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1.
The spin lattice model for the spin-gapped layered magnetic solids Na3Cu2SbO6 and Na2Cu2TeO6 was examined by evaluating the three spin exchange interactions of their Cu2MO6 (M = Sb, Te) layers in terms of spin dimer analysis based on extended Hückel tight binding calculations and mapping analysis based on first principles density functional theory electronic band structure calculations. For both compounds, our calculations show that the two strongest spin exchange interactions, that is, the Cu-O...O-Cu super-superexchange (J2) and the Cu-O-Cu superexchange (J1) interactions, form alternating chains that interact weakly through the Cu-O-Cu superexchange (J3) interactions. The dominant one of the three spin exchange interactions is J2, and it is antiferromagnetic in agreement with the fact that both of the compounds are spin gapped. For Na3Cu2SbO6 and Na2Cu2TeO6, the superexchange J1 is calculated to be ferromagnetic, hence, leading to the alternating chain model in which antiferromagnetic and ferromagnetic spin exchange interactions alternate. This picture does not agree with the recent experimental analysis, which showed that the temperature-dependent magnetic susceptibilities of both compounds should be described by the alternating chain model in which two antiferromagnetic spin exchange interactions of different strengths alternate.  相似文献   

2.
The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta = 94.416(1) degrees, Z = 4.  相似文献   

3.
Cu(5)SbO(6) is found to have a monoclinic, Delafossite-derived structure consisting of alternating layers of O-Cu(I)-O sticks and magnetic layers of Jahn-Teller distorted Cu(II)O(6) octahedra in an edge sharing honeycomb arrangement with Sb(V)O(6) octahedra. This yields the structural formula Cu(I)(3)Cu(II)(2)Sb(V)O(6). Variants with ordered and disordered layer stacking are observed, depending on the synthesis conditions. The spin ? Cu(2+) ions form dimers in the honeycomb layer. The magnetic susceptibility measured between 5 and 300 K is characteristic of the presence of a singlet-triplet spin gap of 189 K. High resolution synchrotron X-ray diffraction studies indicate that changes in the intra- or interdimer distances between 300 and 20 K, such as might indicate an increase in strength of the Peierls-like distortion through the spin gap temperature, if present, are very small. A comparison to the NaFeO(2)-type Cu(2+) honeycomb compounds Na(3)Cu(2)SbO(6) and Na(2)Cu(2)TeO(6) is presented.  相似文献   

4.
We synthesized and structurally and magnetically characterized the novel 3D coordination polymer Cu(HCO2)2(pym) (pym = pyrimidine). The compound crystallizes in the monoclinic space group C2/c with a = 14.4639(8) A, b = 7.7209(4) A, c = 8.5172(5) A, beta = 126.076(2) degrees, and V= 768.76(7) A3. In the structure buckled layers of Cu(HCO2)2 are interconnected by pym ligands to afford 1D Cu-pym-Cu chains. Bulk magnetic susceptibility measurements show a broad maximum at 25 K that is indicative of short-range magnetic ordering. Between 12 and 300 K a least-squares fit of the chi(T) data to a mean-field-corrected antiferromagnetic chain model yielded excellent agreement for g = 2.224(3), J/kB = -26.9(2) K, and zJ'/kB = -1.1(3) K. Below approximately 3 K a transition to long-range magnetic ordering is observed, as suggested by a sharp and sudden decrease in chi(T). This result is corroborated by muon spin relaxation measurements that show oscillations in the muon asymmetry below T(N) = 2.802(1) K and rapidly fluctuating moments above T(N).  相似文献   

5.
We report on the syntheses, crystal structures, and magnetic susceptibilities of a family of copper pyrazine (pz)-based antiferromagnets with moderate in-plane magnetic exchange. These materials fall into two classes: monoclinic complexes [Cu(pz)2]A2 for A = ClO4 (1) or BF4 (2) and the tetragonal complex [Cu(pz)2(NO3)]PF6 (3). Compound 1 and its deuterated version [Cu(pz-d4)2](ClO4)2 (1a) crystallize in the space group C2/m at room temperature with disordered perchlorate anions. For both 1 and 2, the C centering of the Cu(II), S = 1/2, site yields four equivalent nearest neighbors, producing layers of Cu(II) ions bridged by the pz molecules, which map onto a square magnetic lattice. The layers are offset such that Cu(II) ions lie above and below the holes of adjacent layers. Compound 3 crystallizes in the space group I4/mcm with a layer structure similar to those of 1 and 2 but with Cu(II) ions of adjacent layers stacked above each other and bridged by semicoordinate NO3- ions. The variable-temperature susceptibilities in these compounds approximate a two-dimensional Heisenberg antiferromagnet with J values within the layers of 17.5(3) K (1), 15.3(3) K (2), and 10.8(3) K (3). Ordering transitions are observed in the magnetic data at 4.2(3) and 4.3(5) K for 1 and 2, respectively.  相似文献   

