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1.
Chun Y. Chow Hélène Bolvin Victoria E. Campbell Régis Guillot Jeff W. Kampf Wolfgang Wernsdorfer Frédéric Gendron Jochen Autschbach Vincent L. Pecoraro Talal Mallah 《Chemical science》2015,6(7):4148-4159
We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3–)4(Hshi2–)2(H2shi–)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex. 相似文献
2.
Alexandre Abhervé Samuel Ma?as-Valero Miguel Clemente-León Eugenio Coronado 《Chemical science》2015,6(8):4665-4673
The syntheses, structures and magnetic properties of the coordination compounds of formula [FeIII(acac2-trien)][MnIICrIII(Cl2 An)3]·(CH3CN)2 (1), [FeIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (2) and [GaIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (3) are reported. They exhibit a 2D anionic network formed by Mn(ii) and Cr(iii) ions linked through anilate ligands, while the [FeIII(acac2-trien)]+ or [GaIII(acac2-trien)]+ charge-compensating cations are placed inside the hexagonal channels of the 2D network, instead of being inserted in the interlamellar spacing. Thus, these crystals are formed by hybrid layers assembled through van der Waals interactions. The magnetic properties indicate that these compounds behave as magnets exhibiting a long-range ferrimagnetic ordering at ca. 11 K, while the inserted Fe(iii) cations remain in the high-spin state. As for graphene, these layered materials can be exfoliated in atomically-thin layers with heights down to 2 nm by using the well-known Scotch tape method. Hence, this micromechanical procedure provides a suitable way to isolate ultrathin layers of this kind of graphene related magnetic materials. Interestingly, this method can also be successfully used to exfoliate the 2D anilate-based compound [FeIII(sal2-trien)][MnIICrIII(Cl2An)3]·solv (4), which exhibits the typical alternated cation/anion layered structure. This result shows that the micromechanical exfoliation method, which has been extensively used for exfoliating van der Waals layered solids, can also be useful for exfoliating layered coordination compounds, even when they are formed by ionic components. 相似文献
3.
Systematic Investigation of Reaction‐Time Dependence of Three Series of Copper–Lanthanide/Lanthanide Coordination Polymers: Syntheses,Structures, Photoluminescence,and Magnetism
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Dr. Ju‐Wen Zhang Xiao‐Min Kan Bin‐Qiu Liu Guo‐Cheng Liu Dr. Ai‐Xiang Tian Prof. Xiu‐Li Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):16219-16228
Three series of copper–lanthanide/lanthanide coordination polymers (CPs) LnIIICuIICuI(bct)3(H2O)2 [Ln=La ( 1 ), Ce ( 2 ), Pr ( 3 ), Nd ( 4 ), Sm ( 5 ), Eu ( 6 ), Gd ( 7 ), Tb ( 8 ), Dy ( 9 ), Er ( 10 ), Yb ( 11 ), and Lu ( 12 ), H2bct=2,5‐bis(carboxymethylmercapto)‐1,3,4‐thiadiazole acid], LnIIICuI(bct)2 [Ln=Ce ( 2 a ), Pr ( 3 a ), Nd ( 4 a ), Sm ( 5 a ), Eu ( 6 a ), Gd ( 7 a ), Tb ( 8 a ), Dy ( 9 a ), Er ( 10 a ), Yb ( 11 a ), and Lu ( 12 a )], and LnIII2(bct)3(H2O)5 [Ln=La ( 1 b ), Ce ( 2 b ), Pr ( 3 b ), Nd ( 4 b ), Sm ( 5 b ), Eu ( 6 b ), Gd ( 7 b ), Tb ( 8 b ), and Dy ( 9 b )] have been successfully constructed under hydrothermal conditions by modulating the reaction time. Structural characterization has revealed that CPs 1 – 12 possess a unique one‐dimensional (1D) strip‐shaped structure containing two types of double‐helical chains and a double‐helical channel. CPs 2 a – 12 a show a three‐dimensional (3D) framework formed by CuI linking two types of homochiral layers with double‐helical channels. CPs 1 b – 9 b exhibit a 3D framework with single‐helical channels. CPs 6 b and 8 b display visible red and green luminescence of the EuIII and TbIII ions, respectively, sensitized by the bct ligand, and microsecond‐level lifetimes. CP 8 b shows a rare magnetic transition between short‐range ferromagnetic ordering at 110 K and long‐range ferromagnetic ordering below 10 K. CPs 9 a and 9 b display field‐induced single‐chain magnet (SCM) and/or single‐molecule magnet (SMM) behaviors, with Ueff values of 51.7 and 36.5 K, respectively. 相似文献
4.
