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Structure and magnetostructural correlation of ferrimagnetic meso-tetraphenylporphinatomanganese(III) dimethyl-N,N′-dicyanoquinone diiminide, [MnTPP]+[Me2DCNQI]·−

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Abstract

The structure [MnIIITPP][Me2DCNQI] (TPP = tetraphenylporphinato; Me2DCNQI = 2,5-dimethyl-N,N′-dicyanoquinone-diimine) has been determined from X-ray powder diffraction data. The nonsolvated structure is composed of linear (1-D) chains of alternating [MnIIITPP]+ and μ-[Me2DCNQI]·− with intrachain Mn...Mn separations of 12.83 Å, and a Mn-NDCNQI distance of 2.18 Å. The dihedral angle between the mean Mn(N4)TPP and [Me2DCNQI]·− planes, and the Mn-(N-C)DCNQI angle are 84.18° and 143.6°, respectively. [MnIIITPP][Me2DCNQI] has a T c of 4.3 K from the 10 Hz χ″(T) data, 2-K coercivity of 5,600 Oe, and 6,300 emuOe/mol remnant magnetization that are reduced from that observed for related materials, and their inclusion extends the magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn(N4)TPP and [TCNE]·− (TCNE = tetracyanoethylene) planes and Mn-(N-C)TCNE angles. This is in accord with the intrachain coupling arising from the overlap of the MnIII \(d_{z^2 }\)-like singly occupied molecular orbital (SOMO) and the z component of the [TCNE]·− π* (πz*) SOMO, which increases with decreasing dihedral angle between the mean Mn(N4)TPP and [TCNE]·− planes and Mn-(N-C)TCNE angle.

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  1. Department of Chemistry, University of Utah, Salt Lake City, Utah, 84112-0850, USA

    Jordan L. Arthur & Joel S. Miller

  2. Department of Physics & Astronomy, Stony Brook University, Stony Brook, NY, 11794-3800, USA

    Saul H. Lapidus & Peter W. Stephens

  3. Photon Sciences Directorate, Brookhaven National Laboratory, Upton, NY, 11973, USA

    Peter W. Stephens

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Arthur, J.L., Lapidus, S.H., Stephens, P.W. et al. Structure and magnetostructural correlation of ferrimagnetic meso-tetraphenylporphinatomanganese(III) dimethyl-N,N′-dicyanoquinone diiminide, [MnTPP]+[Me2DCNQI]·− . Sci. China Chem. 55, 987–996 (2012). https://doi.org/10.1007/s11426-012-4591-0

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