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1.
Two C3‐Symmetric Dy3III Complexes with Triple Di‐μ‐methoxo‐μ‐phenoxo Bridges,Magnetic Ground State,and Single‐Molecule Magnetic Behavior
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Dr. Mikko M. Hänninen Prof. Dr. Antonio J. Mota Dr. Daniel Aravena Prof. Dr. Eliseo Ruiz Prof. Dr. Reijo Sillanpää Dr. Agustín Camón Dr. Marco Evangelisti Prof. Dr. Enrique Colacio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8410-8420
Two series of isostructural C3‐symmetric Ln3 complexes Ln3 ? [BPh4] and Ln3 ? 0.33[Ln(NO3)6] (in which LnIII=Gd and Dy) have been prepared from an amino‐bis(phenol) ligand. X‐ray studies reveal that LnIII ions are connected by one μ2‐phenoxo and two μ3‐methoxo bridges, thus leading to a hexagonal bipyramidal Ln3O5 bridging core in which LnIII ions exhibit a biaugmented trigonal‐prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self‐consistent field (CASSCF) calculations indicate that the magnetic coupling between the DyIII ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest Dy?O distance, the local magnetic moments are oriented almost perpendicular to the Dy3 plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the DyIII ions are separated by approximately 150 and 177 cm?1, for Dy3 ? [BPh4] and Dy3 ? 0.33[Dy(NO3)6], respectively. As expected for these large energy gaps, Dy3 ? [BPh4] and Dy3 ? 0.33[Dy(NO3)6] exhibit, under zero direct‐current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied Hdc field of 1000 Oe, Dy3 ? [BPh4] exhibits two thermally activated processes with Ueff values of 34.7 and 19.5 cm?1, whereas Dy3 ? 0.33[Dy(NO3)6] shows only one activated process with Ueff=19.5 cm?1. 相似文献
2.
Role of Magnetic Exchange Interactions in the Magnetization Relaxation of {3d–4f} Single‐Molecule Magnets: A Theoretical Perspective
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Dr. Saurabh Kumar Singh Mohammad Faizan Beg Prof. Dr. Gopalan Rajaraman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(2):672-680
Combined density functional and ab initio calculations are performed on two isomorphous tetranuclear {Ni3IIILnIII} star‐type complexes [Ln=Gd ( 1 ), Dy ( 2 )] to shed light on the mechanism of magnetic exchange in 1 and the origin of the slow magnetization relaxation in complex 2 . DFT calculations correctly reproduce the sign and magnitude of the J values compared to the experiments for complex 1 . Acute ?Ni?O?Gd bond angles present in 1 instigate a significant interaction between the 4fxyz orbital of the GdIII ion and 3d orbital of the NiII ions, leading to rare and strong antiferromagnetic Ni???Gd interactions. Calculations reveal the presence of a strong next‐nearest‐neighbour Ni???Ni antiferromagnetic interaction in complex 1 leading to spin frustration behavior. CASSCF+RASSI‐SO calculations performed on complex 2 suggest that the octahedral environment around the DyIII ion is neither strong enough to stabilize the mJ |±15/2〉 as the ground state nor able to achieve a large ground‐state–first‐excited‐state gap. The ground‐state Kramers doublet for the DyIII ion is found to be the mJ |±13/2〉 state with a significant transverse anisotropy, leading to very strong quantum tunneling of magnetization (QTM). Using the POLY_ANISO program, we have extracted the JNiDy interaction as ?1.45 cm?1. The strong Ni???Dy and next‐nearest‐neighbour Ni???Ni interactions are found to quench the QTM to a certain extent, resulting in zero‐field SMM behavior for complex 2 . The absence of any ac signals at zero field for the structurally similar [Dy(AlMe4)3] highlights the importance of both the Ni???Dy and the Ni???Ni interactions in the magnetization relaxation of complex 2 . To the best of our knowledge, this is the first time that the roles of both the Ni???Dy and Ni???Ni interactions in magnetization relaxation of a {3d–4f} molecular magnet have been established. 相似文献
3.
