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Synthesis and X-ray Structure of the MnIICl2 and MnIIIF2 Complexes of N,N-Dimethyl-2,11-diaza[3,3](2,6)pyridinophane. High-Field Electron Paramagnetic Resonance and Density Funtional Theory Studies of the Mn(III) Complex. Evidence for a Low-Lying Spin Triplet State

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journal contribution
posted on 2005-10-03, 00:00 authored by Belén Albela, Riccardo Carina, Clotilde Policar, Sandrine Poussereau, Joan Cano, Jean Guilhem, Luba Tchertanov, Geneviève Blondin, Michel Delroisse, Jean-Jacques Girerd
Two manganese complexes, (py2(NMe)2)MnIICl2 (1) and [(py2(NMe)2)MnIIIF2]+ (2), are here described with the macrocyclic ligand py2(NMe)2 (py2(NMe)2 = N,N-dimethyl-2,11-diaza[3,3](2,6)pyridinophane). For both, the crystal structure is reported. The UV−visible spectrum of 2 exhibits a very broad near-infrared (NIR) band corresponding to the transition between the two eg-type orbitals split by the Jahn−Teller effect. A negative D value of ca. −4 cm-1 was estimated by high-field and high-frequency electron paramagnetic resonance (HF-EPR) spectroscopy, which was consistent with symmetry considerations. Density functional theory (DFT) calculations on 2 support the 5B1 electronic ground state predicted from the X-ray structure. Moreover, to explain the large value of the D parameter, a spin triplet first excited spin state was postulated to occur at low energy. This was confirmed by the DFT calculations.