The crystal structure of the title compound was determined by X-ray diffraction method at room temperature.The crystal belongs to triclinic space group P1 with the following crystallographic parameters:a=13.942(2),b=1...The crystal structure of the title compound was determined by X-ray diffraction method at room temperature.The crystal belongs to triclinic space group P1 with the following crystallographic parameters:a=13.942(2),b=15.540(2),c=10.007(1) A,a=105.16(1)°,β=92.42(1)°,γ=88.12(1)°,V=2090.2(4) Z=4,Dc=1.23g cm-3,F(000)=820,μ(MoKα)=0.74 cm-1,and final R= 0.054 for 3208 observations.Two molecules , which are slightly different in conformation,coexist in an asymmetric unit. Some intermolecular distances are fairly short.The packing arrangement of the molecules in the crystal is also discussed.展开更多
To validate the correctness of the Hartman-Perdok Theory (HPT), which indicates that the { 111 } planes have the lowest surface energy in spinel ferrites, the {111} plane orientated ZnFe204 thin films on Si(100),...To validate the correctness of the Hartman-Perdok Theory (HPT), which indicates that the { 111 } planes have the lowest surface energy in spinel ferrites, the {111} plane orientated ZnFe204 thin films on Si(100), Si(111), and SIO2(500 nm)/Si(111) substrates were obtained through a radio frequency (RF) magnetron sputtering method with a low sputtering power of 80 W. All of the experiments prove that the atom energy determined by sputtering power plays an important role in the orientated growth of the ZnFe204 thin films, and it matches well with HPT. The ZnFe2O4 thin films exhibit ferromagnetism with a magnetization of 84.25 ld/mol at room temperature, which is different from the bulk counterpart (antiferromagnetic as usual). The ZnFe204 thin films can be used as high-quality oriented inducing buffer layers for other spinel (Ni, Mn)Zn ferrite thin films and may have high potential in magnetic thin films-based devices.展开更多
A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized b...A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.展开更多
A new binuclear complex [Ni2(2,2'-bpy)2(C8H3NO6)2(H2O)4] 1 (2,2'-bpy = 2,2'- bipyridine, C8H3NO6 = 4-nitrophthalate) has been synthesized by a hydrothermal reaction and characterized by X-ray single-crystal...A new binuclear complex [Ni2(2,2'-bpy)2(C8H3NO6)2(H2O)4] 1 (2,2'-bpy = 2,2'- bipyridine, C8H3NO6 = 4-nitrophthalate) has been synthesized by a hydrothermal reaction and characterized by X-ray single-crystal diffraction analysis. The complex crystallizes in triclinic, space group P1 with a = 7.206(2), b = 10.337(4), c = 12.480(4) , α = 89.887(11), β = 77.033(9), γ = 78.349(6)o, V = 886.3(5) 3, Z = 1, C36H30Ni2N6O16, Mr = 920.08, Dc = 1.724 g cm-3, F(000) = 472, μ = 1.152 mm-1, the final R = 0.0458 and wR = 0.1163 for 3372 observed reflections with I 2σ(Ⅰ). The two Ni(Ⅱ) ions are bridged by two 4-nitrophthalates both in a bis-monodentate mode. Magnetic measurements reveal that the intramolecular exchange couplings in the dimer are ferromagnetic with 2J/k = 2.32 K, D =-1.44 K and g = 2.18.展开更多
This paper describes interlayer exchange coupling (IEC) phenomena in ferromagnetic multilayer structures, focusing on the unique IEC features observed in ferromagnetic semiconductor (Ga,Mn)As-based systems. The depend...This paper describes interlayer exchange coupling (IEC) phenomena in ferromagnetic multilayer structures, focusing on the unique IEC features observed in ferromagnetic semiconductor (Ga,Mn)As-based systems. The dependence of IEC on the structural parameters, such as non-magnetic spacer thickness, number of magnetic layers, and carrier density in the systems has been investigated by using magnetotransport measurements. The samples in the series show both a typical anisotropic magnetoresistance (AMR) and giant magnetoresistance (GMR)-like effects indicating realization of both ferromagnetic (FM) and antiferromagnetic (AFM) IEC in (Ga,Mn)As-based multilayer structures. The results revealed that the presence of carriers in the nonmagnetic spacer is an important factor to realize AFM IEC in this