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The first photochromic bimetallic assemblies based on Mn(III) and Mn(II) Schiff-base (salpn, dapsc) complexes and pentacyanonitrosylferrate

Abstract : Four cyano-bridged bimetallic complexes, \[Mn(salpn)](2)[Fe(CN)(5)NO]\(n) (1), \[Mn(salpn)(CH3OH)](4)[Mn(CN)(5)NO]\[C(CN)(3)]center dot 3H(2)O (2), \[Mn(dapsc)][Fe(CN)(5)NO]center dot 0.5CH(3)OH center dot 0.25H(2)O\(n) (3) and \[Mn(salpn)(CH3OH)](4)[Fe(CN)(5)NO]\(ClO4)(2)center dot 4H(2)O (4), where salpn(2-) = N, N'-1,3-propylene-bis(salicylideneiminato) dianion and dapsc = 2,6-diacetylpyridine-bis(semicarbazone), have been synthesized and structurally characterized by single crystal X-ray diffraction. In 1, the nitroprusside anion [Fe(CN)(5)NO](2-) coordinates with four [Mn(salpn)](+) via four co-planar CN- groups, whereas each [Mn(salpn)](+) links two [Fe(CN)(5)NO](2-) ions, which results in a two-dimensional network. The structure of 3 contains two independent neutral infinite chains \[Mn(dapsc)][Fe(CN)(5)(NO)]\(infinity) consisting of alternating cationic [Mn-II(dapsc)](2+) and anionic [Fe-II(CN)(5)(NO)](2-) units connected through cyanide bridges. The cation complexes 2 and 4 have a pentanuclear molecular structure in which four [Mn(salpn)(MeOH)](+) fragments are linked by the [Mn(CN)(5)NO](3-) or [Fe(CN)(5)(NO)](2-) moieties, respectively. The magnetic and photochromic properties of 1 and 3 have been studied. The thermal magnetic behaviour of the complexes indicates the presence of weak antiferromagnetic interactions between Mn3+ or Mn2+ mediated by diamagnetic [Fe(CN)(NO)-N-5](2-) bridges. Irradiation of 1 and 3 with light gives birth to the long-lived metastable states of nitroprusside.
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https://hal.univ-lorraine.fr/hal-01521899
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Submitted on : Friday, May 12, 2017 - 2:43:57 PM
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Vyacheslav A. Kopotkov, Valentina D. Sasnovskaya, Denis V. Korchagin, Roman B. Morgunov, Sergey M. Aldoshin, et al.. The first photochromic bimetallic assemblies based on Mn(III) and Mn(II) Schiff-base (salpn, dapsc) complexes and pentacyanonitrosylferrate. CrystEngComm, Royal Society of Chemistry, 2015, 17 (20), pp.3866-3876. ⟨10.1039/c5ce00354g⟩. ⟨hal-01521899⟩

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