SYNTHESIS OF MU-CYANO(2,3-NAPHTHALOCYANIN ATO)IRON(III) AND COMPARISON TO MU-CYANO(PHTHALOCYANINATO)IRON(III)

Potassium dicyano(2,3-naphthalocyaninato)ferrate(III), K[2,3-NcFe(CN)2 ] (2), reacts in water with elimination of KCN to form mu-cyano(2,3-na phthalocyaninato)iron(III), [2,3-NcFe(CN)]n (4a). Dichloro(2,3-naphtha locyaninato)iron(III), 2,3-NcFeCl2 (3), reacts with KCN to yield also [2,3-NcFe(CN)]n (4b). Both compounds 4a and 4b show similar IR spectra with a typical blue-shifted CN valence frequency caused by a bridging function of CN-. Compounds 4a and 4b also show almost identical Fe-57 -Mossbauer spectra which, however, might be interpreted with a Fe(+II) oxidation state of the iron. The measured magnetic moment of 4 howeve r clearly proves the expected oxidation state +III of the iron in [2,3 -NcFe(CN)]n (4). Compounds 4a and 4b both exhibit good semiconducting properties (sigma(RT) almost-equal-to 10(-3) S/cm) without additional external oxidative doping. The property is quite similar to that of th e known mu-cyano(phthalocyaninato) iron [PcFe(CN)]n (sigma(RT) almost- equal-to 10(-2) S/cm).