system. The studies further reveal that the IEC occurs over a much longer distance than predicted by current theories, strongly suggesting that the IEC in (Ga,Mn)As-based multilayers is a long-range interaction. Due to the long-range nature of IEC in the (Ga,Mn)As-based systems, the next nearest neighbor (NNN) IEC cannot be ignored and results in multi-step transitions during magnetization reversal that correspond to diverse spin configurations in the system. The strength of NNN IEC was experimentally determined by measuring minor loops that correspond to magnetization flips in specific (Ga,Mn)As layer in the multilayer system.展开更多
Ferromagnetic transition has generally been considered to involve only an ordering of magnetic moment with no change in the host crystal structure or symmetry, as evidenced by a wealth of crystal structure data from c...Ferromagnetic transition has generally been considered to involve only an ordering of magnetic moment with no change in the host crystal structure or symmetry, as evidenced by a wealth of crystal structure data from conventional X-ray diffractometry (XRD). However, the existence of magnetostriction in all known ferromagnetic systems indicates that the magnetic moment is coupled to the crystal lattice; hence there is a possibility that magnetic ordering may cause a change in crystal structure. With the development of high-resolution synchrotron XRD, more and more magnetic transitions have been found to be accompanied by simultaneous structural changes. In this article, we review our recent progress in understand- ing the structural change at a ferromagnetic transition, including synchrotron XRD evidence of structural changes at the ferromagnetic transition, a phenomenological theory of crystal structure changes accompanying ferromagnetic transitions, new insight into magnetic morphotropic phase boundaries (MPB) and so on. Two intriguing implications of non-centric symmetry in the ferromagnetic phase and the first-order nature of ferromagnetic transition are also discussed here. In short, this review is intended to give a self-consistent and logical account of structural change occurring simultaneously with a ferromagnetic transition, which may provide new insight for developing highly magneto-responsive materials.展开更多
A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes...A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ(MoKα) = 1.422 mm-1, F(000) = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper(H) centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper(Ⅱ) ion and shares the other phenolate group between the two copper(H) ions, affording a Cu2O2 plane. Each copper(Ⅱ) center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data (2-300 K) of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑(Xobsd -Xcalcd)2/∑Xobsd2= 2.76 × 10^-3.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
The reaction of tricyanometallate precursor, Bu_4N[Fe(Tp)(CN)_3] and(Bu_4N)[(pzTp)Fe(CN)_3](Tp = tris(pyrazolyl)hydroborate, pzTp = tetrakis(pyrazolyl)borate) with Ni(ClO_4).26 H_2O in the presence of the monodentate ...The reaction of tricyanometallate precursor, Bu_4N[Fe(Tp)(CN)_3] and(Bu_4N)[(pzTp)Fe(CN)_3](Tp = tris(pyrazolyl)hydroborate, pzTp = tetrakis(pyrazolyl)borate) with Ni(ClO_4).26 H_2O in the presence of the monodentate N-methylimidazole ligand afforded two new cyano-bridged heterobimetallic {Fe2 Ni} trinuclear clusters, {[Fe(Tp)(CN)_3]_2[Ni(Mim)_4]}·8 H_2O(1) and {[Fe(pzTp)(CN)_3]_2[Ni(Mim)_4]}·2 CH_3OH·2H_2O(2). The molecular structure was determined by single-crystal X-ray diffraction. In the two compounds, the FeIII ions were coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp(or pzTp) anions, whereas, the NiII ions were surrounded by two cyanide nitrogen atoms and four nitrogen atoms from four monodentate N-methylimidazole ligands, and they were bridged by tricyanometalate building block to form similar {Fe2Ni} trinuclear clusters. Cyclic voltammetry(CV) measurements indicated that compound 1 exhibited two quasireversible iron-centered reduction processes at –0.71 and –0.17 V and one quasireversible nickel-centered oxidation process at 0.92 V, while compound 2 showed two quasireversible iron-centered reduction processes at –0.66 and –0.09 V and one quasireversible nickel-centered oxidation process at 0.88 V. Magnetic measurements showed that compounds 1 and 2 exhibited strong intrachain ferromagnetic interaction between the low-spin Fe~Ⅲ(S = 1/2) and high-spin Ni~Ⅱ(S = 1) ions.展开更多
