A 1D coordination polymer built on asymmetric µ1,1,3-azide bridge: from unusual topology to magnetic properties and Cu(II)/Cu(I) redox reversibility

Jean-Bernard Tommasino (1) , Guillaume Chastanet (2) , Boris Le Guennic (3, 4) , Vincent Robert (4, 5) , Guillaume Pilet (1)

1 LMI - Laboratoire des Multimatériaux et Interfaces
2 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
3 ISCR - Institut des Sciences Chimiques de Rennes
4 LC - Laboratoire de Chimie - UMR5182
5 Laboratoire de Chimie Quantique

An azide-bridged Cu(II) one dimensional polymer was synthesized in a one pot reaction in the presence of ammonia. The refined crystal structure evidenced the unusual asymmetric μ1,1,3 coordination mode of the azide ion leading to a {Cu(μ1,1,3-N3)(μ1-N3)(NH3)0.8(H2O)1.2}n chain. The redox process of this complex was studied by cyclic voltammetry evidencing the Cu(II)/Cu(I) reversibility. Magnetic measurements were interpreted as a uniform antiferromagnetic chain (J = −15.2 cm−1) holding rather strong inter-chain exchange (zJ′ = −2.8 cm−1). Multireference difference dedicated configuration interaction (DDCI) calculations confirmed the non-negligible intensity of inter-chain interactions and evidenced a strong influence of the type of coordinated solvent, NH3 or H2O, on the nature and magnitude of the magnetic exchange.

Domaines: Matériaux

Jean-Bernard Tommasino, Guillaume Chastanet, Boris Le Guennic, Vincent Robert, Guillaume Pilet. A 1D coordination polymer built on asymmetric µ1,1,3-azide bridge: from unusual topology to magnetic properties and Cu(II)/Cu(I) redox reversibility. New Journal of Chemistry, 2012, 36 (11), pp.2228-2235. ⟨10.1039/C2NJ40302A⟩. ⟨hal-00745737⟩