Large Hexadecametallic {MnIII–LnIII} Wheels: Synthesis,Structural, Magnetic,and Theoretical Characterization
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Kuduva R. Vignesh Dr. Stuart K. Langley Dr. Boujemaa Moubaraki Prof. Keith S. Murray Prof. Gopalan Rajaraman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16364-16369
The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {MnIII8LnIII8} (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2, in the presence of ortho‐toluic or benzoic acid are reported. From the seven wheels studied the {Mn8Dy8} and {Mn8Y8} analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8Y8} complex due to weak ferromagnetic MnIII–MnIII interactions. Ab initio CASSCF+RASSI‐SO calculations on the {Mn8Dy8} wheel estimated the MnIII–DyIII exchange interaction as ?0.1 cm?1. This weak exchange along with unfavorable single‐ion anisotropy of DyIII/MnIII ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g‐anisotropy of the DyIII ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8Ln8} clusters reported here are the largest heterometallic MnIIILnIII wheels and the largest {3d–4f} wheels to exhibit SMM behavior reported to date. 相似文献
4.
《无机化学与普通化学杂志》2018,644(5):293-300
Three dinuclear lanthanide complexes [Ln2(H2L)2(NO3)4] [Ln = Dy ( 1 ), Tb ( 2 ), and Gd ( 3 )] [H3L = 2‐hydroxyimino‐N′‐[(2‐hydroxy‐3‐methoxyphenyl)methylidene]‐propanohydrazone] were solvothermally synthesized by varying differently anisotropic rare earth ions. Single‐crystal structural analyses demonstrate that all the three complexes are crystallographically isostructural with two centrosymmetric LnIII ions aggregated by a pair of monodeprotonated H2L– anions. Weak intramolecular antiferromagnetic interactions with different strength were mediated by a pair of phenoxo bridges due to superexchange and/or single‐ion anisotropy. Additionally, the DyIII‐based entity shows the strongest anisotropy exhibits field‐induced single‐molecule magnetic behavior with two thermally activated relaxation processes. In contrast, 3 with isotropic GdIII ion has a significant cryogenic magnetocaloric effect with the maximum entropy change of 25.7 J · kg–1 · K–1 at 2.0 K and 70.0 kOe. 相似文献
5.
Magnetic Relaxation in Single‐Electron Single‐Ion Cerium(III) Magnets: Insights from Ab Initio Calculations
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Saurabh Kumar Singh Tulika Gupta Dr. Liviu Ungur Prof. Dr. Gopalan Rajaraman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13812-13819
Detailed ab initio calculations were performed on two structurally different cerium(III) single‐molecule magnets (SMMs) to probe the origin of magnetic anisotropy and to understand the mechanism of magnetic relaxations. The complexes [CeIII{ZnII(L)}2(MeOH)]BPh4 ( 1 ) and [Li(dme)3][CeIII(cot′′)2] ( 1 ; L=N,N,O,O‐tetradentate Schiff base ligand; 2 ; DME=dimethoxyethane, COT′′=1,4‐bis(trimethylsilyl)cyclooctatetraenyldianion), which are reported to be zero‐field and field‐induced SMMs with effective barrier heights of 21.2 and 30 K respectively, were chosen as examples. CASSCF+RASSI/SINGLE_ANISO calculations unequivocally suggest that mJ|±5/2〉 and |±1/2〉 are the ground states for complexes 1 and 2 , respectively. The origin of these differences is rooted back to the nature of the ligand field and the symmetry around the cerium(III) ions. Ab initio magnetisation blockade barriers constructed for complexes 1 and 2 expose a contrasting energy‐level pattern with significant quantum tunnelling of magnetisation between the ground state Kramers doublet in complex 2 . Calculations performed on several model complexes stress the need for a suitable ligand environment and high symmetry around the cerium(III) ions to obtain a large effective barrier. 相似文献
6.