A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(...A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(17), c = 31.445(3) ?, γ = 120°, V = 6817.8(12) ?3, Dc = 1.370 g/cm3, Z = 6, μ = 0.566 mm-1, Mr = 937.18, F(000) = 2916, R = 0.0715, wR = 0.2115 and GOF = 1.086. The structure consists of Ag(NIT3Py)3+ cation moiety, one water molecule and one perchloric ion. The Ag(I) ion is in a trigonal planar coordination environment formed by three nitrogen atoms from three NIT3Py ligand molecules.展开更多
Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectr...Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectroscopic techniques, single crystal X-ray diffraction,super conducting quantum interference device(SQUID) measurements and theoretical calculations. The dications have triplet ground states with ferromagnetic interaction exceeding the thermal energy at room temperature. The solid-state structures of these species were tunable by substituent effect, with 1^(2+) as a monomer and 2^(2+) as a dimer.展开更多
Magnetoresistance(MR)phenomenon couples the electron transport with magnetic field,which has been at the forefront of condensed matter physics and materials science.Large-MR behaviors are of particularly importance fo...Magnetoresistance(MR)phenomenon couples the electron transport with magnetic field,which has been at the forefront of condensed matter physics and materials science.Large-MR behaviors are of particularly importance for magnetic sensor and information memory applications,and their scarcity has aroused intensive research.Moreover,due to the different physical origins,combination of large positive and negative MR(pMR and nMR)in one single compound has rarely been reported.In present work,we achieved a coexistence of large pMR and nMR in Cr_(2)Si_(2)Te_(6) ferromagnetic semiconductor single crystal with different field configurations.Specifically,a large nMR of about -60% was obtained under the in-plane field,while a large pMR higher than 1000% took over in the out-of-plane direction.We attribute this field direction-sensitive dualistic large MR behavior to the competition and cooperation effect from the ferromagnetic interaction,orbital scattering and electronic correlation that coexist in Cr_(2)Si_(2)Te_(6),which contribute to n MR,pMR,and nMR,respectively,in dominated temperature and field ranges,and show different weights under different field directions.The elucidated multiple MR mechanism in this ferromagnetic semiconductor will shed light on the pursuit of coexistence of large p MR and nMR for field-sensitive device applications.展开更多
Several rocksalt Sr4X3N (X = O, S, Se, and Te) are predicted to be potential half-metallic ferromagnets free of transition-metal and rare-earth elements by performing the first-principles calculations. Then their ma...Several rocksalt Sr4X3N (X = O, S, Se, and Te) are predicted to be potential half-metallic ferromagnets free of transition-metal and rare-earth elements by performing the first-principles calculations. Then their magnetic properties, such as the half metallicity and the crystal-cell magnetic moments are investigated. The Sr4X3N possibly have higher Curie temperatures and have more stable half metallicity than the Sr4X3C. Their crystal-cell magnetic moments are all 1.00 μB. The crystal-cell magnetic moments and the half metallicity arise mainly from the N ions. The main mechanism is the strong covalent interaction leading to the sp2 hybridized orbitals in the Sr4X3N. Then two Sr-5s and three N-2p electrons enter into three sp2 hybridized orbitals. Among these five electrons, four electrons are paired and one is unpaired, so there are three spin-up electrons and two spin-down electrons in these sp2 hybridized orbitals.展开更多
