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Issue 8, 2001
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Unique structural topologies involving metal–metal and metal–sulfur interactions: salts of [Ni(C3S5)2]x with cis-anti-cis-dicyclohexyl-18-crown-6 complexed counter ions

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Abstract

Preparation by electrocrystallisation has been carried out for the salts [Rb(anti-dchyl-18c6)]2[Ni(dmit)2] 1, [Rb(anti-dchyl-18c6)][Ni(dmit)2] 2, [Cs(anti-dchyl-18c6)]2[Ni(dmit)2] 3 and [Cs(anti-dchyl-18c6)1.5][Ni(dmit)2]64 (anti-dchyl-18c6 = cis-anti-cis-dicyclohexyl-18-crown-6, dmit = C3S5). Salts 1 and 3 involve the planar dianionic nickel complex sandwiched by two metal–crown units. This leads to short Rb+  Ni and Rb+  S interactions in 1 and the shortest recorded Cs+  Ni distance of 3.47 Å in 3, presumably stabilised by the four surrounding S atoms at 3.73–4.44 Å. DFT calculations on the dianionic salts 1 and 3 indicate an essentially electrostatic interaction between the [Ni(dmit)2]2− complex and the Rb+ or Cs+ ion and show frontier orbitals qualitatively similar to those previously derived from EHMO calculations on molecular conductors containing [Ni(dmit)2]. Salt 2 consists of non-stacked nickel complexes arranged in chains linked by S  Rb+ interactions through the terminal sulfurs with the Rb+ ion placed exactly within the plane of the crown oxygens. Magnetic susceptibility measurement indicated weak antiferromagnetic interactions. Salt 4 shows a 2-D sheet of nickel complexes stacked in a herringbone arrangement separated by layers of counter ions complexed by the crowns in a disordered manner with the anion ∶ cation ratio of 6 ∶ 1 uniquely high among [Ni(dmit)2]x− salts. Salt 4 displays semiconductor behaviour with σRT = 10−2 S cm−1.

Graphical abstract: Unique structural topologies involving metal–metal and metal–sulfur interactions: salts of [Ni(C3S5)2]x− with cis-anti-cis-dicyclohexyl-18-crown-6 complexed counter ions

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Publication details

The article was received on 16 Oct 2000, accepted on 09 Feb 2001 and first published on 20 Mar 2001


Article type: Paper
DOI: 10.1039/B008299F
Citation: J. Chem. Soc., Dalton Trans., 2001,0, 1347-1351
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    Unique structural topologies involving metal–metal and metal–sulfur interactions: salts of [Ni(C3S5)2]x with cis-anti-cis-dicyclohexyl-18-crown-6 complexed counter ions

    L. Cronin, S. J. Clark, S. Parsons, T. Nakamura and N. Robertson, J. Chem. Soc., Dalton Trans., 2001, 0, 1347
    DOI: 10.1039/B008299F

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