A dinuclear copper(II) complex with a Cu(O, N-O)Cu bridging core: structural and magnetic (experimental and density functional theory) studies

被引：14

作者：

Bencini, A

Costes, JP

Dahan, F

Dupuis, A

Garcia-Tojal, J

Gatteschi, D

Totti, F

机构：

[1] Univ Florence, Dipartimento Chim, I-50019 Florence, Italy

[2] Univ Toulouse 3, Chim Coordinat Lab, CNRS, UPR 8241, F-31077 Toulouse, France

[3] Inst Polytech Toulouse, F-31077 Toulouse, France

来源：

INORGANICA CHIMICA ACTA | 2004年 / 357卷 / 07期

关键词：

copper; magnetism; X-ray determination; DFT;

D O I：

10.1016/j.ica.2003.12.037

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The molecular and electronic structure, along with the magnetic properties of a dinuclear complex in which two copper ions interact through a phenoxo oxygen atom and an oximato group are presented. The complex [(CuLCu)-Cu-3(O2CCH3)]3H(2)O . 0.5CH(3)OH (3) crystallizes in the monoclinic space group Cc, with a = 28.432(2) Angstrom, b = 12.305(1) Angstrom, c = 13.159(1) Angstrom and beta = 99.580(9)degrees. The X-ray molecular structure shows that the core of the molecule comprising the two metal ions and the seven neighboring donors is nearly planar. The copper(II) ions were found to be antiferromagnetically coupled with a singlet-triplet splitting of 764(4) cm(-1). Density Functional Theory (DFT) showed that the magnetic orbitals are largely delocalized towards the bridging area, and an antiferromagnetic interaction in good agreement with the experimental data was computed using the Broken Symmetry (BS) formalism to obtain the energy of the singlet state. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：2150 / 2156

页数：7

共 33 条

[1] On the calculation and modeling of magnetic exchange interactions in weakly bonded systems:: The case of the ferromagnetic copper(II) μ2-azido bridged complexes
Adamo, C
Barone, V
Bencini, A
Totti, F
Ciofini, I
[J]. INORGANIC CHEMISTRY, 1999, 38 (09) : 1996 - 2004
[2] [Anonymous], 1992, INT TABLES CRYSTALLO, VC
[3] Density functional calculations of magnetic exchange interactions in polynuclear transition metal complexes
Bencini, A
Totti, F
Daul, CA
Doclo, K
Fantucci, P
Barone, V
[J]. INORGANIC CHEMISTRY, 1997, 36 (22) : 5022 - 5030
[4] CRYSTAL AND MOLECULAR-STRUCTURE OF BIS[PERCHLORATO[2-(2-HYDROXYETHYL)IMINO-3-OXIMOBUTANATO]AQUOCOPPER(II)] - COPPER(II) DIMER WITH BRIDGING OXIME GROUPS
BERTRAND, JA
SMITH, JH
ELLER, PG
[J]. INORGANIC CHEMISTRY, 1974, 13 (07) : 1649 - 1653
[5] COPPER(II) COMPLEXES WITH BRIDGING OXIME GROUPS .1. STRUCTURES AND MAGNETIC-PROPERTIES OF COMPLEXES WITH IMINE OXIMES OF 2,3-BUTANEDIONE AS LIGANDS
BERTRAND, JA
SMITH, JH
VANDERVEER, DG
[J]. INORGANIC CHEMISTRY, 1977, 16 (06) : 1477 - 1483
[6] SPIN POPULATION ANALYSIS AND LOCAL SPIN HAMILTONIAN PARAMETERS IN EXCHANGE-COUPLED SYSTEMS
BERTRAND, P
[J]. INORGANIC CHEMISTRY, 1993, 32 (05) : 741 - 745
[7] EXCHANGE COUPLING IN HOMODINUCLEAR HETERODINUCLEAR COMPLEXES CUIIM [M = CR(III), MN(III), MN(II), FE(III), CO(III), CO(II), NI(II), CU(II), ZN(II)] - SYNTHESIS, STRUCTURES, AND SPECTROSCOPIC PROPERTIES
BIRKELBACH, F
WINTER, M
FLORKE, U
HAUPT, HJ
BUTZLAFF, C
LENGEN, M
BILL, E
TRAUTWEIN, AX
WIEGHARDT, K
CHAUDHURI, P
[J]. INORGANIC CHEMISTRY, 1994, 33 (18) : 3990 - 4001
[8] ANOMALOUS PARAMAGNETISM OF COPPER ACETATE
BLEANEY, B
BOWERS, KD
[J]. PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1952, 214 (1119): : 451 - 465
[9] Remarks on the proper use of the broken symmetry approach to magnetic coupling
Caballol, R
Castell, O
Illas, F
Moreira, PR
Malrieu, JP
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (42) : 7860 - 7866
[10] CIOFINI I, 2002, RECENT ADV DFT MET 3, V1, P106

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