Anion encapsulation promoted by anion interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties
Identifieur interne : 000677 ( Main/Exploration ); précédent : 000676; suivant : 000678Anion encapsulation promoted by anion interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties
Auteurs : Enrique Colacio [Espagne] ; Hakima Aouryaghal [Espagne, Maroc] ; Antonio J. Mota [Espagne] ; Joan Cano [Espagne] ; Reijo Sillanp [Finlande] ; A. Rodrguez-Diguez [Espagne]Source :
- CrystEngComm [ 1466-8033 ] ; 2009.
Abstract
The reaction of Kpymca (pymca = pyrimidine-2-carboxylato anion) with MX26H2O 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(-pymca)6(tmda)6]X64H2O (M = NiII, X = ClO41, BF42; M = CoII, X = ClO43). The reaction of pymca with either Cu(ClO4)26H2O or Cu(BF4)26H2O did not lead to any definite product. However, in the presence of strong coordinating chloride anions the linear tetranuclear complex [Cu4(-pymca)3Cl(H2O)](ClO4)44.5H2O 4 could be obtained. The structures of 13 are very similar and consist of wheel-shaped hexanuclear [M6(-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 -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 cm1 for 1, and J1 = 16.3 cm1 and J2 = 43.78 cm1 for 4. The tetranuclear complex 4 has two different magnetic coupling constants accounting for the externalcentral (J1) and centralcentral (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 spinorbit coupling (), orbital reduction factors (Ak), axial zero-field splitting () 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, = 122 cm1, = 650 cm1 and J = 5.2 cm1.
Url:
DOI: 10.1039/b906382j
Affiliations:
- Espagne, Finlande, Maroc
- Andalousie, Catalogne
- Barcelone, Grenade (Espagne)
- Université de Barcelone, Université de Grenade
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The reaction of pymca with either Cu(ClO4)26H2O or Cu(BF4)26H2O did not lead to any definite product. However, in the presence of strong coordinating chloride anions the linear tetranuclear complex [Cu4(-pymca)3Cl(H2O)](ClO4)44.5H2O 4 could be obtained. The structures of 13 are very similar and consist of wheel-shaped hexanuclear [M6(-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 -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 cm1 for 1, and J1 = 16.3 cm1 and J2 = 43.78 cm1 for 4. The tetranuclear complex 4 has two different magnetic coupling constants accounting for the externalcentral (J1) and centralcentral (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 spinorbit coupling (), orbital reduction factors (Ak), axial zero-field splitting () 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, = 122 cm1, = 650 cm1 and J = 5.2 cm1.</div></front></TEI><affiliations><list><country><li>Espagne</li><li>Finlande</li><li>Maroc</li></country><region><li>Andalousie</li><li>Catalogne</li></region><settlement><li>Barcelone</li><li>Grenade (Espagne)</li></settlement><orgName><li>Université de Barcelone</li><li>Université de Grenade</li></orgName></list><tree><country name="Espagne"><region name="Andalousie"><name sortKey="Colacio, Enrique" sort="Colacio, Enrique" uniqKey="Colacio E" first="Enrique" last="Colacio">Enrique Colacio</name></region><name sortKey="Aouryaghal, Hakima" sort="Aouryaghal, Hakima" uniqKey="Aouryaghal H" first="Hakima" last="Aouryaghal">Hakima Aouryaghal</name><name sortKey="Cano, Joan" sort="Cano, Joan" uniqKey="Cano J" first="Joan" last="Cano">Joan Cano</name><name sortKey="Cano, Joan" sort="Cano, Joan" uniqKey="Cano J" first="Joan" last="Cano">Joan Cano</name><name sortKey="Mota, Antonio J" sort="Mota, Antonio J" uniqKey="Mota A" first="Antonio J." last="Mota">Antonio J. Mota</name><name sortKey="Rodrguez Diguez, A" sort="Rodrguez Diguez, A" uniqKey="Rodrguez Diguez A" first="A." last="Rodrguez-Diguez">A. Rodrguez-Diguez</name></country><country name="Maroc"><noRegion><name sortKey="Aouryaghal, Hakima" sort="Aouryaghal, Hakima" uniqKey="Aouryaghal H" first="Hakima" last="Aouryaghal">Hakima Aouryaghal</name></noRegion></country><country name="Finlande"><noRegion><name sortKey="Sillanp, Reijo" sort="Sillanp, Reijo" uniqKey="Sillanp R" first="Reijo" last="Sillanp">Reijo Sillanp</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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