We report a numerical study on the role of longrange dipolar interaction played on the creation and stabilization of skyrmion-(non)crystal structure in chiral ferromagnetic thin films without any anisotropies,based on...We report a numerical study on the role of longrange dipolar interaction played on the creation and stabilization of skyrmion-(non)crystal structure in chiral ferromagnetic thin films without any anisotropies,based on a Monte-Carlo simulation method.With the increase of external magnetic field,the microscopic spin configuration is transformed from a spin-spiral stripe or labyrinth structure,depending on the strength of dipolar interaction,into a skyrmion-(non)crystal structure,and then into a skyrmiongas structure,and finally into a ferromagnetic state.Interestingly,with the increase of dipolar interaction,the skyrmion-crystal structure evolves from a triangular arrangement into a square arrangement with the change of skyrmion shape from circle to square.For larger dipolar interactions,the skyrmion-crystal structure loses the regular arrangements and the skyrmions,remaining topological,exhibit different shapes and sizes and squeeze with each other,whose distributions are analogous to a non-crystal structure.Therefore,different skyrmion-(non)crystal structures are stabilized in different ranges of dipolar interactions,which further promotes the applications of skyrmions as non-volatile information carriers.展开更多
The Nd-Fe-B class alloy is the third generation of rare-earth permanent-magnet materi-al which has significant technological applications because it exhibits large magnetic ener-gy product. Compared with other permane...The Nd-Fe-B class alloy is the third generation of rare-earth permanent-magnet materi-al which has significant technological applications because it exhibits large magnetic ener-gy product. Compared with other permanent-magnet materials, Nd-Fe-B alloys are relative-ly easy to prapare and the raw materials of Nd, Fe and B are relatively economical. This note reports the first observation of Nd<sub>2</sub>Fe<sub>14</sub>B single crystal by means ofphotoelectron microscopy.展开更多
文摘The crystal structure of the title compound was determined by X-ray diffraction method at room temperature.The crystal belongs to triclinic space group P1 with the following crystallographic parameters:a=13.942(2),b=15.540(2),c=10.007(1) A,a=105.16(1)°,β=92.42(1)°,γ=88.12(1)°,V=2090.2(4) Z=4,Dc=1.23g cm-3,F(000)=820,μ(MoKα)=0.74 cm-1,and final R= 0.054 for 3208 observations.Two molecules , which are slightly different in conformation,coexist in an asymmetric unit. Some intermolecular distances are fairly short.The packing arrangement of the molecules in the crystal is also discussed.
基金financially supported by the National Natural Science Foundation of China(No.51101028)the Fundamental Research Funds for the Central Universities of China(No.E022050205)
文摘To validate the correctness of the Hartman-Perdok Theory (HPT), which indicates that the { 111 } planes have the lowest surface energy in spinel ferrites, the {111} plane orientated ZnFe204 thin films on Si(100), Si(111), and SIO2(500 nm)/Si(111) substrates were obtained through a radio frequency (RF) magnetron sputtering method with a low sputtering power of 80 W. All of the experiments prove that the atom energy determined by sputtering power plays an important role in the orientated growth of the ZnFe204 thin films, and it matches well with HPT. The ZnFe2O4 thin films exhibit ferromagnetism with a magnetization of 84.25 ld/mol at room temperature, which is different from the bulk counterpart (antiferromagnetic as usual). The ZnFe204 thin films can be used as high-quality oriented inducing buffer layers for other spinel (Ni, Mn)Zn ferrite thin films and may have high potential in magnetic thin films-based devices.
基金supported by the National Natural Science Foundation of China (No. 20901059)the Technological Development Foundation Project of Tianjin Educational Committee (No. 20080503)
文摘A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.