6.
A new chlorocuprate(II), [(C(2)H(5))(4)N](2)Cu(5)Cl(12), was prepared by reaction of CuCl(2).2H(2)O and (C(2)H(5))(4)NCl in 1,1,2-trichloroethane-ethanol followed by water-ethanol evaporation. The crystal structure, solved by single-crystal X-ray diffraction at room temperature, was found to be triclinic, space group P&onemacr;, with cell parameters a = 8.9123(9) ?, b = 11.0690(8) ?, c = 11.2211(9) ?, alpha = 118.766(6) degrees beta = 109.041(8) degrees, gamma = 97.465(7) degrees, and Z = 1, and consists of a two-dimensional network of [(Cu(5)Cl(12))(2)(-)](infinity) parallel to the a, b plane, alternating with layers of the organic cations along c. The anionic sheets are built up by aggregation of infinite zigzag chains of alternating tetranuclear and mononuclear subsequences. This structure can be related to the anhydrous CuCl(2) structure by systematic removal of (Cu(2)Cl(6))(2+) fragments. The magnetic susceptibility of this compound can be described by a simple model, suggested by the structural data, that considers independent contributions of linear tetramers, with antiferromagnetically coupled pairs of copper atoms (J(1)/k = -64(2) K), and almost magnetically isolated Cu(II) centers, that obey a Curie-Weiss law with a Θ = -2.7(8) K.  相似文献   

7.
Belik AA  Azuma M  Takano M 《Inorganic chemistry》2005,44(21):7523-7529
Magnetic properties of three isostructural compounds BaMP2O7 (M = Co, Ni, and Cu) were investigated by dc and ac magnetization and specific heat measurements. BaCuP2O7 was shown to be an excellent quasi-one-dimensional linear-chain Heisenberg antiferromagnet with an exchange constant (J/kB) of 103.8 K (Hamiltonian H = J Sigma SiS(i+1)) and a temperature for the long-range magnetic order (TN) of 0.81 K giving the ratio kBTN/J = 0.78%. BaCoP2O7 and BaNiP2O7 exhibited long-range antiferromagnetic order at TN = 10.4 and 10.1 K, respectively. BaCoP2O7 and BaNiP2O7 showed a large contribution of the short-range correlation above TN. BaNiP2O7 remained in the antiferromagnetic state up to 90 kOe at 2 K, whereas BaCoP2O7 demonstrated two metamagnetic phase transitions at about 52 and 71 kOe at 2 K if the magnetic field was parallel to the easy direction. BaMP2O7 melted incongruently at 1323 K (M = Co), 1344 K (M = Ni), and 1338 K (M = Cu).  相似文献   