The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI
4CuII
1.5(L1)3(CN)6]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu3(L2)4(H2O)3]·6(OTf)·n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (43.123)(42.122) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII analogue [Cu2(L1)2(NMP)(H2O)]·4BF4·12NMP·1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.82 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C60 through soaking the crystals in a toluene solution. 相似文献
5.
[Ga(en)3][Ga3Se7(en)] · H2O: A Gallium Chalcogenide with Chains of [Ga3Se6Se2/2(en)]3– Bicycles The new selenidogallate [Ga(en)3][Ga3Se7(en)] · H2O ( I ) was produced from a ethylendiamine suspension of Ga and Se at 130 °C. I crystallizes in the orthorhombic space group Pna21 with unit constants a = 1347.9(3) pm, b = 961.6(1) pm, c = 1967.6(4) pm and Z = 4. The crystal structure contains an anion so far not observed in gallium chalcogenides. It is built from [Ga3Se6Se2/2(en)]3– bicycles of three GaIIIL4 tetrahedra (L = en, Se) connected via selenium corners to linear chains. The cations, GaIII ions coordinated by three ethylendiamine in a distorted octahedral geometry are positioned in the holes of the hexagonal rod packing of these chains. 相似文献
6.
Samia Benmansour Antonio Hernndez-Paredes María Bayona-Andrs Carlos J. Gmez-García 《Molecules (Basel, Switzerland)》2021,26(4)
The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: C6O4X22−, with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy2(C6O4H2)3(dmso)2(H2O)2]·2dmso·18H2O (1) and [Dy2(C6O4Cl2)3(dmso)4]·2dmso·2H2O (2) show distorted hexagonal honeycomb layers with the solvent molecules (dmso and H2O) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers. The magnetic measurements of compounds 1, 2 and [Dy2(C6O4(CN)Cl)3(dmso)6] (3), a recently reported related compound, show that the three compounds present slow relaxation of the magnetization. In compound 1 the SIM behaviour does not need the application of a DC field whereas 2 and 3 are field-induced SIM (FI-SIM) since they show slow relaxation of the magnetization when a DC field is applied. We discuss the differences observed in the crystal structures and magnetic properties based on the X group of the anilato ligands (H, Cl and Cl/CN) in 1–3 and in the recently reported derivative [Dy2(C6O4Br2)3(dmso)4]·2dmso·2H2O (4) with X = Br, that is also a FI-SIM. 相似文献
7.
J. Wang X. D. Zhang Y. Wang Y. Zhang Z. R. Liu J. Tong P. L. Kang 《Journal of Structural Chemistry》2004,45(6):1022-1030
Syntheses and structure determination of TbIII and ErIII complexes with nitrilotriacetic acids (nta) are reported. Their crystal and molecular structures, molecular formulas, and compositions were determined by single-crystal X-ray structure analyses and elementary analyses, respectively. The crystal of the (NH4)3[TbIII(nta)2(H2O)]·4H2O complex belongs to the monoclinic crystal system and C2/c space group. Crystal data are as follows: a = 16.357(8) Å, b = 8.552(4) Å, c = 17.390(9) Å, β = 104.748(7)°, V = 2352.6(19) Å3, Z = 4, Mr = 675.32, Dc = 1.932 g·cm−3, μ = 3.112 mm−1, and F(000) = 1368. The final R and Rw are 0.0220 and 0.0494 for 2357 (I > 2σ(I)) unique reflections, R and Rw are 0.0266 and 0.0510 for all 5613 reflections, respectively. The TbIIIN2O7 moiety in the [TbIII(nta)2(H2O)]3− complex anion has a pseudo-monocapped square antiprismatic nine-coordinate structure, in which the eight coordinate atoms (two N and six O) are from two nta ligands and the water molecule is coordinated to the central TbIII ion directly as the ninth coordinate atom. The crystal of the (NH4)3[ErIII(nta)2] complex belongs to the trigonal crystal system and R-3c space group. Crystal data are as follows: a = 7.9181(16) Å, b = 7.9181(16) Å, c = 54.27(2) Å, γ = 120°, V = 2946.7(14) Å3, Z = 6, Mr = 597.61, D
c = 2.021 g·cm−3, μ = 4.345 mm−1, and F(000) = 1770. The final R and Rw are 0.0295 and 0.0673 for 677 (I > 2σ(I)) unique reflections, R and Rw are 0.0366 and 0.0700 for all 4827 reflections, respectively. The ErIIIN2O6 part in the [ErIII(nta)2]3− complex anion is an eight-coordinate structure with a pseudo-dicapped octahedron, in which the eight coordinate atoms (two N and six O) are from two nta ligands.Original Russian Text Copyright © 2004 by J. Wang, X. D. Zhang, Y. Wang, Y. Zhang, Z. R. Liu, J. Tong, and P. L. Kang__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1067–1075, November–December, 2004. 相似文献
8.
