Chemical analyses and x-ray diffraction patterns of powders and films of chloroaluminum phthalocyanine

Fine powders and sublimed films (15 micrometers thick) of pure chloroaluminum phthalocyanine (ClAlPc) undergo both, chemical reaction and structural modification, when immersed in aqueous solutions containing anions (I3-/I- or Br- at various acid pH values). The x-ray diffraction diagrams of powder and films of untreated ClAlPc exhibit a strong characteristic peak corresponding to a d-spacing of 3.29 angstrom. A 48 h. immersion of ClAlPc (powder or film) resulted in the appearance of a new peak at 3.45 angstrom in the diffraction diagram. The peak intensity at d equals 3.45 angstrom is only 11% (powder) or 47% (film) of the main peak intensity at d equals 3.29 angstrom. It clearly shows that the crystal structure of ClAlPc has only been partially modified in both cases. However, the modification is more complete for the film than for the powder. Chemical analyses by neutron activation were performed on fine powders of ClAlPc before and after immersion. For instance ClAlPc absorbs 7.6% by weight of iodine after 24 h of immersion in I3-/I- (0.005 M/0.4 M) redox electrolyte at pH 1.0. The decrease in the chlorine content of untreated ClAlPc from 6.1% to 3.7% after immersion could be explained in terms of an hydrolysis reaction of some ClAlPc. These results lead us to a model where by the surface of the ClAlPc crystallites would be hydrolyzed to HOAlPc and heavily doped with anions taken up from the aqueous solution. These transformations improve the photoactivity of the material.