8.
The formation of mixed molybdenum-tellurium oxides MoTeO5, Mo2TeO8, Mo3TeO11, MoTe2O7 in the gas phase has been studied by mass spectrometry (MS) experiments at temperatures of about 938 K and studied theoretically by quantum chemical (QC) methods. Structural and thermodynamic data for the molecules was calculated. The mixed oxides MoTeO5, Mo2TeO8, Mo3TeO11 and MoTe2O7 in the gas phase have been reported for the first time. Experimental thermodynamic data have been determined by means of MS and confirmed theoretically by DFT and ab initio (MP2) calculations. Adiabatic ionisation potentials (IPs) were obtained experimentally and compared with theoretical vertical ionisation potentials. The following values are given: Δ(f)H(298)(0) (MoTeO5) = ?730.2 kJ mol(?1) (MS), Δ(f)H(298)(0) (MoTeO5) = ?735.4 kJ mol(?1) (DFT), ?717.3 kJ mol(?1) (MP2), S(298)(0) (MoTeO5) = 389.5 J mol(?1) K(?1) (DFT), c(p)(0)(T)(MoTeO5) = 141.71 + 13.54 × 10(?3)T ? 2.53 × 10(6)T(?2) J mol(?1) K(?1) (298 < T < 940 K) (DFT), Δ(f)H(298)(0) (Mo2TeO8) = ?1436.3 kJ mol(?1) (MS), Δ(f)H(298)(0) (Mo2TeO8) = ?1436.1 kJ mol(?1) (DFT), ?1455.9 kJ mol(?1) (MP2), S(298)(0) (Mo2TeO8) = 517.1 J mol(?1) K(?1) (DFT), c(p)(0)(T)(Mo2TeO8) = 228.64 + 24.15 × 10(?3)T ? 4.09 × 10(6)T(?2) J mol(?1) K(?1) (298 < T < 940 K) (DFT), Δ(f)H(298)(0) (Mo3TeO11) = ?2132.7 kJ mol(?1) (MS), Δ(f)H(298)(0) (Mo3TeO11) = ?2110.7 kJ mol(?1) (DFT), ?2163.2 kJ mol(?1) (MP2), S(298)(0) (Mo3TeO11) = 629.3 J mol(?1) K(?1) (DFT), c(p)(0)(T)(Mo3TeO11) = 316.40 + 34.10 × 10(?3)T ? 5.74 × 10(6)T(?2) J mol(?1) K(?1) (298 < T < 940 K) (DFT), Δ(f)H(298)(0) (MoTe2O7) = ?999.7 kJ mol(?1) (MS), Δ(f)H(298)(0) (MoTe2O7) = ?1002.7 kJ mol(?1) (DFT), ?1000.9 kJ mol(?1) (MP2), S(298)(0) (MoTe2O7) = 504.8 J mol(?1) K(?1) (DFT), c(p)(0)(T)(MoTe2O7) = 211.19 + 18.02 × 10(?3)T ? 3.53 × 10(6)T(?2) J mol(?1) K(?1) (298 < T < 940 K) (DFT), IP(MoTeO5) = 10.68 eV (DFT), IP(Mo2TeO8) = 10.4 ± 0.5 eV (MS), IP(Mo2TeO8) = 10.41 eV (DFT), IP(Mo3TeO11) = 10.7 ± 0.5 eV (MS), IP(Mo3TeO11) = 10.18 eV (DFT), IP(MoTe2O7) = 9.91 eV (DFT).  相似文献   

9.
Using aqueous conditions, three new coordination polymers containing Cu(2+) cations, dicyanamide (dca) anions, and pyrimidine (pym) were isolated and structurally and magnetically characterized. Comprising the bulk of the product yield, Cu(dca)(2)(pym)(2), 1, crystallizes in the monoclinic space group P2(1)/c with a = 7.3569(5) A, b = 13.4482(9) A, c = 7.4559(5) A, beta = 98.984(3) degrees, and V = 728.6(1) A and forms linear 1D chains. The second compound, Cu(dca)(NO(3))(pym)(H(2)O), 2, is also monoclinic, P2(1)/n, with a = 7.6475(3) A, b = 12.2422(5) A, c = 11.0286(4) A, beta = 106.585(2) degrees, and V = 989.6(1) A(3). A 2D network structure consisting of both bridging mu-dca and pym ligands is formed while the NO(3)(-) and H(2)O are axially bonded to the Cu center. Cu(3)(dca)(6)(pym)(2).0.75H(2)O, 3, is triclinic, Ponemacr;, with a = 7.7439(4) A, b = 9.3388(5) A, c = 10.1779(5) A, alpha = 86.014(2) degrees, beta = 88.505(2) degrees, gamma = 73.623(2) degrees, and V = 704.46(9) A(3). The structure of 3 is quite unique in that [Cu(3)(pym)(2)](6+) trimers are interconnected via mu-dca ligands affording a complex 3D self-penetrating framework. Magnetically, 1 exhibits extremely weak exchange interactions along the Cu-(dca)(2)-Cu ribbons while 2 and 3 display very strong magnetic couplings mediated by the mu-bonded pym ligands. Moreover, 2 shows a broad maximum in chi(T) at 40 K and behaves as a uniform 1D antiferromagnetic chain with g = 2.09(1), J/k(B) = -42.6(1) K, and TIP = -66 x 10(-)(6) emu/mol. An S = (1)/(2) trimer model that includes intertrimer interactions successfully described the magnetic behavior of 3, yielding g = 2.10(1), J/k(B) = -69.4(5) K, theta = -0.28(3) K, and TIP = -180 x 10(-)(6) emu/mol. It is found that mu-bonded dca and pym ligands mediate very weak and very strong exchange interactions, respectively, between Cu(2+) centers.  相似文献   

