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I19-Small Molecule Single Crystal Diffraction	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 Hardie , Stephen Sproules , Malcolm A. Halcrow Chemical Science DOI: 10.1039/C5SC02776D Diamond Proposal Number(s): [7847] Open Access Show Abstract ▼ Abstract: Three complexes of cyclotricatechylene (H6ctc), [{PtL}3(m3-ctc)], have been synthesised: (L ¼ 1,2-bis(diphenylphosphino)benzene {dppb}, 1; L ¼ 1,2-bis(diphenylphosphino)ethane {dppe}, 2; L ¼ 4,40- bis(tert-butyl)-2,20-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 ystem. The SOMO composition of [1c]+ and [3c]+ has been delineated by cw EPR, ENDOR and HYSCORE spectroscopies, with the aid of two monometallic model compounds [PtL(DBsqc)]+ (DBsqH ¼ 3,5-bis(tert-butyl)-1,2-benzosemiquinone; L ¼ dppe or tBu2bipy). DF and time-dependent DF calculations confirm these interpretations, and emonstrate changes to spin-delocalisation in the ctc macrocycle as it is sequentially oxidised.	Aug 2015

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I19-Small Molecule Single Crystal Diffraction

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 Hardie , Stephen Sproules , Malcolm A. Halcrow

Chemical Science

DOI: 10.1039/C5SC02776D

Diamond Proposal Number(s): [7847]