Eva Lucaccini Matteo Briganti Dr. Mauro Perfetti Dr. Laure Vendier Dr. Jean‐Pierre Costes Dr. Federico Totti Prof. Dr. Roberta Sessoli Prof. Dr. Lorenzo Sorace 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5552-5562
The magnetic behaviour of a Dy(LH)3 complex (LH? is the anion of 2‐hydroxy‐N′‐[(E)‐(2‐hydroxy‐3‐methoxyphenyl)methylidene]benzhydrazide) was analysed in depth from both theoretical and experimental points of view. Cantilever torque magnetometry indicated that the complex has Ising‐type anisotropy, and provided two possible directions for the easy axis of anisotropy due to the presence of two magnetically non‐equivalent molecules in the crystal. Ab initio calculations confirmed the strong Ising‐type anisotropy and disentangled the two possible orientations. The computed results obtained by using ab initio calculations were then used to rationalise the composite dynamic behaviour observed for both pure DyIII phase and YIII diluted phase, which showed two different relaxation channels in zero and non‐zero static magnetic fields. In particular, we showed that the relaxation behaviour at the higher temperature range can be correctly reproduced by using a master matrix approach, which suggests that Orbach relaxation is occurring through a second excited doublet. 相似文献
7.
Jun‐Liang Liu Wei‐Quan Lin Yan‐Cong Chen Silvia Gómez‐Coca Daniel Aravena Prof. Dr. Eliseo Ruiz Ji‐Dong Leng Prof. Dr. Ming‐Liang Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17567-17577
A series of heterometallic [LnIIIxCuIIy] complexes, [Gd2Cu2]n ( 1 ), [Gd4Cu8] ( 2 ), [Ln9Cu8] (Ln=Gd, 3?Gd ; Ln=Dy, 3?Dy ), were successfully synthesized by a one‐pot route at room temperature with three kinds of in situ carbonyl‐related reactions: Cannizzaro reaction, aldol reaction, and oxidation. This strategy led to dysprosium analogues that behaved as single‐molecule magnets (SMMs) and gadolinium analogues that showed significant magnetocaloric effect (MCE). In this study a numerical DFT approach is proposed by using pseudopotentials to calculate the exchange coupling constants in three polynuclear [GdxCuy] complexes; with these values exact diagonalization or quantum Monte Carlo simulations have been performed to calculate the variation of the magnetic entropy involved in the MCE. For the [Dy9Cu8] complexes, local magnetic properties of the DyIII centers have been determined by using the CASSCF+RASSI method. 相似文献
8.
Analysis of the Role of Peripheral Ligands Coordinated to ZnII in Enhancing the Energy Barrier in Luminescent Linear Trinuclear Zn‐Dy‐Zn Single‐Molecule Magnets
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Dr. Jean Pierre Costes Dr. Silvia Titos‐Padilla Itziar Oyarzabal Tulika Gupta Dr. Carine Duhayon Prof. Gopalan Rajaraman Prof. Enrique Colacio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15785-15796
Three new Dy complexes have been prepared according to a complex‐as‐ligand strategy. Structural determinations indicate that the central Dy ion is surrounded by two LZn units (L2? is the di‐deprotonated form of the N2O2 compartmental N,N′‐2,2‐dimethylpropylenedi(3‐methoxysalicylideneiminato) Schiff base. The Dy ions are nonacoordinate to eight oxygen atoms from the two L ligands and to a water molecule. The Zn ions are pentacoordinate in all cases, linked to the N2O2 atoms from L, and the apical position of the Zn coordination sphere is occupied by a water molecule or bromide or chloride ions. These resulting complexes, formulated (LZnX)‐Dy‐(LZnX), are tricationic with X=H2O and monocationic with X=Br or Cl. They behave as field‐free single‐molecule magnets (SMMs) with effective energy barriers (Ueff) for the reversal of the magnetization of 96.9(6) K with τ0=2.4×10?7 s, 146.8(5) K with τ0=9.2×10?8 s, and 146.1(10) K with τ0=9.9×10?8 s for compounds with Zn?OH2, Zn?Br, and Zn?Cl motifs, respectively. The Cole–Cole plots exhibit semicircular shapes with α parameters in the range of 0.19 to 0.29, which suggests multiple relaxation processes. Under a dc applied magnetic field of 1000 Oe, the quantum tunneling of magnetization (QTM) is partly or fully suppressed and the energy barriers increase