Do π-π stacking interactions really play a role in the magnetic coupling mechanisms of [Cu2(μ2-CH3COO)2L2(H2O)2]n+ (L = heterocyclic base, n = 0, 2) complexes? An ab initio inspection.

Nuno A.G. Bandeira (1) , Daniel Maynau (2) , Vincent Robert (3, 1) , Boris Le Guennic (4, 1)

1 LC - Laboratoire de Chimie - UMR5182
2 GMO - Groupe THEO (LCPQ)
3 Laboratoire de Chimie Quantique
4 ISCR - Institut des Sciences Chimiques de Rennes

The magnetic properties of two bis-acetate binuclear copper(II) complexes, namely [Cu2(μ2-CH3COO)2(bpydiol-H)2(H2O)2] (bpydiol-H = mono deprotonated 2,2'-bipyridine-3,3'-diol) and [Cu2(μ2-CH3COO)2(phen)2(H2O)2](2+) (phen = 1,10-phenantroline), is revisited using ab initio wave function-based calculations (CASSCF, DDCI). Thanks to an analysis of the magnetic exchange coupling based on localized orbitals, it is shown that, unlike stated in the original work [C. Hou et al. Dalton Trans. 2008, 5970], π-π interactions do not contribute to the overall antiferromagnetism character of these complexes.

Domaines: Autre

Nuno A.G. Bandeira, Daniel Maynau, Vincent Robert, Boris Le Guennic. Do π-π stacking interactions really play a role in the magnetic coupling mechanisms of [Cu2(μ2-CH3COO)2L2(H2O)2]n+ (L = heterocyclic base, n = 0, 2) complexes? An ab initio inspection.. Inorganic Chemistry, 2013, 52 (14), pp.7980-7986. ⟨10.1021/ic400517z⟩. ⟨hal-00871258⟩