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1.
Sourav Dey Gopalan Rajaraman Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(68):e202201883
[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2-pyridylmethyl)amine and Mesaldien=N,N’-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014 , 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [UVO2]+ is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component JZ twice larger as the perpendicular one J⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the JZ/J⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding gS-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [UVO2]+ 5 f orbitals. 相似文献
2.
3.
Boudalis AK Sanakis Y Clemente-Juan JM Donnadieu B Nastopoulos V Mari A Coppel Y Tuchagues JP Perlepes SP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(8):2514-2526
Complexes [Fe9(X)2(O2CMe)8{(2‐py)2CO2}4] (X?=OH? ( 1 ), N3? ( 2 ), and NCO? ( 3 )) have been prepared by a route previously employed for the synthesis of analogous Co9 and Ni9 complexes, involving hydroxide substitution by pseudohalides (N3?, NCO?). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3 , leading to higher ground spin states compared to that of 1 . Variable‐field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out‐of‐phase signals, which suggests that these complexes exhibit a slow relaxation of magnetization that follows Arrhenius behavior, as observed in single‐molecule magnets, with energy barriers of 41 K for 2 (τ0=3.4×10?12 s) and 44 K for 3 (τ0=2.0×10?11 s). Slow magnetic relaxation has also been observed by zero‐field 57Fe Mössbauer spectroscopy. Characteristic integer‐spin electron paramagnetic resonance (EPR) signals have been observed at X‐band for 1 , whereas 2 and 3 were found to be EPR‐silent at this frequency. 1H NMR spectrometry in CD3CN has shown that complexes 1 – 3 are stable in solution. 相似文献
4.
Dr. Michał Rams Aleksej Jochim Michael Böhme Dr. Thomas Lohmiller Magdalena Ceglarska Dr. Marek M. Rams Dr. Alexander Schnegg Prof. Dr. Winfried Plass Prof. Dr. Christian Näther 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2837-2851
The cobalt(II) in [Co(NCS)2(4-methoxypyridine)2]n are linked by pairs of thiocyanate anions into linear chains. In contrast to a previous structure determination, two crystallographically independent cobalt(II) centers have been found to be present. In the antiferromagnetic state, below the critical temperature (Tc=3.94 K) and critical field (Hc=290 Oe), slow relaxations of the ferromagnetic chains are observed. They originate mainly from defects in the magnetic structure, which has been elucidated by micromagnetic Monte Carlo simulations and ac measurements using pristine and defect samples. The energy barriers of the relaxations are Δτ1=44.9(5) K and Δτ2=26.0(7) K for long and short spin chains, respectively. The spin excitation energy, measured by using frequency-domain EPR spectroscopy, is 19.1 cm−1 and shifts 0.1 cm−1 due to the magnetic ordering. Ab initio calculations revealed easy-axis anisotropy for both CoII centers, and also an exchange anisotropy Jxx/Jzz of 0.21. The XXZ anisotropic Heisenberg model (solved by using the density renormalization matrix group technique) was used to reconcile the specific heat, susceptibility, and EPR data. 相似文献
5.
Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex
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Lucile Chatelain James P. S. Walsh Dr. Jacques Pécaut Dr. Floriana Tuna Dr. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2014,53(49):13434-13438
Mixed‐metal uranium compounds are very attractive candidates in the design of single‐molecule magnets (SMMs), but only one 3d–5f hetero‐polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d–5f complexes self‐assembled by cation–cation interactions between a uranyl(V) complex and a TPA‐capped MII complex (M=Mn ( 1 ), Cd ( 2 ); TPA=tris(2‐pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1 , which contains an almost linear {Mn? O?U?O? Mn} core, exhibits SMM behavior with a relaxation barrier of 81±0.5 K—the highest reported for a mono‐uranium system—arising from intramolecular Mn–U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K. 相似文献
6.