J. Q. Gao T. Wu J. Wang X. D. Jin D. Li B. X. Wang K. Li Y. Li 《Russian Journal of Coordination Chemistry》2011,37(11):817-824
In this work, the title complexes, (EnH2)1.5[ErIII(Ttha)] · 3H2O (I) and (EnH2)[ErIII(Egta)(H2O)]2 · 6H2O (II), where En = ethylenediamine, H6Ttha = triethylenetetramine-N,N,N′,N″,N″’,N″′-hexaacetic acid, H4Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized. Their structures have been characterized by IR spectroscopy and single-crystal
X-ray diffraction techniques. The X-ray diffraction reveals that I is nine-coordinated and crystallizes in the monoclinic crystal space group P2/n with cell dimensions a = 17.6058(16), b = 9.6249(9), c = 20.560(2) ?, β = 109.7440(10)°, and V = 3279.1(5) ?3. Compound II is also nine-coordinated and crystallizes in the monoclinic crystal space group P21/n with the cell dimensions a = 12.938(6), b = 12.651(5), c = 14.943(6) ?, β = 105.441(5)°, and V = 2357.5(17) ?3. In I, each EnH22+ cation connects three adjacent [ErIII(Egta)(H2O)]− complex anions through hydrogen bonds, while in I, there are two types of EnH2
2+ anions. One is highly symmetrical, forming hydrogen bonds with two neighboring [ErIII(Ttha)]3− complex anions. The other anion connects three adjacent [ErIII(Ttha)]3− complex anions through hydrogen bonds. These hydrogen bonds lead to the formation of 2D ladder-like layer structure. 相似文献
9.
Mathias S. Wickleder 《无机化学与普通化学杂志》1999,625(9):1548-1555
Syntheses, Crystal Structures, and Thermal Behavior of Er2(SO4)3 · 8 H2O and Er2(SO4)3 · 4 H2O Evaporation of aqueous solutions of Er2(SO4)3 yields light pink single crystals of Er2(SO4)3 · 8 H2O. X-ray single crystal investigations show that the compound crystallizes monoclinically (C2/c, Z = 8, a = 1346.1(3), b = 667.21(1), c = 1816.2(6) pm, β = 101.90(3)°, Rall = 0.0169) with eightfold coordination of Er3+, according to Er(SO4)4(H2O)4. DSC- and temperature dependent X-ray powder investigations show that the decomposition of the hydrate follows a two step mechanism, firstly yielding Er2(SO4)3 · 3 H2O and finally Er2(SO4)3. Attempts to synthesize Er2(SO4)3 · 3 H2O led to another hydrate, Er2(SO4)3 · 4 H2O. There are two crystallographically different Er3+ ions in the triclinic structure (P 1, Z = 2, a = 663.5(2), b = 905.5(2), c = 1046.5(2) pm, α = 93.59(3)°, β = 107.18(2)°, γ = 99.12(3)°, Rall = 0.0248). Er(1)3+ is coordinated by five SO42– groups and three H2O molecules, Er(2)3+ is surrounded by six SO42– groups and one H2O molecule. The thermal decomposition of the tetrahydrate yields Er2(SO4)3 in a one step process. In both cases the dehydration produces the anhydrous sulfate in a modification different from the one known so far. 相似文献
10.
