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Tuba Iftikhar Dr. Natalya V. Izarova Dr. Jan van Leusen Prof. Dr. Paul Kögerler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(33):8500-8508
The propensity of the new, phenylphosphonate-stabilized polyoxotungstate [(C6H5PVO)2P4W24O92]16− to act as a precursor for new 3d metal-functionalized polyanions has been investigated. Reactions with MnII and CuII induce the formation of the previously unknown polyoxotungstate archetype {P4W27}, isolated as salts of the polyanions [Na⊂{MnII(H2O)}{WO(H2O)}P4W26O98]13− ( 1 ) and [K⊂{CuII(H2O)}{W(OH)(H2O)}P4W27O99]14− ( 2 ), which were characterized in the solid state (single-crystal X-ray diffraction, elemental and TG analyses, IR spectroscopy, SQUID magnetometry) and in aqueous solution (UV/Vis spectroscopy, cyclic voltammetry). 相似文献
3.
《Journal of Coordination Chemistry》2012,65(3):467-478
Abstract The chemical and direct electrochemical syntheses of copper, cobalt, nickel and zinc chelates of 2-[N-tosylamine)benzaldoxime (L1H2) and 2-[N-tosylamine)benzal-O-methyloxime (L2H) are reported. On the basis of the elemental analyse IR and EPR spectra and magnetic properties, dimeric structures ML are suggested from L1H2 under the conditions of the chemical synthesis, while electrosynthesis leads to the monomeric complexes M(L1H)2. Using L2H as a ligand, only the chelates ML2 2 are formed, regardless of the method of synthesis. The copper dimers CuL1 have antiferromagnetic properties, while the chelates M(L1H)2 and ML2 have normal magnetic moments. In agreement with the magnetic properties and literature data on structures of four-coordinate complexes a tetrahedral structure is assigned. 相似文献
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Supramolecular Recognition Influences Magnetism in [X@HVIV8VV14O54]6− Self‐Assemblies with Symmetry‐Breaking Guest Anions
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Dr. Kirill Yu. Monakhov Oliver Linnenberg Dr. Piotr Kozłowski Dr. Jan van Leusen Dr. Claire Besson Tim Secker Dr. Arkady Ellern Dr. Xavier López Prof. Dr. Josep M. Poblet Prof. Dr. Paul Kögerler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2387-2397
Mixed‐valence polyoxovanadates(IV/V) have emerged as one of the most intricate class of supramolecular all‐inorganic host species, able to encapsulate a wide variety of smaller guest templates during their self‐assembly formation process. As showcased herein, the incorporation of guests, though governed solely by ultra‐weak electrostatic and van der Waals interactions, can cause drastic effects on the electronic and magnetic characteristics of the shell complex of the polyoxovanadate. We address the question of methodology for the magnetochemical analysis of virtually isostructural {VIV/V22O54}‐type polyoxoanions of D2d symmetry enclosing diamagnetic VO2F2? (C2v), SCN? (C∞v), or ClO4? (Td) template anions. These induce different polarization effects related to differences in their geometric structures, symmetry, ion radii, and valence shells, eventually resulting in a supramolecular modulation of magnetic exchange between the V(3d) electrons that are partly delocalized over the {V22O54} shells. We also include the synthesis and characterization of the novel [VVO2F2@HVIV8VV14O54]6? system that comprises the rarely encountered discrete difluorovanadate anion as a quasi‐isolated guest species. 相似文献
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Manganesecomplexeswithnuclearitiesupt0l8havebeenreported',whichhasbeenstimulatedbyanumberoffactors.TheseMn.sh0wnewandingeni0usstructures.Tetfa'nuclearclustersmaybethemodelsofthephotosyntheticwateroxidationcenter(W0C)ingreenplantsandcyarobacteria'.Thep0ly-nuclearmanganeseclustersexhibit,indeed,highlyunusualmagneticproperties.They0ftendisplayhighspin(S)valuesinthegr0undstate3andcertaincomplexeshavebeenidentifiedasbeingabletobemagnetizedbel0wacriticaItemperaturei.e.,theycanberegardsas"single-mo… 相似文献