基金supported by the Science and Technology Foundation of Guizhou Province (No.[2008]2216)
文摘A new binuclear complex [Ni2(2,2'-bpy)2(C8H3NO6)2(H2O)4] 1 (2,2'-bpy = 2,2'- bipyridine, C8H3NO6 = 4-nitrophthalate) has been synthesized by a hydrothermal reaction and characterized by X-ray single-crystal diffraction analysis. The complex crystallizes in triclinic, space group P1 with a = 7.206(2), b = 10.337(4), c = 12.480(4) , α = 89.887(11), β = 77.033(9), γ = 78.349(6)o, V = 886.3(5) 3, Z = 1, C36H30Ni2N6O16, Mr = 920.08, Dc = 1.724 g cm-3, F(000) = 472, μ = 1.152 mm-1, the final R = 0.0458 and wR = 0.1163 for 3372 observed reflections with I 2σ(Ⅰ). The two Ni(Ⅱ) ions are bridged by two 4-nitrophthalates both in a bis-monodentate mode. Magnetic measurements reveal that the intramolecular exchange couplings in the dimer are ferromagnetic with 2J/k = 2.32 K, D =-1.44 K and g = 2.18.
基金supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1D1A1A 02042965)Ministry of Science ICT (2018R1A4A1024157)+1 种基金a Korea University Future Research Grantthe National Science Foundation Grant DMR 1400432
文摘This paper describes interlayer exchange coupling (IEC) phenomena in ferromagnetic multilayer structures, focusing on the unique IEC features observed in ferromagnetic semiconductor (Ga,Mn)As-based systems. The dependence of IEC on the structural parameters, such as non-magnetic spacer thickness, number of magnetic layers, and carrier density in the systems has been investigated by using magnetotransport measurements. The samples in the series show both a typical anisotropic magnetoresistance (AMR) and giant magnetoresistance (GMR)-like effects indicating realization of both ferromagnetic (FM) and antiferromagnetic (AFM) IEC in (Ga,Mn)As-based multilayer structures. The results revealed that the presence of carriers in the nonmagnetic spacer is an important factor to realize AFM IEC in this system. The studies further reveal that the IEC occurs over a much longer distance than predicted by current theories, strongly suggesting that the IEC in (Ga,Mn)As-based multilayers is a long-range interaction. Due to the long-range nature of IEC in the (Ga,Mn)As-based systems, the next nearest neighbor (NNN) IEC cannot be ignored and results in multi-step transitions during magnetization reversal that correspond to diverse spin configurations in the system. The strength of NNN IEC was experimentally determined by measuring minor loops that correspond to magnetization flips in specific (Ga,Mn)As layer in the multilayer system.
基金Project supported by the National Basic Research Program of China (Grant No. 2012CB619401)the National Natural Science Foundation of China (Grant Nos. 51222104 and 51071117)the Fundamental Research Funds for Central Universities
文摘Ferromagnetic transition has generally been considered to involve only an ordering of magnetic moment with no change in the host crystal structure or symmetry, as evidenced by a wealth of crystal structure data from conventional X-ray diffractometry (XRD). However, the existence of magnetostriction in all known ferromagnetic systems indicates that the magnetic moment is coupled to the crystal lattice; hence there is a possibility that magnetic ordering may cause a change in crystal structure. With the development of high-resolution synchrotron XRD, more and more magnetic transitions have been found to be accompanied by simultaneous structural changes. In this article, we review our recent progress in understand- ing the structural change at a ferromagnetic transition, including synchrotron XRD evidence of structural changes at the ferromagnetic transition, a phenomenological theory of crystal structure changes accompanying ferromagnetic transitions, new insight into magnetic morphotropic phase boundaries (MPB) and so on. Two intriguing implications of non-centric symmetry in the ferromagnetic phase and the first-order nature of ferromagnetic transition are also discussed here. In short, this review is intended to give a self-consistent and logical account of structural change occurring simultaneously with a ferromagnetic transition, which may provide new insight for developing highly magneto-responsive materials.
基金supported by the Natural Science Research Program of the Education Department of Hebei Province (No. Z2008107)the National Natural Science Foundation of China (No. 20601014)the National Basic Research Program of China (973 Program, 2007CB815305)
文摘A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ(MoKα) = 1.422 mm-1, F(000) = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper(H) centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper(Ⅱ) ion and shares the other phenolate group between the two copper(H) ions, affording a Cu2O2 plane. Each copper(Ⅱ) center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data (2-300 K) of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑(Xobsd -Xcalcd)2/∑Xobsd2= 2.76 × 10^-3.
