuII2] (LnIII = Gd, Er) units by oxamide and benzotriazole‐5‐carboxylate bridges. They are isomorphic except that one free water molecule of 1 is replaced by a methanol molecule. All 1D chains are further interlinked by hydrogen bonds resulting in a 3D supramolecular architecture. The magnetic properties of the compound 1 and 2 are also discussed. 相似文献
9.
Two new 1‐D silver( I ) complexes, [Ag( I )1.5(IM‐oBA)(NO3)0.5] ( 1 ) and [Ag( I )(NIT‐pBA)] ( 2 ), (IM‐oBAH = 2‐(2‐carboxyphenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazol‐1‐yloxyl, NIT‐pBAH = 2‐(4‐carboxyphenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐3‐oxido‐H‐imidazol‐3‐ium‐1‐yloxyl) have been prepared and structurally characterized. Complexes 1 and 2 crystallized in the monoclinic space groups of C2/c and P21/c, respectively. In complex 1 , the structure consists of trinuclear Ag(I) atoms with different linkages of IM‐oBA and nitrates. The trinuclear Ag(I) atoms are further coordinated to the neighbor IM‐oBA radicals via self‐assembly of the nitrogen atom of imine moiety and extended into formation of a polymeric chain. Complex 2 is constructed from a bis(carboxylato‐O,O')‐bridged centrosymmetric dimeric subunit and extended into a polymeric chain through self‐assembly coordination between metal ions and nitroxide groups of NIT‐pBA radicals. Temperature dependence of magnetic susceptibility measurements showed a weak ferromagnetic coupling between nitroxide radicals in 1 and 2 with J = 5.62 for 1 and 6.62 cm?1 for 2 , respectively. 相似文献
10.
Preparation and Structure of (3‐Methylpyridinium)3[DyCl6] and (3‐Methylpyridinium)2[DyCl5(Ethanol)] The complex chlorides (3‐Methylpyridinium)3[DyCl6] ( 1 ) and (3‐Methylpyridinium)2[DyCl5(Ethanol)] ( 2 ) have been prepared for the first time. The crystal structures have been determined from single crystal X‐ray diffraction data. 1 crystallizes in the trigonal space group R3c (Z = 36) with a = 2953.3(3) pm, b = 2953.3(3) pm and c = 3252.5(4) pm, compound 2 crystallizes in the triclinic space group P1 (Z = 2) with a = 704.03(8) pm, b = 808.10(8) pm, c = 1937.0(2) pm, α = 77.94(1)°, β = 87.54(1)° and γ = 83.26(1)°. The structures contain isolated octahedral building units [DyCl6]3– and [DyCl5(Ethanol)]2–, respectively. 相似文献
11.
LI Dong-Jiaoa GAO Dong-Zhaoa LI Li-Cuna b LIAO Dai-Zhenga b JIANG Zong-Huia② YAN Shi-Pinga a 《结构化学》2005,(8)
1 INTRODUCTION Nitronyl nitroxides, independently or in combina- tion with metal ions, have been one of the most widely studied systems in molecular magnetism for understanding the radical-radical or metal-radical interactions as well as for synthesizing organic ferro- magnets and metal-radical magnetic materials[1~3]. Meanwhile, investigations on molecular coordina- tion compounds of lanthanide ions have also attrac- ted great attention due to their luminescence[4, 5] or magnetic propert… 相似文献
12.
Heterometallic 3d‐4f complexes are being investigated, for some time, as being useful in molecular magnetism, particularly as single‐molecule magnets (SMMs). This interest is primarily because of the possibility of an increased ligand‐mediated super‐exchange phenomenon between the 3d and 4f metal ions. Such an interaction, apart from bestowing a favorable ground‐state spin to the complex, also assists in reducing quantum tunneling of magnetization that is widely prevalent in SMMs making them to lose magnetization. However, assembling both 3d as well as 4f ions using same ligand system is challenging and involves the design of multi‐site coordination ligands with specific coordination compartments for the 3d and the 4f metal ions while at the same time allowing these disparate metal ions to be linked to each other through a bridging ligating atom. This review presents a summary of the 3d‐4f complexes primarily derived from the author's work while alluding to important examples from the literature. We also provide an outlook for the future design of such complexes. 相似文献
13.
Preparation and Structure of (2‐Methylpyridinium)3[TbCl6] and (2‐Methylpyridinium)2[TbCl5(1‐Butanol)] The complex chlorides (2‐Methylpyridinium)3[TbCl6] (1) and (2‐Methylpyridinium)2[TbCl5(1‐Butanol)] (2) have been prepared for the first time. The crystal structures have been determinated from single crystal X‐ray diffraction data. 1 crystallizes in the monoclinic space group C2/c (Z = 8) with a = 3241,2(5) pm, b = 897,41(9) pm, c = 1774,2(2) pm and β = 97,83(2)°, 2 in the monoclinic space group P21/n (Z = 4) with a = 1372,96(16) pm, b = 997,57(9) pm, c = 1820,5(2) pm and β = 108,75(1)°. The structures contain isolated octahedral building units [TbCl6]3– and [TbCl5(1‐Butanol)]2–, respectively. 相似文献
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15.
