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Issue 40, 2017
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Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (Cp*2Cr+)(H+)(H2TPCor˙2−)·C6H4Cl2

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Abstract

The reduction of 5,10,15-triphenylcorrole (H3TPCor) with decamethylchromocene yields (Cp*2Cr+)(H+)(H2TPCor˙2−)·C6H4Cl2 (1). It is accompanied by the deprotonation of H3TPCor and the formation of planar H2TPCor˙2− radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of H2TArylCor˙2− and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10μB at 300 K indicates the contribution of Cp*2Cr+ (S = 3/2) and H2TPCor˙2− (S = 1/2). These paramagnetic species alternate in the π-stacks providing rather effective antiferromagnetic coupling of spins at the Weiss temperature of −31 K. To distinguish the H2TPC˙2− dianions from the deprotonated H2TPCor anions, we also studied the {cryptand[2,2,2](Na+)}(H2TPCor)·0.5C6H4Cl2 (2) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of H2TPCor in 2 differ from those of H2TPCor˙2− in 1.

Graphical abstract: Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (Cp*2Cr+)(H+)(H2TPCor˙2−)·C6H4Cl2

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Publication details

The article was received on 06 Aug 2017, accepted on 18 Sep 2017 and first published on 18 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02901B
Citation: Dalton Trans., 2017,46, 13994-14001
  • Open access: Creative Commons BY license
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    Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (Cp*2Cr+)(H+)(H2TPCor˙2−)·C6H4Cl2

    D. V. Konarev, D. R. Karimov, S. S. Khasanov, A. F. Shestakov, A. Otsuka, H. Yamochi, H. Kitagawa and R. N. Lyubovskaya, Dalton Trans., 2017, 46, 13994
    DOI: 10.1039/C7DT02901B

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