State Miao Ming-Ming Liao Dai-Zheng Jiang Zong-Hui Cheng Peng Wang Geng-Lin 《中国化学》1996,14(4):326-330
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO2-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)23H2O has been studied in the 4–300 K range, giving the exchange integral J—109 cm?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(5):425-434
[Ni(phen)2(H2O)Br]Br·3H2O where phen is 1,10-phenanthroline, is a light-blue material which crystallizes in the monoclinic space group P21/c with Z = 4, a = 10.4300(4), b = 25.310(2), c = 9.7790(9)?Å and β = 102.932(6)°. The structure was determined at ambient temperature from 5161 reflections with R = 0.0643 and R w = 0.1306. The structure consists of a complex cation, a bromide anion and three waters of hydration. The Ni atom is pseudo-octahedral with a cis arrangement of Br and H2O. This cis geometry persists in solution, as evidenced by 1H NMR spectroscopy, although the Br may be replaced by another H2O. [Ni(phen)3]Br2·8H2O is a light-red material which crystallizes in the monoclinic space group C2/m with Z = 8, a = 23.6320(11), b = 21.4880(13), c = 15.5470(9)?Å and β = 107.927(3)°. The structure was determined at 120?K from 6820 reflections with R = 0.0733 and R w = 0.1022. The structure consists of a complex cation, two bromide anions and eight waters of hydration. The anions and waters are extensively disordered. The Ni atom is pseudo-octahedral. 相似文献
8.
Inside Back Cover: Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex (Angew. Chem. Int. Ed. 49/2014)
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Lucile Chatelain James P. S. Walsh Dr. Jacques Pécaut Dr. Floriana Tuna Dr. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2014,53(49):13621-13621
9.
The thermal analysis of CoC2O4·2H2O, Co(HCOO)2·2H2O and Co(CH3COO)2·4H2O was carried out with simultaneous TG-DTG-DTA measurements under non-isothermal conditions in air and argon atmospheres.
The intermediates and the end products of decomposition were characterised by X-ray diffraction and IR and UV-VIS spectroscopy.
The decomposition of the studied compounds occur in several stages. The first stage of dissociation of each compound is dehydration
both in air and argon. The next stages differ in air and argon. The final product of the decomposition of each compound in
air is Co3O4. In argon it is a mixture of Co and CoO for cobalt(II) oxalate and cobalt(II) formate but CoO for cobalt(II) acetate.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
10.
Newton L. Dias Filho 《Mikrochimica acta》1999,130(4):233-240
The isotherms of adsorption of MeX2 (Me = Cu2+, Co2+; X = Cl–, Br–, ClO
4
–
) by silica gel chemically modified with 2-mercaptoimidazole (SiMI) were studied in acetone and ethanol solutions, at 25 °C. Covalently attached 2-mercaptoimidazole molecule to silica gel surface adsorbs MeX2 from solvent by forming a surface complex. The metal is bonded to the surface through the nitrogen atom of attached 2-mercaptoimidazole. At low loading, the electronic and ESR spectral parameters indicated that the Cu2+ complexes are in a distorted-tetragonal symmetry field. The d-d electronic transition spectra showed that for Cu(ClO4)2 complex, the peak of absorption did not change for any degree of metal loading and for Cl– and Br– complexes, the peak maxima shifted to higher energy with lower metal loading. The CoX2(X = Cl–, Br–, ClO
4
–
) analogues possess a distorted-tetrahedral field. 相似文献
11.
Mononuclear copper(Ⅱ), nickel(Ⅱ) and cobalt(Ⅲ) tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray crystallography. The electrochemical experimental results indicate that the three complexes could interact with DNA mainly by electrostatic interaction. The interaction of tetracoordinate macrocyclic cobalt(Ⅲ) complex with DNA was studied by cyclic voltammetry and UV-vis spectroscopy. The experimental results reveal that tetracoordinate macrocyc- lic cobalt(Ⅲ) complex could interact with DNA by electrostatic interaction to form a 1 : 1 DNA association complex with a binding constant of 7.50 ×10^3 L·mol^-1. 相似文献
12.
《Analytica chimica acta》2002,459(2):229-234
The ligand 1,4,8-tri(n-octyl)-1,4,8,11-tetraazacyclotetradecane (L1) containing pendant octyl groups has been synthesised. L1 is a tetraazamacrocycle derived from the well-known cyclam unit, and the Ni2+ and Co2+ complexes, [Ni(L1)]2+ and [Co(L1)]2+, have been isolated and characterised. The ability of the nickel(II) and cobalt(II) complexes to act as anion receptors has been studied by using them as ionophores in membrane-based ion-selective electrodes (ISEs). The PVC membrane containing the complex [Ni(L1)]2+ and 2-nitrophenyloctylether as plasticizer shows a Nernstian response against iodide in a concentration range from 1×10−1 to 4×10−5 M I− with a detection limit of 1.6×10−5 M I− and a slope of 58.6 mV/pI− at pH 7 (25 °C). In comparison, the electrode containing [Co(L1)]2+ as ionophore gave a sub-Nernstian slope and a low lifetime. A comparison between the iodide-selective electrode containing [Ni(L1)]2+ and other reported iodide-selective electrodes is also reported. 相似文献
13.