Volkmar Derstroff Jürgen Ensling Vadim Ksenofontov Philipp Gütlich Wolfgang Tremel 《无机化学与普通化学杂志》2002,628(6):1346-1354
A new chromium thiophosphate, K3Cr2(PS4)3 has been prepared and characterized by single‐crystal diffraction, temperature dependent magnetic susceptibility measurements and optical spectroscopy. K3Cr2(PS4)3 crystallizes in the monoclinic space group P21/n (No. 14) with a = 9.731(2) Å, b = 11.986(2) Å, c = 17.727(4) Å, β = 96.52(2)°, V = 2054.2(2) Å3, Z = 4, and R = 0.044. The anionic part of the structure consists of dimeric Cr2(μ3‐S3PS)2 units which are linked by bidentate PS4 groups to form infinite one‐dimensional [S2PS2Cr2(μ3S3PS)2]3— chains separated by K+ cations. The CrIII centers of the Cr2(μ3‐S3PS)2 units are antiferromagnetically coupled. The magnetic susceptibility data may be fitted using a D‐Heisenberg model for S = 3/2 with g = 2.02 and J/k = 10K. K3Cr2(PS4)3 is semiconducting with an optical band gap of 1.35 eV. 相似文献
16.
A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H2O)4] · [CuBr(2‐pzc)2] · 4H2O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)2 cationic units through hydrogen bonds. 相似文献
17.
GAO Dong-Zhaoa WANG Shu-Pinga CHEN Jina LI Li-Cuna b LIAO Dai-Zhenga JIANG Zong-Huia② YAN Shi-Pinga a 《结构化学》2006,25(2)
1 INTRODUCTION Nitronyl nitroxides, independently or in combina- tion with metal ions, have been one of the most wi- dely studied systems in molecular magnetism for understanding radical-radical or metal-radical inte- ractions as well as for synthesizing organic ferroma- gnets and metal-radical magnetic materials[1~4]. Up to now, lots of metal-radical complexes have been reported[5~8]. On the other hand, cooperative inter- molecular interactions, such as coordination bonds, hydrogen bon… 相似文献
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Preparation and Crystal Structures of New Complex Clorides of Lanthanides containing 3, 5‐Dimethylpyridinium Cations: (3, 5‐Dimethylpyridinium)2[LnCl4(H2O)2]Cl (Ln = La, Pr) and (3, 5‐Dimethylpyridinium)3[TbCl6] Crystals of the complex chlorides (3, 5‐dimethylpyridinium)2[LaCl4(H2O)2]Cl ( 1 ), (3, 5‐dimethylpyridinium)2[PrCl4(H2O)2]Cl ( 2 ) and (3, 5‐dimethylpyridinium)3[TbCl6] ( 3 ) have been prepared by reaction of LnCl3 · x H2O (Ln = La, Pr, Tb; x = 6‐7) with 3, 5‐dimethylpyridiniumchloride in ethanol/butanol solution. The crystal structures have been determined from single crystal X‐ray diffraction data. The compounds 1 and 2 are isotypic with each other and crystallize in the triclinic space group P1¯ (Z = 2). The 3, 5‐dimethylpyridinium cations are linked by hydrogen bonds to the anionic part of the structure built up by isolated chloride ions and strings of edge coupled triangulated dodecahedra [LnCl4/2Cl2(H2O)2]—. The organic units are arranged forming a “π‐stacking”. 3 cristallizes monoclinically in the space group P21/c (Z = 4). The structure contains octahedral building units [TbCl6]3—. These octahedra are interconnected by the organic cations via hydrogen bonds forming chains parallel to [0 0 1]. 相似文献
20.
The neodymium borohydride [Li(thf)4]2[Nd2(μ‐Cl)2(BH4)6(thf)2] was synthesized from neodymium chloride and lithium borohydride. The compound crystallized in the triclinic crystal system, space group (No. 2) with the cell constants a = 14.8613(11), b = 17.8715(13), c = 23.5846(18) Å, α = 100.760(6), β = 90.648(6) and γ = 103.294(6)°. Each neodymium atom is coordinated by three borohydride anions and a THF molecule whereas two neodymium cations are bridged through two chloro ligands. The charge of the [Nd2(μ‐Cl)2(BH4)6(thf)2]2− anion, which represents the first structurally characterized binuclear mixed borohydride chlorido complex, is compensated by two [Li(thf)4]+ cations. 相似文献