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.
基金partly supported by the NNSFC(Nos.21301023,21501021,11474045)the 2014 Program for Liaoning Excellent Talents in University(No.LJQ2014138)+2 种基金the Program for Dalian Excellent Talents(No.2017RQ148)the Fundamental Research Funds for the Central Universities(wd01157)the 2017 Training Program of Innovation and Entrepreneurship for Undergraduates in Dalian Minzu University(201712026150 and 201812026150)
文摘The reaction of tricyanometallate precursor, Bu_4N[Fe(Tp)(CN)_3] and(Bu_4N)[(pzTp)Fe(CN)_3](Tp = tris(pyrazolyl)hydroborate, pzTp = tetrakis(pyrazolyl)borate) with Ni(ClO_4).26 H_2O in the presence of the monodentate N-methylimidazole ligand afforded two new cyano-bridged heterobimetallic {Fe2 Ni} trinuclear clusters, {[Fe(Tp)(CN)_3]_2[Ni(Mim)_4]}·8 H_2O(1) and {[Fe(pzTp)(CN)_3]_2[Ni(Mim)_4]}·2 CH_3OH·2H_2O(2). The molecular structure was determined by single-crystal X-ray diffraction. In the two compounds, the FeIII ions were coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp(or pzTp) anions, whereas, the NiII ions were surrounded by two cyanide nitrogen atoms and four nitrogen atoms from four monodentate N-methylimidazole ligands, and they were bridged by tricyanometalate building block to form similar {Fe2Ni} trinuclear clusters. Cyclic voltammetry(CV) measurements indicated that compound 1 exhibited two quasireversible iron-centered reduction processes at –0.71 and –0.17 V and one quasireversible nickel-centered oxidation process at 0.92 V, while compound 2 showed two quasireversible iron-centered reduction processes at –0.66 and –0.09 V and one quasireversible nickel-centered oxidation process at 0.88 V. Magnetic measurements showed that compounds 1 and 2 exhibited strong intrachain ferromagnetic interaction between the low-spin Fe~Ⅲ(S = 1/2) and high-spin Ni~Ⅱ(S = 1) ions.
基金This work was supported by the National Natural Science Foundation of China (No. 20331010) and Natural Science Foundation (No.033602011) of Tianjin
文摘A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(17), c = 31.445(3) ?, γ = 120°, V = 6817.8(12) ?3, Dc = 1.370 g/cm3, Z = 6, μ = 0.566 mm-1, Mr = 937.18, F(000) = 2916, R = 0.0715, wR = 0.2115 and GOF = 1.086. The structure consists of Ag(NIT3Py)3+ cation moiety, one water molecule and one perchloric ion. The Ag(I) ion is in a trigonal planar coordination environment formed by three nitrogen atoms from three NIT3Py ligand molecules.
基金supported by the National Natural Science Foundation of China(21525102,21690062)the Natural Science Foundation of Jiangsu Province(BK20140014)
文摘Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectroscopic techniques, single crystal X-ray diffraction,super conducting quantum interference device(SQUID) measurements and theoretical calculations. The dications have triplet ground states with ferromagnetic interaction exceeding the thermal energy at room temperature. The solid-state structures of these species were tunable by substituent effect, with 1^(2+) as a monomer and 2^(2+) as a dimer.
