Structural and Magnetic Properties of MnIII and CuII Tetranuclear Azido Polyoxometalate Complexes: Multifrequency High‐Field EPR Spectroscopy of Cu4 Clusters with S=1 and S=2 Ground States
作者： Pierre Mialane , Carole Duboc , Jérôme Marrot , Eric Rivière , Anne Dolbecq
关键词: Paramagnetism 、 Crystallography 、 Chemistry 、 Excited state 、 Polyoxometalate 、 Antiferromagnetism 、 Spin states 、 Magnetic susceptibility 、 Inorganic chemistry 、 Electron paramagnetic resonance 、 Ground state
摘要: Two new azido-bridged polyoxometalate compounds were synthesized in acetonitrile/methanol media and their molecular structures have been determined by X-ray crystallography. The [[(gamma-SiW10O36)Mn2(OH)2(N3)(0.5)(H2O)(0.5)]2(mu-1,3-N3)](10-) (1 a) tetranuclear Mn(III) complex, which an end-to-end N3- ligand acts as a linker between two [(gamma-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. magnetic properties studied considering spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions paramagnetic centers (g 1.98) occur both through di-(mu-OH) bridge (J1 -25.5 cm(-1)) mu-1,3-azido (J2 -19.6 cm(-1)). [(gamma-SiW10O36)2Cu4(mu-1,1,1-N3)2(mu-1,1-N3)2]12- (2 Cu(II) complex consists of [gamma-SiW10O36Cu2(N3)2]6- subunits connected mu-1,1,1-azido ligands, four forming lozenge. susceptibility data fitted. This reveals ferromagnetic centers, leading to S=2 ground state (H -J1(S1S2+S1*S2*)-J2(S2S2*), J1 +294.5 cm(-1), J2 +1.6 g 2.085). coupling each subunit is strongest ever observed either compound or diazido-bridged complex. Considering 2 previously reported basal-basal di-(mu-1,1-N3)-bridged complexes metallic are not other magnetically linear correlation 2639.5-24.95*theta(av) theta(av) bridging angle parameter has proposed. electronic structure also investigated using multifrequency high-field electron resonance (HF-EPR) spectroscopy 95 285 GHz. parameters S (D -0.135(2) E -0.003(2) g(x) 2.290(5), g(y) 2.135(10), g(z) 2.158(5)) well excited 1 -0.960(4) -0.080(5) 2.042(5), 2.335(5), 2.095(5)) determined, since energy gap these states very small (1.6
archives-ouvertes.fr
sci-hub.se 参考文章(60)
Michael Thor Pope, Heteropoly and isopoly oxometalates Inorganic chemistry concepts. ,vol. 8, ,(1983) , 10.1007/978-3-662-12004-0
Juan M. Clemente-Juan, Hanspeter Andres, Juan J. Borrás-Almenar, Eugenio Coronado, Hans U. Güdel, Michael Aebersold, Gordon Kearly, Herma Büttner, Markus Zolliker, Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering: Evidence for Ferromagnetic Exchange Interactions and Spin Anisotropy in the Tetrameric Nickel(II) Cluster [Ni4(H2O)2(PW9O34)2]10- and Comparison with the Magnetic Properties Journal of the American Chemical Society. ,vol. 121, pp. 10021- 10027 ,(1999) , 10.1021/JA990197Z
Ulrich Kortz, Saritha Nellutla, Ashley C. Stowe, Naresh S. Dalal, Johan van Tol, Bassem S. Bassil, Structure and Magnetism of the Tetra-Copper(II)-Substituted Heteropolyanion [Cu4K2(H2O)8(α-AsW9O33)2]8-† Inorganic Chemistry. ,vol. 43, pp. 144- 154 ,(2004) , 10.1021/IC034697B
Timothy J. R. Weakley, Richard G. Finke, Single-crystal x-ray structures of the polyoxotungstate salts K8.3Na1.7[Cu4(H2O)2(PW9O34)2].cntdot.24H2O and Na14Cu[Cu4(H2O)2(P2W15O56)2].cntdot.53H2O Inorganic Chemistry. ,vol. 29, pp. 1235- 1241 ,(1990) , 10.1021/IC00331A025
F. Muller, M. A. Hopkins, N. Coron, M. Grynberg, L. C. Brunel, G. Martinez, A high magnetic field EPR spectrometer Review of Scientific Instruments. ,vol. 60, pp. 3681- 3684 ,(1989) , 10.1063/1.1140474
Carlos J. Gómez-García, Eugenio Coronado, Lahcéne Ouahab, A Novel Polyoxotungstate Containing atriangulo Ni3II Cluster with Ferromagnetic Exchange Interactions and anS= 3 Ground State Angewandte Chemie International Edition in English. ,vol. 31, pp. 649- 651 ,(1992) , 10.1002/ANIE.199206491
Jorgen Glerup, Patricia A. Goodson, Alan Hazell, Rita Hazell, Derek J. Hodgson, Christine J. McKenzie, Kirsten Michelsen, Urszula Rychlewska, Hans Toftlund, Synthesis and Characterization of Bis(.mu.-oxo)dimanganese(III,III), -(III,IV), and -(IV,IV) Complexes with Ligands Related to N,N'-Bis(2-pyridylmethyl)-1,2-ethanediamine (Bispicen) Inorganic Chemistry. ,vol. 33, pp. 4105- 4111 ,(1994) , 10.1021/IC00096A040
B. Ray. Stults, Robert S. Marianelli, Victor W. Day, Distortions of the coordination polyhedron in high-spin manganese(III) complexes. I. Synthesis and characterization of a series of five- and six-coordinate bis(acetylacetonato)manganese(III) complexes. Crystal structure of azidobis(acetylacetonato)manganese(III) Inorganic Chemistry. ,vol. 14, pp. 722- 730 ,(1975) , 10.1021/IC50146A004
Gerard A. Van Albada, Miles T. Lakin, Nora Veldman, Anthony L. Spek, Jan Reedijk, Synthesis, Characterization, Spectroscopy, and Magnetism of Dinuclear Azido- and Alkoxo-Bridged Copper(II) Complexes of Bis(2-benzimidazolyl)alkanes. X-ray Structures of [Cu2(tbz)2(CH3O)2](ClO4)2(CH3OH)2, [Cu2(tbz)2(NO3)(CH3O)2](NO3)(CH3OH)2, and [Cu(tbz)(N3)2]2(CH3OH)2 (tbz = Bis(2-benzimidazolyl)propane) Inorganic Chemistry. ,vol. 34, pp. 4910- 4917 ,(1995) , 10.1021/IC00123A028
Lei Zhang, Liang-Fu Tang, Zhi-Hong Wang, Miao Du, Miguel Julve, Francesc Lloret, Ji-Tao Wang, Ferromagnetic coupling in a one-dimensional molecular railroad copper(II) azido compound containing a defective double cubane motif. Inorganic Chemistry. ,vol. 40, pp. 3619- 3622 ,(2001) , 10.1021/IC001406F