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Thomas Eifert Klaus Handrick Felix Hüning Ulrich Neuhausen Helmut Schilder Heiko Lueken 《无机化学与普通化学杂志》2006,632(4):521-529
Magnetic behaviour of condensed magnetic d and f systems with localised ‘magnetic electrons’ is essentially controlled by both single ion effects (interelectronic and spin‐orbit coupling, ligand field potential) and interionic exchange interactions. The latter act according to the spin dimensionality forced upon the magnetic centre via the single ion effects. For a complete understanding of magnetic behaviour on the basis of quantum mechanical models a two‐step procedure presents itself that determines in a complementary way first the ‘easy’ direction of the centres' magnetic dipoles connected with the single ion ground state. Subsequently, the relevant isotropic/anisotropic spin‐spin coupling model is applied (Heisenberg, XY, Ising). With the help of the textbook compounds CrBr3 and Cs3 CoCl5 as well as β‐RuCl3 the way of acting is pointed out. 相似文献
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G. A. Abakumov V. K. Cherkasov M. P. Bubnov L. G. Abakumova V. N. Ikorskii G. V. Romanenko A. I. Poddel’sky 《Russian Chemical Bulletin》2006,55(1):44-52
New five-coordinate complexes Co(ISQ-Pri)2Cl, Co(ISQ-Me)2Cl, Co(ISQ-Me)2I, Co(ISQ-Me)2(SCN), Mn(ISQ-Pri)2Cl, and Fe(ISQ-Me)2Br (ISQ-Pri and ISQ-Me are the 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-and 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzosemiquinone radical anions, respectively) were synthesized. The complexes were characterized by UV-Vis and IR spectroscopy
and magnetochemistry. The molecular structures of the Fe(ISQ-Me)2Br and Mn(ISQ-Pri)2Cl complexes were established by X-ray diffraction. The singlet ground state (S = 0) of the cobalt complexes is caused by
antiferromagnetic coupling between the unpaired electrons of the radical ligands (S = 1/2) through the fully occupied atomic orbitals of low-spin cobalt(III) (d6, S = 0). The effective magnetic moments of the complexes at 10 K are 0.18 μB for Co(ISQ-Pri)2Cl and 0.16 μB for Co(ISQ-Me)2I. The ground state of the manganese complex is triplet (S = 1). Two unpaired electrons of the o-iminobenzosemiquinone ligands are strongly antiferromagnetically coupled with two of four unpaired electrons of high-spin
manganese(III) (d4, S = 2).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–51, January, 2006. 相似文献
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Vladimir Yu. Osipov Fedor M. Shakhov Nikolai M. Romanov Kazuyuki Takai 《Mendeleev Communications》2021,31(3):415-418
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10.
The reviews and monographs on magnetochemistry of boron compounds are discussed. The structural peculiarities of borane derivatives relevant to magnetochemical calculations of diamagnetic contributions are are considered. Experimental measurements of diamagnetic susceptibility for deltahedral B10H
10
2–
and B12H
12
2–
cluster closo-anions were used to derive the diamagnetic atomic increments of the B atoms (B) with coordination numbers 5 and 6. The atomic increments B thus obtained were used to calculate molecular diamagnetic susceptibility M of borane derivatives. Diamagnetic susceptibility M was measured and calculated for the series of borane derivatives BnH
n
2–
and B10H12L2 (L is a Lewis base)and cobalt(III) derivatives of ortho-carborane(12) [(B9C2H11)2Con(B8C2H10)
n–1]
n–. Diamagnetic increments were obtained for |B10H12| fragments and (B9C2H11)2– and (B8C2H10)4– ligands. The increments can be employed for calculating M for novel compounds. The calculated values of M coincide with the experimental values within 2%–6%.Original Russian Text Copyright © 2004 by V. V. Volkov and V. N. IkorskiiTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 729–740, July–August 2004.This revised version was published online in April 2005 with a corrected cover date. 相似文献