to Ueff=128.6(5) K and τ0=1.8×10?8 s for 1 , Ueff=214.7 K and τ0=9.8×10?9 s for 2 , and Ueff=202.4 K and τ0=1.5×10?8 s for 3 . The two pairs of largely negatively charged phenoxido oxygen atoms with short Dy?O bonds are positioned at opposite sides of the Dy3+ ion, which thus creates a strong crystal field that stabilizes the axial MJ=±15/2 doublet as the ground Kramers doublet. Although the compound with the Zn?OH2 motifs possesses the larger negative charges on the phenolate oxygen atoms, as confirmed by using DFT calculations, it exhibits the larger distortions of the DyO9 coordination polyhedron from ideal geometries and a smaller Ueff value. Ab initio calculations support the easy‐axis anisotropy of the ground Kramers doublet and predict zero‐field SMM behavior through Orbach and TA‐QTM relaxations via the first excited Kramers doublet, which leads to large energy barriers. In accordance with the experimental results, ab initio calculations have also shown that, compared with water, the peripheral halide ligands coordinated to the Zn2+ ions increase the barrier height when the distortions of the DyO9 have a negative effect. All the complexes exhibit metal‐centered luminescence after excitation into the UV π–π* absorption band of ligand L2? at λ=335 nm, which results in the appearance of the characteristic DyIII (4F9/2→6HJ/2; J=15/2, 13/2) emission bands in the visible region. 相似文献
9.
《无机化学与普通化学杂志》2018,644(8-9):443-448
A salen‐type Dy2 complex [Dy2(L)(MeOH)2(CH3COO)4] · 2(MeOH) was isolated and magnetically characterized, in which one hexadentate ligand H2L [H2L = N,N‐bis(2‐oxy‐3‐methoxybenzylidene)‐1,2‐phenylenediamine] chelated two DyIII ions, one is located on the apical position of the inner N2O2 site, leaving the outer O2O2 cavity for another DyIII ion. There are two distinct local coordination environments presented as square antiprism (D4d) for Dy1 and biaugmented trigonal prism (C2v) for Dy2. Magnetic measurements reveal that the ferromagnetic interaction between two DyIII ions occurred within low temperature range and accompanied with significant slow magnetic relaxation behavior with energy barriers to the reversal of magnetization Ueff/KB = 40 K under zero dc field. 相似文献
10.
Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties
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Dr. Maria‐Gabriela Alexandru Dr. Diana Visinescu Prof. Marius Andruh Dr. Nadia Marino Dr. Donatella Armentano Dr. Joan Cano Prof. Francesc Lloret Prof. Miguel Julve 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5429-5446
The use of the [FeIII(AA)(CN)4]? complex anion as metalloligand towards the preformed [CuII(valpn)LnIII]3+ or [NiII(valpn)LnIII]3+ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H2valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[CuII(valpn)LnIII(H2O)3(μ‐NC)2FeIII(phen)(CN)2 {(μ‐NC)FeIII(phen)(CN)3}]NO3 ? 7 H2O}n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [CuII(valpn)LaIII(OH2)3(O2NO)(μ‐NC)FeIII(phen)(CN)3] ? NO3 ? H2O ? CH3CN ( 4 ) were obtained with the [CuII(valpn)LnIII]3+ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[NiII(valpn)LnIII(ONO2)2(H2O)(μ‐NC)3FeIII(bipy)(CN)] ? 2 H2O ? 2 CH3CN}n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [NiII(valpn)LnIII]3+ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [CuII(valpn)LaIII(OH2)3(O2NO)(μ‐NC)FeIII(phen)(CN)3]+, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {FeIII(bipy)(CN)4} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {NiII(valpn)LnIII} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the CuII?LnIII ( 1 – 3 ) and NiII?LnIII ( 5 – 7 ) units, as well as through the single cyanide bridge between the FeIII and either NiII ( 5 – 7 ) or CuII ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τo) and energy barrier (Ea) through the Arrhenius equation being 2.0×10?12 s and 29.1 cm?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (NiII–DyIII) and single cyanide (FeIII–NiII) pathways are masked by the depopulation of the Stark levels of the DyIII ion, this feature most likely accounting for the continuous decrease of χM T upon cooling observed for this last compound. 相似文献
11.
