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Article Dans Une Revue Chemistry - A European Journal Année : 2012

Three-dimensional porous metal-radical frameworks based on triphenylmethyl radicals.

Georges Mouchaham

Résumé

Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2) H(2) O]⋅x H(2) O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αHPTMTC)(EtOH)(2) H(2) O]⋅x H(2) O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-) ) or closed-shell (αHPTMTC(3-) ) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2) .8)⋅(4(4) .6(2) .8(5) .10(4) ) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2) H(2) O] and [Tb(αHPTMTC)(EtOH)(2) H(2) O] materials. Accessible voids represent 40 % of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III) -ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

Domaines

Matériaux

Dates et versions

hal-00659772 , version 1 (13-01-2012)

Identifiants

Citer

Angela Datcu, Nans Roques, Veronique Jubera, Daniel Maspoch, Xavier Fontrodona, et al.. Three-dimensional porous metal-radical frameworks based on triphenylmethyl radicals.. Chemistry - A European Journal, 2012, 18 (1), pp.152-62. ⟨10.1002/chem.201102278⟩. ⟨hal-00659772⟩
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