J. Wang X. Zh. Liu Zh. H. Zhang X. D. Zhang G. R. Gao Y. M. Kong Y. Li 《Russian Journal of Coordination Chemistry》2006,32(8):590-599
The title complexes, Na[ErIII(Cydta)(H2O)2] · 5H2O (I) and Na2[SmIII(Cydta)][SmIII(Cydta)(H2O)3] · 11H2O (II) (Cydta is trans-1,2-cyclohexanediaminetetraacetic acid), are prepared and characterized using IR, elemental analyses, and single-crystal X-ray diffraction techniques. Crystal I belongs to triclinic system (space group P1), which has a mononuclear eight-coordinate slightly distorted square antiprismatic conformation. The crystal data are as follows: a = 8.371(12) Å, b = 9.952(14) Å, c = 14.74(2) Å, α = 88.32(2)°, β = 76.30(2)°, γ = 87.87(2)°, V = 1192(3) Å3, Z = 1, ρ = 1.835 g/cm3, μ = 3.612 mm?1, F(000) = 658, R = 0.0194, and wR = 0.0520 for 4130 observed reflections with I≥2σ(I). Crystal II belongs to monoclinic system (space group P21/n), which has the binuclear nine-coordinate structure with tricapped trigonal prismatic conformation for Sm(1) and the pseudomonocapped square antiprismatic conformation for Sm(2). The crystal data are as follows: a = 12.283(6) Å, b = 15.626(7) Å, c = 25.875(12) Å, β = 97.962(7)°, V = 4919(4) Å3, Z = 4, ρ = 1.717 g/cm3, μ = 2.476 mm?1, F(000) = 2536, R = 0.0781, and wR = 0.1745 for 8554 observed reflections with I ≥ 2σ(I). 相似文献
11.
Junhao Wang Jakub J. Zakrzewski Mikolaj Zychowicz Veacheslav Vieru Liviu F. Chibotaru Koji Nakabayashi Szymon Chorazy Shin-ichi Ohkoshi 《Chemical science》2021,12(2):730
Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores tunable anisotropy and the luminescence re-absorption effect of HoIII complexes. Our concept is shown in dinuclear cyanido-bridged molecules, {[HoIII(4-pyridone)4(H2O)2][MIII(CN)6]}·nH2O (M = Co, 1; Rh, 2; Ir, 3) and their magnetically diluted analogues, {[HoIIIxYIII1–x(4-pyridone)4(H2O)2][MIII(CN)6]}·nH2O (M = Co, x = 0.11, 1@Y; Rh, x = 0.12, 2@Y; Ir, x = 0.10, 3@Y). They are built of pentagonal bipyramidal HoIII complexes revealing the zero-dc-field SMM effect. Experimental studies and the ab initio calculations indicate an Orbach magnetic relaxation with energy barriers varying from 89.8 to 86.7 and 78.7 cm−1 K for 1, 2, and 3, respectively. 1–3 also differ in the strength of quantum tunnelling of magnetization which is suppressed by hyperfine interactions, and, further, by the magnetic dilution. The YIII-based dilution governs the optical properties as 1–3 exhibit poor emission due to the dominant re-absorption from HoIII while 1@Y–3@Y show room-temperature blue emission of 4-pyridone. Within ligand emission bands, the sharp re-absorption lines of the HoIII electronic transitions were observed. Their strong thermal variation was used in achieving highly sensitive ratiometric optical thermometers whose good performance ranges, lying between 25 and 205 K, are adjustable by using hexacyanidometallates. This work shows that HoIII complexes are great prerequisites for advanced opto-magnetic systems linking slow magnetic relaxation with unique optical thermometry exploiting a luminescence re-absorption phenomenon.HoIII complexes bearing organic luminophores and inorganic metalloligands are an effective tool for achieving the unique conjunction of single-molecule magnetism and thermometric luminescence re-absorption phenomenon. 相似文献
12.
Firasat Hussain Stefan Sandriesser Greta R. Patzke 《Journal of solid state chemistry》2011,184(1):214-219
A series of head-on complexes of lanthanoid containing germanotungstates was isolated from a one pot reaction in an acetate buffer at pH 4.5. This convenient approach brought forward the [{Ln(CH3COO)GeW11O39(H2O)}2]12− (Ln=EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, and YbIII) family with acetate chelators in the rarely observed μ2: η2-η1 mode. All compounds were structurally characterized using various solid state analytics, such as single crystal X-ray diffraction, FT-IR spectroscopy, and thermogravimetric analysis. The isostructural polyanions crystallize in the monoclinic system (S.G. P21/c). Temperature-dependent magnetic susceptibility measurements were performed on the GdIII-complex which exhibits near perfect Curie-type behavior. 相似文献
13.