Trinuclear [CoIII2–LnIII] (Ln=Tb,Dy) Single‐Ion Magnets with Mixed 6‐Chloro‐2‐Hydroxypyridine and Schiff Base Ligands
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Prof. Dr. Cai‐Ming Liu Prof. Dr. De‐Qing Zhang Prof. Dr. Xiang Hao Prof. Dao‐Ben Zhu 《化学:亚洲杂志》2014,9(7):1847-1853
The Schiff base ligand N1,N3‐bis(3‐methoxysalicylidene)diethylenetriamine (H2valdien) and the co‐ligand 6‐chloro‐2‐hydroxypyridine (Hchp) were used to construct two 3d–4f heterometallic single‐ion magnets [Co2Dy(valdien)2(OCH3)2(chp)2] ? ClO4 ? 5 H2O ( 1 ) and [Co2Tb(valdien)2(OCH3)2(chp)2] ? ClO4 ? 2 H2O ? CH3OH ( 2 ). The two trinuclear [CoIII2LnIII] complexes behave as a mononuclear LnIII magnetic system because of the presence of two diamagnetic cobalt(III) ions. Complex 1 has a molecular symmetry center, and it crystallizes in the C2/c space group, whereas complex 2 shows a lower molecular symmetry and crystallizes in the P21/c space group. Magnetic investigations indicated that both complexes are field‐induced single‐ion magnets, and the CoIII2–DyIII complex possesses a larger energy barrier [74.1(4.2) K] than the CoIII2–TbIII complex [32.3(2.6) K]. 相似文献
12.
Guo FS Liu JL Leng JD Meng ZS Lin ZJ Tong ML Gao S Ungur L Chibotaru LF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(8):2458-2466
A family of linear Dy3 and Tb3 clusters have been facilely synthesized from the reactions of DyCl3, the polydentate 3‐methyloxysalicylaldoxime (MeOsaloxH2) ligand with auxiliary monoanionic ligands, such as trichloroacetate, NO3?, OH?, and Cl?. Complexes 1 – 5 contain a nearly linear Ln3 core, with similar Ln???Ln distances (3.6901(4)–3.7304(3) Å for the Dy3 species, and 3.7273(3)–3.7485(5) Å for the Tb3 species) and Ln???Ln???Ln angles of 157.036(8)–159.026(15)° for the Dy3 species and 157.156(8)–160.926(15)° for the Tb3 species. All three Ln centers are bridged by the two doubly‐deprotonated [MeOsalox]2? ligands and two of the four [MeOsaloxH]? ligands through the N,O‐η2‐oximato groups and the phenoxo oxygen atoms (Dy‐O‐Dy angles=102.28(16)–106.85(13)°; Tb‐O‐Tb angles=102.00(11)–106.62(11)°). The remaining two [MeOsaloxH]? ligands each chelate an outer LnIII center through their phenoxo oxygen and oxime nitrogen atoms. Magnetic studies reveal that both Dy3 and Tb3 clusters exhibit significant ferromagnetic interactions and that the Dy3 species behave as single‐molecule magnets, expanding upon the recent reports of the pure 4f type SMMs. 相似文献
13.
