TY - JOUR
T1 - Platinum(II) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene
AU - Loughrey, Jonathan J.
AU - Patmore, Nathan J.
AU - Baldansuren, Amgalanbaatar
AU - Fielding, Alistair J.
AU - McInnes, Eric J L
AU - Hardie, Michaele J.
AU - Sproules, Stephen
AU - Halcrow, Malcolm A.
PY - 2015/12/1
Y1 - 2015/12/1
N2 - Three complexes of cyclotricatechylene (H6ctc), [{PtL}3(μ3-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.
AB - Three complexes of cyclotricatechylene (H6ctc), [{PtL}3(μ3-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.
KW - Oxidation
KW - Spectroelectrochemistry
KW - Platinum complexes
UR - http://www.scopus.com/inward/record.url?scp=84946913843&partnerID=8YFLogxK
U2 - 10.1039/c5sc02776d
DO - 10.1039/c5sc02776d
M3 - Article
AN - SCOPUS:84946913843
VL - 6
SP - 6935
EP - 6948
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 12
ER -