Trialkylated pentaerythritol was chosen as a bulky substituent for a set of 3 free-base phthalocyanines: a symmetric, a twinned, and a double-decker derivative. The bulkiness of this substituent lowered the aggregation of the phthalocyanines. The electronic absorptions were comparatively investigated: the twinned phthalocyanine exhibited a significant near-infrared shifted absorption. The neutral radical Eu(III) complex was oxidized by bromine. These 3 phthalocyanines are promising for use as molecular materials.