Fengying Zhou Suyun Zhang Yang Zhao Chongguang Zhang Xiaojuan Cheng Lina Zheng Yong Zhang Yahong Li Prof. Dr. 《无机化学与普通化学杂志》2009,635(15):2636-2641
Reaction of DyCl3 with two equivalents of NaN(SiMe3)2 in THF yielded {Dy(μ‐Cl)[N(SiMe3)2]2(THF)}2 ( 1 ). X‐ray crystal structure analysis revealed that 1 is a centrosymmetric dimer with asymmetrically bridging chloride ligands. The metal coordination arrangement can be best described as distorted trigonal bipyramid. The bond lengths of Ln–Cl and Ln–N showed a decreasing trend with the contraction of the size of Ln3+. Treatment of N,N‐bis(pyrrolyl‐α‐methyl)‐N‐methylamine (H2dpma) with 1 and known compound {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2, respectively, led to the formations of [Dy(μ‐Cl)(dpma)(THF)2]2 ( 2 ) and {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2 ( 3 ). Compounds 2 and 3 were fully characterized by single‐crystal X‐ray crystallography, elemental analysis, and 1H NMR spectroscopy. Structure determination indicated that 2 and 3 exhibit as centrosymmetric dimers with asymmetrically bridging chloride ligands. One pot reactions involving LnCl3 (Ln = Dy and Yb), LiN(SiMe3)2, and H2dpma were explored and desired products 2 and 3 were not yielded, which indicated that 1 and {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2 are the demanding precursors to synthesize Dysprosium and Ytterbium complexes supported by dpma2– ligand. Compounds 2 and 3 are the first reported lanthanide complexes chelated by dpma2– ligand. 相似文献
14.
Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties
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Mei Zhu Peng Hu Yungai Li Xiufeng Wang Prof. Licun Li Prof. Daizheng Liao V. M. L. Durga Prasad Goli Prof. S. Ramasesha Dr. Jean‐Pascal Sutter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13356-13365
Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd , Tb 2Tb , Dy 2Dy , Ho 2Ho , Yb 2Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd , Tb 3Tb , Dy 3Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior. 相似文献
15.
Huilu Wu Yuchen Bai Yanhui Zhang Guolong Pan Jin Kong Furong Shi Xiaoli Wang 《无机化学与普通化学杂志》2014,640(10):2062-2071
The Schiff base N,N′‐bis(salicylidene)‐1,5‐diamino‐3‐oxapentane (H2L) and its lanthanide(III) complexes, PrL(NO3)(DMF)(H2O) ( 1 ) and Ho2L2(NO3)2 · 2H2O ( 2 ), were synthesized and characterized by physicochemical and spectroscopic methods. Single crystal X‐ray structure analysis revealed that complex 1 is a discrete mononuclear species. The PrIII ion is nine‐coordinate, forming a distorted capped square antiprismatic arrangement. Complex 2 is a centrosymmetric dinuclear neutral entity in which the HoIII ion is eight‐coordinate with distorted square antiprismatic arrangement. The DNA‐binding properties of H2L and its LnIII complexes were investigated by spectrophotometric methods and viscosity measurements. The results suggest that the ligand H2L and its LnIII complexes both connect to DNA in a groove binding mode; the complexes bind more strongly to DNA than the ligand. Moreover, the antioxidant activities of the LnIII complexes were in vitro determined by superoxide and hydroxyl radical scavenging methods, which indicate that complexes 1 and 2 have OH · and O2– · radical scavenging activity. 相似文献
16.
Magnetic Properties of a Terbium–[1]Ferrocenophane Complex: Analogies between Lanthanide–Ferrocenophane and Lanthanide–Bis‐phthalocyanine Complexes
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Trevor P. Latendresse Dr. Veacheslav Vieru Branford O. Wilkins Dr. Nattamai S. Bhuvanesh Prof. Dr. Liviu F. Chibotaru Prof. Dr. Michael Nippe 《Angewandte Chemie (International ed. in English)》2018,57(27):8164-8169
A rare example of an organometallic terbium single‐ion magnet is reported. A Tb3+–[1]ferrocenophane complex displays a larger barrier to magnetization reversal than its isostructural Dy3+ analogue, which is reminiscent of trends observed for lanthanide–bis‐phthalocyanine complexes. Detailed ab initio calculations support the experimental observations and suggest a significantly larger ground‐state stabilization for the non‐Kramers ion Tb3+ in the Tb complex than for the Kramers‐ion Dy3+ in the Dy complex. 相似文献
17.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(34):10237-10241
Assembly of the triangular, organic radical‐bridged complexes Cp*6Ln3(μ3‐HAN) (Cp*=pentamethylcyclopentadienyl; Ln=Gd, Tb, Dy; HAN=hexaazatrinaphthylene) proceeds through the reaction of Cp*2Ln(BPh4) with HAN under strongly reducing conditions. Significantly, magnetic susceptibility measurements of these complexes support effective magnetic coupling of all three LnIII centers through the HAN3−. radical ligand. Thorough investigation of the DyIII congener through both ac susceptibility and dc magnetic relaxation measurements reveals slow relaxation of the magnetization, with an effective thermal relaxation barrier of Ueff=51 cm−1. Magnetic coupling in the DyIII complex enables a large remnant magnetization at temperatures up to 3.0 K in the magnetic hysteresis measurements and hysteresis loops that are open at zero‐field up to 3.5 K. 相似文献
18.