10.
The crystal structure of the low-temperature form of AgCuPO4 (i.e., alpha-AgCuPO4) was determined by powder X-ray diffraction and was compared with that of the high-temperature form of AgCuPO4 (i.e., beta-AgCuPO4). The magnetic properties of the two forms were examined by measuring their magnetic susceptibilities and evaluating the relative strengths of their spin-exchange interactions on the basis of spin-dimer analysis. Both forms of AgCuPO4 have layers of Cu2P2O8 alternating with silver-atom double layers; beta-AgCuPO4 has two Cu2P2O8 layers per unit cell, while alpha-AgCuPO4 has one. The coordinate environment of each Cu2+ ion is close to being a distorted square pyramid in alpha-AgCuPO4, but it is close to being a distorted trigonal bipyramid in beta-AgCuPO4. The magnetic susceptibilities of alpha- and beta-AgCuPO4 are well simulated by an antiferromagnetic alternating-chain model, which leads to J/k(B) = -146.1 K and alphaJ/k(B) = -75.8 K for alpha-AgCuPO4, and J/k(B) = -82.6 K and alphaJ/k(B) = -31.7 K for beta-AgCuPO4 (with the convention in which the spin-exchange parameter between two adjacent spin sites is written as 2J). The spin gaps, delta/k(B), obtained from these parameters are 93.7 K for alpha-AgCuPO4 and 62.3 K for beta-AgCuPO4. The strongest spin exchange in both forms of AgCuPO4 comes from a super-superexchange path, and this interaction is stronger for alpha-AgCuPO4 than for beta-AgCuPO4 by a factor of approximately 2, in good agreement with the experiment. Our analysis supports the use of this model for beta-AgCuPO4 and indicates that the spin lattice of alpha-AgCuPO4 would be better described by a two-dimensional net made up of weakly interacting alternating chains.  相似文献   

11.
The novel heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8)(-) (1) has been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic studies. Single-crystal X-ray analysis was carried out on [K(7)Na[Cu(4)K(2)(H(2)O)(6)(alpha-AsW(9)O(33))(2)].5.5H(2)O](n)(K(7)Na-1), which crystallizes in the tetragonal system, space group P42(1)m, with a = 16.705(4) A, b = 16.705(4) A, c = 13.956(5) A, and Z = 2. Interaction of the lacunary [alpha-AsW(9)O(33)](9)(-) with Cu(2+) ions in neutral, aqueous medium leads to the formation of the dimeric polyoxoanion 1 in high yield. Polyanion 1 consists of two alpha-AsW(9)O(33) units joined by a cyclic arrangement of four Cu(2+) and two K(+) ions, resulting in a structure with C(2)(v)() symmetry. All copper ions have one terminal water molecule, resulting in square-pyramidal coordination geometry. Three of the copper ions are adjacent to each other and connected via two micro(3)-oxo bridges. EPR studies on K(7)Na-1 and also on Na(9)[Cu(3)Na(3)(H(2)O)(9)(alpha-AsW(9)O(33))(2)].26H(2)O (Na(9)-2) over 2-300 K yielded g values that are consistent with a square-pyramidal coordination around the copper(II) ions in 1 and 2. No hyperfine structure was observed due to the presence of strong spin exchange, but fine structure was observed for the excited (S(T) = 3/2) state of Na(9)-2 and the ground state (S(T) = 1) of K(7)Na-1. The zero-field (D) parameters have also been determined for these states, constituting a rare case wherein one observes EPR from both the ground and the excited states. Magnetic susceptibility data show that Na(9)-2 has antiferromagnetically coupled Cu(2+) ions, with J = -1.36 +/- 0.01 cm(-)(1), while K(7)Na-1 has both ferromagnetically and antiferromagnetically coupled Cu(2+) ions (J(1) = 2.78 +/- 0.13 cm(-)(1), J(2) = -1.35 +/- 0.02 cm(-)(1), and J(3) = -2.24 +/- 0.06 cm(-)(1)), and the ground-state total spins are S(T) = 1/2 in Na(9)-2 and S(T) = 1 in K(7)Na-1.  相似文献   

