PHOTOASSISTED REDUCTION OF THIONYL CHLORIDE BY NEODYMIUM, EUROPIUM, THULIUM AND LUTETIUM DIPHTHALOCYANINES

Diphthalocyanine complexes of Nd-III, Eu-III, Tm-III and Lu-III ([Pc(- 2)(NdPc)-Pc-III(-2)](-), [Pc(-2) (EuPc)-Pc-III(-2)](-), [Pc(-2)(TmPc)- Pc-III(-2)](-) and [Pc(-2)(LuPc)-Pc-III(-2)](-), respectively), underg o one or two-electron oxidation in the presence of thionyl chloride. T he oxidation products depend on the concentration of the thionyl chlor ide. At low concentrations of SOCl2 (<10(-4) mol dm(-3)) one-electron oxidation occurs only upon photolysis, giving the neutral lanthanide d iphthalocyanine, Pc(-2)LnPc(-1), complexes. The Pc(-2)LnPc(-1) species undergo one-electron photooxidation to the [Pc(-1)LnPc(-1)](+) in dic hloromethane and in the presence of SOCl2. At large concentrations of SOCl2 (>10(-2) mol dm(-3)), two electron oxidation of the [Pc(-2)LnPc( -2)](-) species directly to [Pc(-1)LnPc(-1)](+) occurs. (C) 1998 Elsev ier Science Ltd. All rights reserved.