基金financially supported by the National Natural Science Foundation of China(U1832142 and 21805269)the National Key R&D Program of China(2018YFB0703602 and 2017YFA0303500)+6 种基金the Youth Innovation Promotion Association,CAS(Y202092)the Fundamental Research Funds for the Central Universities(WK2340000094)The University Synergy Innovation Program of Anhui Province(GXXT-2020-003)Anhui Provincial Natural Science Foundation(1808085QA08)the Key Research Program of Frontier Sciences(QYZDYSSW-SLH011)China Postdoctoral Science Foundation(2017M620261,2019TQ0293 and 2020M671868)the National Synchrotron Radiation Laboratory Joint funds of University of Science and Technology of China(KY2060000156 and KY2340000114)。
文摘Magnetoresistance(MR)phenomenon couples the electron transport with magnetic field,which has been at the forefront of condensed matter physics and materials science.Large-MR behaviors are of particularly importance for magnetic sensor and information memory applications,and their scarcity has aroused intensive research.Moreover,due to the different physical origins,combination of large positive and negative MR(pMR and nMR)in one single compound has rarely been reported.In present work,we achieved a coexistence of large pMR and nMR in Cr_(2)Si_(2)Te_(6) ferromagnetic semiconductor single crystal with different field configurations.Specifically,a large nMR of about -60% was obtained under the in-plane field,while a large pMR higher than 1000% took over in the out-of-plane direction.We attribute this field direction-sensitive dualistic large MR behavior to the competition and cooperation effect from the ferromagnetic interaction,orbital scattering and electronic correlation that coexist in Cr_(2)Si_(2)Te_(6),which contribute to n MR,pMR,and nMR,respectively,in dominated temperature and field ranges,and show different weights under different field directions.The elucidated multiple MR mechanism in this ferromagnetic semiconductor will shed light on the pursuit of coexistence of large p MR and nMR for field-sensitive device applications.
基金Project supported by Chongqing Natural Science Foundation,China (Grant Nos.CSCT2010BB4405 and CSTC2008BB4083)the Doctoral Foundation of Chongqing University of Posts and Telecommunications,China(Grant No.A2008-63)
文摘Several rocksalt Sr4X3N (X = O, S, Se, and Te) are predicted to be potential half-metallic ferromagnets free of transition-metal and rare-earth elements by performing the first-principles calculations. Then their magnetic properties, such as the half metallicity and the crystal-cell magnetic moments are investigated. The Sr4X3N possibly have higher Curie temperatures and have more stable half metallicity than the Sr4X3C. Their crystal-cell magnetic moments are all 1.00 μB. The crystal-cell magnetic moments and the half metallicity arise mainly from the N ions. The main mechanism is the strong covalent interaction leading to the sp2 hybridized orbitals in the Sr4X3N. Then two Sr-5s and three N-2p electrons enter into three sp2 hybridized orbitals. Among these five electrons, four electrons are paired and one is unpaired, so there are three spin-up electrons and two spin-down electrons in these sp2 hybridized orbitals.
基金financially supported by the National Natural Science Foundation of China(No.11774045)the Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(No.20180510008)。
文摘We report a numerical study on the role of longrange dipolar interaction played on the creation and stabilization of skyrmion-(non)crystal structure in chiral ferromagnetic thin films without any anisotropies,based on a Monte-Carlo simulation method.With the increase of external magnetic field,the microscopic spin configuration is transformed from a spin-spiral stripe or labyrinth structure,depending on the strength of dipolar interaction,into a skyrmion-(non)crystal structure,and then into a skyrmiongas structure,and finally into a ferromagnetic state.Interestingly,with the increase of dipolar interaction,the skyrmion-crystal structure evolves from a triangular arrangement into a square arrangement with the change of skyrmion shape from circle to square.For larger dipolar interactions,the skyrmion-crystal structure loses the regular arrangements and the skyrmions,remaining topological,exhibit different shapes and sizes and squeeze with each other,whose distributions are analogous to a non-crystal structure.Therefore,different skyrmion-(non)crystal structures are stabilized in different ranges of dipolar interactions,which further promotes the applications of skyrmions as non-volatile information carriers.
文摘The Nd-Fe-B class alloy is the third generation of rare-earth permanent-magnet materi-al which has significant technological applications because it exhibits large magnetic ener-gy product. Compared with other permanent-magnet materials, Nd-Fe-B alloys are relative-ly easy to prapare and the raw materials of Nd, Fe and B are relatively economical. This note reports the first observation of Nd<sub>2</sub>Fe<sub>14</sub>B single crystal by means ofphotoelectron microscopy.