It is crucial to investigate the slow relaxation mechanisms of binuclear ErIII‐based single‐molecule magnets (SMMs) and explore strategies for optimizing their magnetic properties. Herein, a doped compound, [Y1.75Er0.25(thd)4Pc] ? 2C6H6 ( YEr ? 2C6H6 , Hthd=2,2,6,6‐tetramethylheptanedione, H2Pc=phthalocyanine), was synthesized by doping the paramagnetic erbium(III) compound Er2 ? 2C6H6 in the diamagnetic yttrium(III) matrix Y2 ? 2C6H6 . The doping effect was studied using SQUID magnetization measurements. The results suggest that magnetic‐site dilution improves the magnetic property from a fast relaxation of the pure ErIII compound to a typical SMM relaxation process of the doped sample. In this binuclear system, the dominant single‐ion relaxation is entangled with the neighboring ErIII ion through the intramolecular ErIII???ErIII interaction, which plays an important role in suppressing the quantum tunneling of the magnetization (QTM) process. Furthermore, the influence of lattice solvents on single‐ion relaxation was studied. By releasing the benzene molecules, compound YEr ? 2C6H6 can be successfully transformed to a desolvated sample YEr accompanied by structural alteration and improved SMM performance. 相似文献
14.
Valentina D. Sasnovskaya Leokadiya V. Zorina Sergey V. Simonov Artem D. Talantsev Eduard B. Yagubskii 《Molecules (Basel, Switzerland)》2022,27(23)
Four new heterometallic complexes combining [MII(H2dapsc)]2+ cations with the chelating H2dapsc {2,6-diacetylpyridine-bis(semicarbazone)} Schiff base ligand and [Cr(CN)6]3− anion were synthesized: {[MII(H2dapsc)]CrIII(CN)6K(H2O)2.5(EtOH)0.5}n·1.2n(H2O), M = Mn (1) and Co (2), {[Mn(H2dapsc)]2Cr(CN)6(H2O)2}Cl·H2O (3) and {[Co(H2dapsc)]2Cr(CN)6(H2O)2}Cl·2EtOH·3H2O (4). In all the compounds, M(II) centers are seven-coordinated by N3O2 atoms of H2dapsc in the equatorial plane and N or O atoms of two apical –CN/water ligands. Crystals 1 and 2 are isostructural and contain infinite negatively charged chains of alternating [MII(H2dapsc)]2+ and [CrIII(CN)6]3− units linked by CN-bridges. Compounds 3 and 4 consist of centrosymmetric positively charged trimers in which two [MII(H2dapsc)]2+ cations are bound through one [CrIII(CN)6]3− anion. All structures are regulated by π-stacking of coplanar H2dapsc moieties as well as by an extensive net of hydrogen bonding. Adjacent chains in 1 and 2 interact also by coordination bonds via a pair of K+ ions. The compounds containing MnII (1, 3) and CoII (2, 4) show a significant difference in magnetic properties. The ac magnetic measurements revealed that complexes 1 and 3 behave as a spin glass and a field-induced single-molecule magnet, respectively, while 2 and 4 do not exhibit slow magnetic relaxation in zero and non-zero dc fields. The relationship between magnetic properties and non-covalent interactions in the structures 1–4 was traced. 相似文献
15.