12.
Zhu Z  Karasawa S  Koga N 《Inorganic chemistry》2005,44(17):6004-6011
Three metal complexes, [M(II)Cl2(4NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C(radical)...C(beta) = 3.17 and 3.23 A) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (C(radical)...C(alpha) = 3.46 and 3.52 A for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the chi(mol)T values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the chi(mol)T vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/kB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the chi(mol)T value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/chi(mol) vs T plot for 2 was analyzed by a Curie-Weiss model to give theta = 6.25 K and C = 2.02 cm3 K mol(-1) with g(Ni) = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of T(c) = 2.14 K and exhibited a glasslike magnetic behavior below T(c).  相似文献   

13.
A new Cu(II) complex, [Cu(3)(dcp)(2)(H(2)O)(4)](n), with the ligand 3,5-pyrazoledicarboxylic acid monohydrate (H(3)dcp) has been prepared by hydrothermal synthesis, and it crystallizes in the monoclinic space group P2(1)/c with a = 11.633(2) A, b = 9.6005(14) A, c = 6.9230(17) A, beta = 106.01(2) degrees, and Z = 2. In the solid state structure of [Cu(3)(dcp)(2)(H(2)O)(4)](n), trinuclear [Cu(3)(dcp)(2)(H(2)O)(4)] repeating units in which two dcp(3-) ligands chelate the three Cu(II) ions with the central Cu(II) ion, Cu(1) (on an inversion center), link to form infinite 2D sheets via syn-anti equatorial-equatorial carboxylate bridges between Cu(2) atoms in adjacent trimers. These layers are further linked by syn-anti axial-equatorial carboxylate bridging between Cu(1) atoms in adjacent sheets resulting in the formation of a crystallographic 3D network. A detailed analysis of the magnetic properties of [Cu(3)(dcp)(2)(H(2)O)(4)](n) reveals that the dcp(3-) ligand acts to link Cu(II) centers in three different ways with coupling constants orders of magnitude apart in value. In the high temperature region above 50 K, the dominant interaction is strongly antiferromagnetic (J/k(B) = -32 K) within the trimer units mediated by the pyrazolate bridges. Below 20 K, the trimer motif can be modeled as an S = 1/2 unit. These units are coupled to their neighbors by a ferromagnetic interaction mediated by the syn-anti equatorial-equatorial carboxylate bridge. This interaction has been estimated at J(2D)/k(B) = +2.8 K on the basis of a 2D square lattice Heisenberg model. Finally, below 3.2 K a weak antiferromagnetic coupling (J(3D)/k(B) = -0.1 K) which is mediated by the syn-anti axial-equatorial carboxylate bridges between the 2D layers becomes relevant to describe the magnetic (T, H) phase diagram of this material.  相似文献   

14.
马恩  江海龙 《结构化学》2007,26(10):1159-1164
TbCu(TeO3)2Cl was obtained in high yield from high temperature solid-state reac-ion of Tb4O7,CuO,CuCl2 and TeO2 in a 1:2:2:8 molar ratio at 710 ℃ in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. The title compound crystal-lizes in monoclinic,space group P21/c,with a=5.409(2),b=14.994(6),c=9.183(4),β= 98.884(5)°,V=735.8(5) ?3 and Z=4. TbCu(TeO3)2Cl is isostructural with LnCu(TeO3)2X (Ln= Dy,X= Cl; Ln=Er,X=Cl,Br). Its structure features a three-dimensional (3D) network built from Tb(Ⅲ) and Cu(II) ions interconnected by tellurite and chloride anions; the chloride anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels in the network. Solid-state luminescent spectrum of TbCu(TeO3)2Cl shows a strong emission band at 545 nm with a luminescent life time of 291 μs.  相似文献   

