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

Jonathan J. Loughrey, Nathan J. Patmore, Amgalanbaatar Baldansuren, Alistair J. Fielding, Eric J L McInnes, Michaele J. Hardie, Stephen Sproules, Malcolm A. Halcrow

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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.

Original languageEnglish
Pages (from-to)6935-6948
Number of pages14
JournalChemical Science
Volume6
Issue number12
DOIs
Publication statusPublished - 2015

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Loughrey, J. J., Patmore, N. J., Baldansuren, A., Fielding, A. J., McInnes, E. J. L., Hardie, M. J., ... Halcrow, M. A. (2015). Platinum(II) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene. Chemical Science, 6(12), 6935-6948. https://doi.org/10.1039/c5sc02776d