Silicon complexation of a[ 38]octaphyrin (1)w as accomplished by reaction with an excess amount of MeSiCl 3 in the presence of N,N-diisopropylethylamine,t hus giving an aromatic [38]octaphyrin bis(silicon) complex 2.This complex was interconvertible with an antiaromatic [36]octaphyrin congener (3)b yo xidation with MnO 2 and reduction with NaBH 4 .C uriously,m ild oxidation of 2 with ferrocenium hexafluorophosphate afforded a[ 37]octaphyrin bis(silicon) complex 4 as an stable radical cation that can be stored under ambient conditions in the solid state.O wing to the two NNNCC-five-coordinated Si atoms bearing trigonal bipyramidal geometry,t hese octaphyrin bis(silicon) complexes take on similar and rigid figure-of-eight structures with different consecutive numbers of conjugated p-electrons (38, 37, and 36), and are all stable.