15.
We have exploited potential utility of 4,4,5,5-tetramethylimidazolin-1-oxyl (hin) and 4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide (hnn) as mu-1,4 and mu-1,5 bridging ligands, respectively, carrying an unpaired electron in development of metal-radical hybrid magnets. X-ray diffraction measurements of [Cu(hfac)(2)hin] (1), [Mn(hfac)(2)hin] (2), and [Mn(hfac)(2)hnn] (3) revealed one-dimensional metal-radical alternating chain structures, where hfac denotes 1,1,1,5,5,5-hexafluoropentane-2,4-dionate. Magnetic measurements of 1 indicate the presence of intrachain ferromagnetic coupling between copper and radical spins. The magnetic exchange parameter was estimated as 2J/k = 56.8 K based on an S = 1/2 equally spaced ferromagnetic chain model (H = -2J summation operator S(i).S(i+1)). This ferromagnetic interaction can be explained in terms of the axial coordination of the hin nitrogen or oxygen to Cu(II). The chi(m)T value of 2 and 3 increased on cooling, and the magnetic data could be analyzed by Seiden's ferrimagnetic chain model, giving 2J/k = -325 and -740 K, respectively. The antiferromagnetic interaction of 2 and 3 can be attributed to orbital overlap between the manganese and the oxygen or nitrogen magnetic orbitals. The exchange interactions between Cu-hin and Mn-hnn are larger than those of typical Cu- and Mn-nitronyl nitroxide complexes, indicating that the choice of small ligands is a promising strategy to bestow strong exchange interaction. Compound 3 became a ferrimagnet below 4.4 K, owing to ferromagnetic coupling among the ferrimagnetic chains.  相似文献   

16.
Two novel Cu6 and Mn6 hexagon sandwiched polyoxometalates, [(CuCl)6(AsW9O33)2]12- (1a) and [(MnCl)6(SbW9O33)2]12- (2a), have been synthesized and characterized by X-ray single-crystal analysis and magnetic measurements. These complexes are D3d symmetric and were isolated as [n-BuNH3]+ salts from aqueous solutions: (n-BuNH3)12[(CuCl)6(AsW9O33)2].6H2O (1), rhombohedral, R, a = 20.33(1) A, c = 26.35(2) A, Z = 3 and (n-BuNH3)12[(MnCl)6(SbW9O33)2].6H2O (2). Six Cu (or Mn) atoms, each of which shows 5-fold coordination, make an approximately equatorial hexagon with a first-neighboring Cu...Cu (Mn...Mn) distance of 2.913(2) A (3.248(1) A) and a Cu-O-Cu (Mn-O-Mn) bond angle of 94.5(2) degrees (100.4(2) degrees ). The magnetic behavior investigated by magnetic susceptibility measurements shows the ferromagnetic exchange interactions with J/k = +12.7 K (J/hc = +8.82 cm(-1)) and a S = 3 ground state for 1 and J/k = +0.20 K (J/hc = +0.14 cm(-1)) and a S = 15 ground state for 2, when only J refers to the isotropic magnetic-exchange interactions for first-neighbor atoms of the approximately equilateral Cu6(12+) and Mn6(12+) hexagons. The single-crystal ESR spectroscopy of 1 under the orientation of the magnetic field along a Cu6 hexagon's nearly 6-fold axis equal to the c axis on the variation of temperature supports the S = 3 ground state and allows an estimate of the zero-field (fine-structure) energy separation between Sz = 0 and Sz = +/-1 of D = -0.182 K to be obtained.  相似文献   

17.
The novel dimeric silicotungstates [[SiM2W9O34(H2O)]2]12- (M = Mn2+, Cu2+, Zn2+) have been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic measurements. X-ray single-crystal analyses were carried out on K4Na6Mn[[SiMn2W9O34(H2O)]2].33H2O (1), which crystallizes in the triclinic system, space group P1, with a = 12.2376(7) A, b = 13.6764(8) A, c = 15.6177(9) A, alpha = 70.2860(10) degrees, beta = 79.9150(10) degrees, gamma = 70.2760(10) degrees, and Z = 1; K3Na5[[SiCu2W9O34(H2O)]2].26H2O (2) crystallizes in the triclinic system, space group P1, with a = 11.4271(12) A, b = 12.5956(13) A, c = 15.3223(16) A, alpha = 80.456(2)degrees, beta = 76.383(2) degrees, gamma = 76.968(2) degrees, and Z = 1; K4Na6[[SiZn2W9O34(H2O)]2].34H2O (3) crystallizes also in the triclinic system, space group P1, with a = 12.2596(14) A, b = 13.2555(15) A, c = 16.2892(18) A, alpha = 96.431(2) degrees, beta = 100.944(2) degrees, gamma = 110.404(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[SiW9O34]10- Keggin moieties linked via a rhomblike M4O16 (M = Mn, Cu, Zn) group leading to a sandwich-type structure. Magnetic measurements show that the central Mn4 unit in 1 exhibits antiferromagnetic (J = -1.77(5) cm(-1)) as well as weak ferromagnetic (J' = 0.08(2) cm(-1)) Mn-Mn exchange interactions. In 2 the Cu-Cu exchange interactions are antiferromagnetic (J = -0.10(2) cm(-1), J' = -0.29(2) cm(-1)).  相似文献   