Bipyrimidines have been chosen as (N∧N)(N∧N) bridging ligands for connecting metal centers. IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O. The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration. The obvious quenching of visible emission from IrIII complex in the IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes indicates that energy transfer occurred from IrIII center to lanthanides. NIR emissions from NdIII, YbIII, and ErIII were obtained under the excitation of visible light by selective excitation of the IrIII-based chromophore. It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdIII, YbIII, and ErIII. 相似文献
16.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):187-203
Heteronuclear cationic complexes, [LCuLn]3+ and [(LCu)2Ln]3+, were employed as nodes in designing high‐nuclearity complexes and coordination polymers with a rich variety of network topologies (L is the dianion of the Schiff base resulting from the 2:1 condensation of 3‐methoxysalycilaldehyde with 1,3‐propanediamine). Two families of linkers have been chosen: the first consists of exo‐dentate ligands bearing nitrogen‐donor atoms (bipyridine (bipy), dicyanamido (dca)), whereas the second consists of exo‐dentate ligands with oxygen‐donor atoms (anions derived from the acetylenedicarboxylic (H2acdca), fumaric (H2fum), trimesic (H3trim), and oxalic (H2ox) acids). The ligands belonging to the first family prefer copper(II ) ions, whereas the ligands from the second family interact preferentially with oxophilic rare‐earth cations. The following complexes have been obtained and crystallographically characterized: [LCuII(OH2)GdIII(NO3)3] ( 1 ), [{LCuIIGdIII(NO3)3}2(μ‐4,4′‐bipy)] ( 2 ), [LCuIIGdIII(acdca)1.5(H2O)2] ? 13 H2O ( 3 ), [LCuIIGdIII(fum)1.5(H2O)2] ? 4 H2O ? C2H5OH ( 4 ), [LCuIISmIII(H2O)(Hfum)(fum)] ( 5 ), [LCuIIErIII(H2O)2(fum)]NO3 ? 3 H2O ( 6 ), [LCuIISmIII(fum)1.5(H2O)2] ? 4 H2O ? C2H5OH ( 7 ), [{(LCuII)2SmIII}2fum2](OH)2 ( 8 ), [LCuIIGdIII(trim)(H2O)2] ? H2O ( 9 ), [{(LCuII)2PrIII}(C2O4)0.5(dca)]dca ? 2 H2O ( 10 ), [LCuIIGdIII(ox)(H2O)3][CrIII(2,2′‐bipy)(ox)2] ? 9 H2O ( 11 ), and [LCuGd(H2O)4{Cr(CN)6}] ? 3 H2O ( 12 ). Compound 1 is representative of the whole family of binuclear CuII–LnIII complexes which have been used as precursors in constructing heteropolymetallic complexes. The rich variety of the resulting structures is due to several factors: 1) the nature of the donor atoms of the linkers, 2) the preference of the copper(II ) ion for nitrogen atoms, 3) the oxophilicity of the lanthanides, 4) the degree of deprotonation of the polycarboxylic acids, 5) the various connectivity modes exhibited by the carboxylato groups, and 6) the stoichiometry of the final products, that is, the CuII/LnIII/linker molar ratio. A unique cluster formed by 24 water molecules was found in crystal 11 . In compounds 2 , 3 , 4 , 9 , and 11 the CuII–GdIII exchange interaction was found to be ferromagnetic, with J values in the range of 3.53–8.96 cm?1. Compound 12 represents a new example of a polynuclear complex containing three different paramagnetic ions. The intranode CuII–GdIII ferromagnetic interaction is overwhelmed by the antiferromagnetic interactions occurring between the cyanobridged GdIII and CrIII ions. 相似文献
17.
Y. Bai J. Q. Gao J. Wang X. D. Jin Y. Li B. Wang T. Wu X. D. Zhang 《Russian Journal of Coordination Chemistry》2013,39(1):49-57
Two novel complexes, (EnH2)1.5[HoIII(Ttha)] · 4.5H2O (I) (En = ethylenediamine and H6Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid) and (EnH2)[HoIII(Egta)(H2O)]2 · 6H2O (II) (H4Egta = ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid), were synthesized and their crystal structures were determined by single crystal X-ray diffraction techniques. Complex I has a nine-coordinate mononuclear structure with distorted tricapped trigonal prismatic conformation and crystallizes in the monoclinic crystal system with P2/n space group. The crystal data are as follows: a = 17.7541(18), b = 9.6810(10), c = 22.166(2) Å, β = 118.913(2)°, and V = 3335.0(6) Å3. Complex II has a mononuclear nine-coordinate structure with pseudo-monocapped square antiprismatic conformation and crystallizes in the monoclinic crystal system with P21/n space group. The crystal data are as follows: a = 12.978(8), b = 12.685(8), c = 14.905(9) Å, β = 105.333(7)°, and V = 2366(2) Å3. In I, there are two types of EnH 2 2+ anions. They connect to [HoIII(Ttha)]3? by hydrogen bonds leading to the formation of 3D pore structure along z axis. In II, EnH 2 2+ cation connects three adjacent [HoIII(Egta)(H2O)]? complex anions through hydrogen bonds, these hydrogen bonds lead to the formation of 2D network structure in [101] plane. The results showed that ligand structures play a crucial role in crystal and molecular structure of their complexes. In addition, the protonated (EnH 2 2+ ) cations conjugating to [HoIII(Ttha)]3? and [HoIII(Egta)(H2O)]? complex anions are reviewed, which act as an important beginning for study of Ho(III) complexes conjugating with other various amino and heterocyclic biomolecule. 相似文献
18.