Unprecedented Sensitization of Visible and Near‐Infrared Lanthanide Luminescence by Using a Tetrathiafulvalene‐Based Chromophore
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Min Feng Dr. Fabrice Pointillart Dr. Boris Le Guennic Bertrand Lefeuvre Dr. Stéphane Golhen Dr. Olivier Cador Dr. Olivier Maury Dr. Lahcène Ouahab 《化学:亚洲杂志》2014,9(10):2814-2825
Ligand L was synthesized and then coordinated to [Ln(hfac)3] ? 2 H2O (LnIII=Tb, Dy, Er; hfac?=1,1,1,5,5,5‐hexafluoroacetylacetonate anion) and [Ln(tta)3]?2 H2O (LnIII=Eu, Gd, Tb, Dy, Er, Yb; tta?=2‐thenoyltrifluoroacetonate) to give two families of dinuclear complexes [Ln2(hfac)6( L )] ? C6H14 and [Ln2(tta)6( L )] ? 2 CH2Cl2. Irradiation of the ligand at 37 040 cm?1 and 29 410 cm?1 leads to tetrathiafulvalene‐centered and 2,6‐di(pyrazol‐1‐yl)‐4‐pyridine‐centered fluorescence, respectively. The ligand acts as an organic chromophore for the sensitization of the infrared ErIII (6535 cm?1) and YbIII (10 200 cm?1) luminescence. The energies of the singlet and triplet states of L are high enough to guarantee an efficient sensitization of the visible EuIII luminescence (17 300–14 100 cm?1). The EuIII luminescence decay can be nicely fitted by a monoexponential function that allows a lifetime estimation of (0.49±0.01) ms. Finally, the magnetic and luminescence properties of [Yb2(hfac)6( L )] ? C6H14 were correlated, which allowed the determination of the crystal field splitting of the 2F7/2 multiplet state with MJ=±1/2 as ground states. 相似文献
19.
Lena Scherthan Sebastian F. M. Schmidt Hendrik Auerbach Tim Hochdrffer Juliusz A. Wolny Wenli Bi Jiyong Zhao Michael Y. Hu Tom Toellner E. Ercan Alp Dennis E. Brown Christopher E. Anson Annie K. Powell Volker Schünemann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3482-3487
Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of 161Dy has been used to investigate the magnetic properties of a DyIII‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy3PO)2(H2O)5]Br3?2 (Cy3PO)?2 H2O?2 EtOH is with B0=582.3(5) T significantly larger than that of the free‐ion DyIII with a 6H15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the DyIII ion. This study demonstrates that 161Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds. 相似文献
20.
Jun‐Liang Liu Jie‐Yi Wu Yan‐Cong Chen Dr. Valeriu Mereacre Prof. Dr. Annie K. Powell Dr. Liviu Ungur Prof. Dr. Liviu F. Chibotaru Prof. Dr. Xiao‐Ming Chen Prof. Dr. Ming‐Liang Tong 《Angewandte Chemie (International ed. in English)》2014,53(47):12966-12970
A record anisotropy barrier (319 cm?1) for all d‐f complexes was observed for a unique FeII‐DyIII‐FeII single‐molecule magnet (SMM), which possesses two asymmetric and distorted FeII ions and one quasi‐D5h DyIII ion. The frozen magnetization of the DyIII ion leads to the decreased FeII relaxation rates evident in the Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks to the exchange doublets. 相似文献