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Issue 12, 2015
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Platinum(II) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene

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Abstract

Three complexes of cyclotricatechylene (H6ctc), [{PtL}33-ctc)], have been synthesised: (L = 1,2-bis(diphenylphosphino)benzene {dppb}, 1; L = 1,2-bis(diphenylphosphino)ethane {dppe}, 2; L = 4,4′-bis(tert-butyl)-2,2′-bipyridyl {tBu2bipy}, 3). The complexes show three low-potential, chemically reversible voltammetric oxidations separated by ca. 180 mV, corresponding to stepwise oxidation of the [ctc]6− catecholato rings to the semiquinonate level. The redox series [1]0/1+/2+/3+ and [3]0/1+/2+/3+ have been characterised by UV/vis/NIR spectroelectrochemistry. The mono- and di-cations have class II mixed valent character, with reduced radical delocalisation compared to an analogous bis-dioxolene system. The SOMO composition of [1˙]+ and [3˙]+ has been delineated by cw EPR, ENDOR and HYSCORE spectroscopies, with the aid of two monometallic model compounds [PtL(DBsq˙)]+ (DBsqH = 3,5-bis(tert-butyl)-1,2-benzosemiquinone; L = dppe or tBu2bipy). DF and time-dependent DF calculations confirm these interpretations, and demonstrate changes to spin-delocalisation in the ctc macrocycle as it is sequentially oxidised.

Graphical abstract: Platinum(ii) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene

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Publication details

The article was received on 29 Jul 2015, accepted on 18 Aug 2015 and first published on 20 Aug 2015


Article type: Edge Article
DOI: 10.1039/C5SC02776D
Citation: Chem. Sci., 2015,6, 6935-6948
  • Open access: Creative Commons BY license
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    Platinum(II) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene

    J. J. Loughrey, N. J. Patmore, A. Baldansuren, A. J. Fielding, E. J. L. McInnes, M. J. Hardie, S. Sproules and M. A. Halcrow, Chem. Sci., 2015, 6, 6935
    DOI: 10.1039/C5SC02776D

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