A fluorescent cobalt(Ⅱ) complex, 1 [Co(H2bibim)2(5-nipa)], for the recognition of cations and small molecules constructed with 5-nitroisophthalic acid (5-H2nipa) and 2,2-biben-zimidazole(H2bibim) has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, PL and single-crystal X-ray diffraction. The cobalt units are six-coordinated by two H2bibim ligands and one 5-nitroisophthalic acid group, which are further connected into a three-dimensional (3D) network by intermolecular hydrogen bonds. Complex 1 exhibits fluorescence and thus has detection capabilities for different cations and small solvent molecules in the solution state at room temperature. 相似文献
14.
Konstantina A. Kounavi Constantina Papatriantafyllopoulou Anastasios J. Tasiopoulos Spyros P. Perlepes Vassilios Nastopoulos 《Polyhedron》2009
An investigation of the MII/X−/L [MII = Co, Ni, Cu, Zn; X− = Cl−, Br−, I−, NCS−, NO3−, N3−, CH3COO−; L = 1-methyl-4,5-diphenylimidazole] general reaction system towards the detailed study of the intermolecular interactions utilized for controlling the supramolecular organization and the structural consequences on the structures produced has been initiated. Three representative complexes with the formulae [Co(NO3)2(L)2] (1), [Zn(NO3)2(L)2] (2) and [Co(NCS)2(L)2]·EtOH (3·EtOH) have been synthesized and characterized by spectroscopic methods and single-crystal X-ray analysis. Compounds 1 and 2 are isomorphous (tetragonal, I41cd) with their metal ions in a severely distorted octahedral Co/ZnN2O4 environment, while 3·EtOH crystallizes in P21/c with a tetrahedral CoN4 coordination. The structural analysis of 1, 2 and 3·EtOH reveals a common mode of packing among neighbouring ligands (expressed through intramolecular π–π interactions between the 4,5-diphenylimidazole moieties), enhancing thus the rigidity and stability of the complexes. The bent coordination of the two isothiocyanates in 3 [Co–NCS angles of 173.8(2) and 160.8(2)°] seems to be caused by intermolecular hydrogen bonding and crystal packing effects. 相似文献
15.
A series of homoleptic complexes of hexacoordinate cobalt(II) and copper(II) complexes with 3,5-disubstituted homo- and heteroscorpionate tris(pyrazolyl)borate anionic ligands (Tp′) were synthesized, i.e. bis[hydrotris(3-phenyl,5-methylpyrazol-1-yl)borato]cobalt(II), bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) and bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]copper(II) and their structures were elucidated crystallographically. The complexes were also formed spontaneously during attempted metathesis of the corresponding Tp′M(NCS) complexes into Tp′M(OOCCH(OH)CH3) complexes. In the case of the analogous conversion applied for the thiocyanato [hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3,5-dimethylpyrazol-1-yl)boratocobalt(II) complex with sodium carboxylates (lactate, pyruvate and 2-hydroxybutyrate), the cross-transfer of pyrazolyl residues between starting anionic ligands was observed resulting in formation of bis-ligand homo- and heteroleptic Tp′CoTp″ complexes, where Tp′, Tp″ were tris(pyrazolyl)borates composed of n 3(5)-phenyl,5(3)-methylpyrazolyl and (3−n) 3,5-dimethylpyrazolyl residues (n=0–3) identified by mass spectrometry. Metathesis of thiocyanate in thiocyanato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) into pyruvate led to the isolation of stable the pyruvato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) complex, the structure of which was determined crystallographically. The Tp′ ligands are η3 coordinated to metal ions in every case, whereas the pyruvate anion is coordinated through carboxylate and carbonyl oxygen atoms to the cobalt center. Two rotational isomers distinguishable by 1H NMR spectroscopy for the hexacoordinate bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) complex were detected in solution. 相似文献
16.
Zeinab Mohamed Anwar 《中国化学会会志》2005,52(5):863-871
The interaction of zinc(II), lead(II), and cadmium(II) with Glutathione (S‐L‐glutamyl‐Lcysteinylglycine) as primary ligand and zwitterionic buffers (N‐[2‐Hydroxyethyl]piperazine‐N′‐[2‐ethanesulfonic acid]) (HEPES) and (N‐Hydroxyethyl]piperazine‐N′‐[2‐hydroxy‐propanesulfonic acid]) (HEPPSO) as secondary ligands were studied by potentiometric‐pH titration in 1:1:1 ratio at 25.0 °C and I = 0.1 mol.dm?3 (KNO3). The formation constants of different normal and protonated binary and ternary complex species were calculated. Formation constants for the monohydroxy, and dihydroxy complexes for the binary systems M(II) + HEPES and M(II) + HEPPSO have been evaluated. The distribution curves for the various complex species as a function of pH were constructed. 相似文献
17.