18.
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy.  相似文献   

19.
The novel dimeric germanotungstates [M(4)(H(2)O)(2)(GeW(9)O(34))(2)](12)(-) (M = Mn(2+), Cu(2+), Zn(2+), Cd(2+)) have been synthesized and characterized by IR spectroscopy, elemental analysis, magnetic measurements, and (183)W-NMR spectroscopy. X-ray single-crystal analyses were carried out on Na(12)[Mn(4)(H(2)O)(2)(GeW(9)O(34))(2)].38H(2)O (Na(12)()-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.0419(8) A, b = 17.8422(10) A, c = 21.1626(12) A, beta = 93.3120(10) degrees, and Z = 2; Na(11)Cs(2)[Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)]Cl.31H(2)O (Na(11)()Cs-2) crystallizes in the triclinic system, space group P, with a = 12.2338(17) A, b = 12.3833(17) A, c = 15.449(2) A, alpha = 100.041(2) degrees, beta = 97.034(2) degrees, gamma = 101.153(2) degrees, and Z = 1; Na(12)[Zn(4)(H(2)O)(2)(GeW(9)O(34))(2)].32H(2)O (Na(12)()-3) crystallizes in the triclinic system, space group P, with a = 11.589(3) A, b = 12.811(3) A, c = 17.221(4) A, alpha = 97.828(6) degrees, beta = 106.169(6) degrees, gamma = 112.113(5) degrees, and Z = 1; Na(12)[Cd(4)(H(2)O)(2)(GeW(9)O(34))(2)].32.2H(2)O (Na(12)()-4) crystallizes also in the triclinic system, space group P, with a = 11.6923(17) A, b = 12.8464(18) A, c = 17.616(2) A, alpha = 98.149(3) degrees, beta = 105.677(3) degrees, gamma = 112.233(2) degrees, and Z = 1. The polyanions consist of two lacunary B-alpha-[GeW(9)O(34)](10)(-) Keggin moieties linked via a rhomblike M(4)O(16) (M = Mn, Cu, Zn, Cd) group leading to a sandwich-type structure. (183)W-NMR studies of the diamagnetic Zn and Cd derivatives indicate that the solid-state polyoxoanion structures are preserved in solution. EPR measurements on Na(12)()-1 at frequencies up to 188 GHz and temperatures down to 4 K yield a single, exchange-narrowed peak, at g(iso) = 1.9949, typical of Mn systems, and an upper limit of |D| = 20.0 mT; its magnetization studies still await further theoretical treatment. Detailed EPR studies on Na(11)()Cs-2 over temperatures down to 2 K and variable frequencies yield g( parallel ) = 2.4303 and g( perpendicular ) = 2.0567 and A( parallel ) = 4.4 mT (delocalized over the Cu(4) framework), with |D| = 12.1 mT. Magnetization studies in addition yield the exchange parameters J(1) = -11 and J(2) = -82 cm(-)(1), in agreement with the EPR studies.  相似文献   

20.
The hydrothermal reaction of Th(NO3)4.xH2O with V2O5 and H6TeO6 at 200 degrees C under autogenously generated pressure results in the formation of Th(VO2)2(TeO6)(H2O)2 as a pure phase. The single-crystal X-ray data indicate that Th(VO2)2(TeO6)(H2O)2 possesses a three-dimensional structure constructed from ThO9 tricapped trigonal prisms, VO5 distorted square pyramids, VO4 distorted tetrahedra, and TeO6 distorted octahedra. Both of the vanadium polyhedra contain VO2+ vanadyl units with two short V=O bond distances. The tellurate octahedron is tetragonally distorted and utilizes all of its oxygen atoms to bond to adjacent metal centers, sharing edges with ThO9 and VO5 units, and corners with two ThO9, one VO5, and two VO4 polyhedra. Crystallographic data: Th(VO2)2(TeO6)(H2O)2, orthorhombic, space group Pbca, a = 12.6921(7), b = 11.5593(7), c = 13.0950(8) A, Z = 8 (T = 193 K). The UV-vis diffuse reflectance spectrum of Th(VO2)2(TeO6)(H2O)2 shows vanadyl-based charge-transfer absorption features. Th(VO2)2(TeO6)(H2O)2 decomposes primarily to Th(VO3)4 when heated at 600 degrees C in air.  相似文献   

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