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Issue 10, 2009
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Anion encapsulation promoted by anion⋯π interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties

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Abstract

The reaction of Kpymca (pymca = pyrimidine-2-carboxylato anion) with MX2·6H2O and tmda (N,N,N′,N′-tetramethylethylenediamine) in 1 : 3 : 3 molar ratio, using a MeOH/water mixture (3 : 1) as solvent, afforded the hexanuclear complexes [M6(µ-pymca)6(tmda)6]X6·4H2O (M = NiII, X = ClO41, BF42; M = CoII, X = ClO43). The reaction of pymca with either Cu(ClO4)2·6H2O or Cu(BF4)2·6H2O did not lead to any definite product. However, in the presence of strong coordinating chloride anions the linear tetranuclear complex [Cu4(µ-pymca)3Cl(H2O)](ClO4)4·4.5H2O 4 could be obtained. The structures of 1–3 are very similar and consist of wheel-shaped hexanuclear [M6(µ-pymca)6(tmda)6]6+ cations, with pseudo-D3d symmetry in which the ligand acts in a bis(chelating)/bridging mode. The pyrimidine rings of the ligands converge alternatively above and below the plane of the wheel toward the normal to this plane, leading to the formation of a bowl-shaped capsule, which is occupied by one ClO4 (1 and 3) or BF4 (2) anion. There exist tight contacts between ClO4/BF4 and the π-electron density of the pyrimidine rings of the ligands. The tetranuclear cations of 4 exhibit a zig-zag linear conformation, in which copper ions are bridged by three bis(chelating)/bridging pymca ligands. Variable-temperature magnetic susceptibility studies reveal that complexes 1 and 4 show moderate antiferromagnetic coupling between the metal ions through the pymca ligands with J = −26.3 cm−1 for 1, and J1 = −16.3 cm−1 and J2 = −43.78 cm−1 for 4. The tetranuclear complex 4 has two different magnetic coupling constants accounting for the external–central (J1) and central–central (J2) copper interactions. The magnitude of the J1 and J2 values for 4 has been discussed on the basis of the geometrical factors affecting the magnetic pathways. Moreover, DFT calculations have been performed to support the relative magnitude of the J parameters in 4. A model accounting for spin–orbit coupling (λ), orbital reduction factors (Ak), axial zero-field splitting (Δ) and magnetic exchange coupling (J) was used to analyse the magnetic data of 3. The values of these parameters after the diagonalisation process were: Ak = 1.15, λ = −122 cm−1, Δ = 650 cm−1 and J = −5.2 cm−1.

Graphical abstract: Anion encapsulation promoted by anion⋯π interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties

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The article was received on 31 Mar 2009, accepted on 26 May 2009 and first published on 09 Jun 2009


Article type: Paper
DOI: 10.1039/B906382J
Citation: CrystEngComm, 2009,11, 2054-2064
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    Anion encapsulation promoted by anion⋯π interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties

    E. Colacio, H. Aouryaghal, A. J. Mota, J. Cano, R. Sillanpää and A. Rodríguez-Diéguez, CrystEngComm, 2009, 11, 2054
    DOI: 10.1039/B906382J

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