Installation of a Rigid EDTA‐Like Motif into a Protein α‐Helix for Paramagnetic NMR Spectroscopy with Cobalt(II) Ions
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Dr. James D. Swarbrick Dr. Phuc Ung Matthew L. Dennis Michael D. Lee Dr. Sandeep Chhabra Dr. Bim Graham 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1228-1232
Coupling two copies of an iminodiacetic acid–cysteine hybrid ligand to a pair of cysteine residues positioned in an i, i+4 arrangement within a protein α‐helix leads to generation of an EDTA‐like metal ion‐binding motif. Rigid binding of a CoII ion by this motif produces pseudo‐contact shifts suitable for paramagnetic NMR structural studies. 相似文献
18.
I. F. Tcholakova R. D. Shopova D. D. Rustschev 《Journal of Thermal Analysis and Calorimetry》1995,44(5):1155-1158
The thermal behaviour of some Cu(II) compounds formed with 1,4-disubstituted piperazine derivatives has been studied. The investigations were performed on a MOM 1500 derivatograph. The endothermic effects observed at 170–180°C are associated with the processes of dehydration and dehalogenation of the compounds, with general formula LH2·CuCl4·H2O, whereL is the piperazine derivative. The residue at 600°C remains relatively constant. 相似文献
19.
Krzysztof Kurzak 《Journal of solution chemistry》1998,27(7):621-643
Mixed cobalt(II) complexes with the monodentate ligands: 2-hydroxybenzoic acid deprotonated (sal–, the salicylate ion) and water, have been investigated. The combined results of the spectrophotometric and conductance measurements, as well as known the X-ray structure for solids, were used to determine the structure of the studied complexes in solution. The electronic absorption spectra in aqueous acid (0.01M HClO4), ethylene glycol (glycol), formamide (FM), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) solutions have been recorded. The d-d electronic spectra have been treated by the crystal-field model (CFM) and angular overlap model (AOM). Low-symmetry splittings of the broad asymmetric bands in the experimental spectra (solutions at room temperature) were found by Gaussian analysis. The effect of the and bonding of the monodentate ligands (with oxygen-donor ligators) on the central metal ion was described in the ligand–field framework. A comparison of the stereochemistry of the complex species in various solutions was made. 相似文献
20.
Ahmad R. Esmaeilbeig Hamid R. Samouei Mehdi Rashidi 《Journal of organometallic chemistry》2008,693(15):2519-2526
The phosphite complexes cis-[PtMe2L(SMe2)] in which L = P(OiPr)3, 1a, or L = P(OPh)3, 1b, were synthesized by the reaction of cis,cis-[Me2Pt(μ-SMe2)2PtMe2] with 2 equiv. of L. If 4 equiv. of L was used the bis-phosphite complexes cis-[PtMe2L2] in which L = P(OiPr)3, 2a, or L = P(OPh)3, 2b, were obtained. The reaction of cis-[Pt(p-MeC6H4)2(SMe2)2] with 2 equiv. of L gave the aryl bis-phosphite complexes cis-[Pt(p-MeC6H4)2L2] in which L = P(OiPr)3, 2a′, or L = P(OPh)3, 2b′. Use of 1 equiv. of L in the latter reaction gave the bis-phosphite complex along with the starting complex in a 1:1 ratio.The complexes failed to react with MeI. The reaction of cis,cis-[Me2Pt(μ-SMe2)2PtMe2] with 2 equiv. of the phosphine PPh3 gave cis-[PtMe2(PPh3)2] and cis-[PtMe2(PPh3)(SMe2)] along with unreacted starting material. Reaction of cis-[PtMe2L(SMe2)], 1a and 1b with the bidentate phosphine ligand bis(diphenylphosphino)methane, dppm = Ph2PCH2PPh2, gave [PtMe2(dppm)], 8, along with cis-[PtMe2L2], 2. The reaction of cis-[PtMe2L(SMe2)] with 1/2 equiv. of the bidentate N-donor ligand NN = 4,4′-bipyridine yielded the binuclear complexes [PtMe2L(μ-NN)PtMe2L] in which L = P(OiPr)3, 3a, or L = P(OPh)3, 3b.The complexes were fully characterized using multinuclear NMR (1H, 13C, 31P, and 195Pt) spectroscopy. 相似文献