Photoassisted reduction of thionyl chloride by neodymium, europium, thulium and lutetium diphthalocyanines

Diphthalocyanine complexes of Nd III, EuIII, TmIII and LuIII ( [Pc (−2) Nd IIIPc (−2) ] −, [Pc (−2) EuIIIPc (−2) ] −, [Pc (−2) TmIIIPc (−2) ] − and [Pc (−2) LuIIIPc (−2) ] −, respectively) , undergo one or two-electron oxidation in the presence of thionyl chloride. The oxidation products depend on the concentration of the thionyl chloride. At low concentrations of SOCl2 (larger than 10−4 mol dm−3) one-electron oxidation occurs only upon photolysis, giving the neutral lanthanide diphthalocyanine, Pc (−2) LnPc (−1) , complexes. The Pc (−2) LnPc (−1) species undergo one-electron photooxidation to the [Pc (−1) LnPc (−1) ] + in dichloromethane 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