The reduction of the octahedral cobalt(III) complex CoIII(HL)·9H2O, H4L = 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane by glutathione (GSH) has been studied by conventional spectrophotometry at 25.0 ≤ t/°C ≤ 45.0, 0.02 ≤ [H+]/mol dm?3 ≤ 0.20 and I = 0.3 mol dm?3 (NaClO4). The reaction is biphasic. The fast initial phase is attributed to the H+-induced formation of the mixed ligand complex, [CoIII(H2L)GSH]+, for which the rate-limiting step is the chelate ring opening via CoIII–NH (amide–N) bond cleavage of the protonated species, [CoIII(H2L)]+. Outer-sphere association equilibria between GSH/GSH2 + and [CoIII(H2L)]+ substantially retard the ring opening process and consequently the mixed ligand complex formation. This is then followed by a slow phase involving reduction of [CoIII(H2L)GSH]+ by both GSH and GSH2 +. The final products are the corresponding Co(II) complex and the oxidized form of GSH, GS–SG. The kinetic data and activation parameters for the redox process are interpreted in terms of an outer-sphere electron transfer mechanism. 相似文献
19.
M.C. BerniniE.V. Brusau G.E. Narda G. Echeverria A. FantoniG. Punte A.P. Ayala 《Polyhedron》2012,31(1):729-737
The synthesis, crystal structure and characterization of [Er2(C4H4O4)3(H2O)4]·6H2O, with particular emphasis on the structural details and the vibrational behavior of the highly organized sub-net of water are reported. X-ray structural analysis reveals that the hybrid framework, which can be classified as belonging to the I0O2 type, acts as a host of an infinite tape of six-membered water rings with distorted chair conformation. The water network extends between the hybrid layers helping the close packing and the stabilization of the structure through H-bond interactions, with further development of the supramolecular tridimensional structure. The self-assembly of the hydration water molecules is conditioned by the hybrid host, forcing them to adopt a less stable conformation when compared with hexagonal ice. The vibrational spectra of partially and completely dehydrated samples as well as of partially isotopic diluted ones have been obtained and analyzed. In order to guide the assignment of the vibrational spectra a theoretical calculation was performed at the B3LYP/6-31G∗∗ level for a model consisting of three water clusters. 相似文献
20.
J. Wang X. D. Zhang Y. Zhang W. G. Jia Zh. R. Liu 《Journal of Structural Chemistry》2004,45(1):114-123
The crystal and molecular structures of the [PrIII(nta)(H2O)2]·H2O (nta = nitrilotriacetic acids), K3[GdIII(nta)2(H2O)]·6H2O, and K3[YbIII(nta)2]·5H2O complexes have been determined by single-crystal X-ray structure analyses. In [PrIII(nta)(H2O)2]·H2O, the PrIIINO8 part forms a nine-coordinate pseudo-monocapped square antiprismatic structure in which one N and three O atoms are from one nta ligand in the same molecule, three O atoms from another nta ligand in the neighboring molecule and two O atoms from two coordinate water molecules. In K3[GdIII(nta)2(H2O)]·6H2O, the [GdIII(nta)2(H2O)3- complex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which each nta acts as a tetradentate ligand with one N atom of the amino group and three O atoms of the carboxylic groups. In K3[YbIII(nta)2]·5H2O, each nta also acts as a tetradentate ligand with one N atom of amino group and three O atoms of the carboxylic groups, but the [YbIII(nta)2
3- complex anion has an eight-coordinate structure with a distorted square antiprismatic prism. All the results including those for [TmIII(nta)(H2O)2]·2H2O confirm the inferences on the coordinate structures and coordination numbers of rare earth metal complexes with the nta ligand. 相似文献