Solvent effects on the absorption, circular dichroism and Raman spectroscopy of meso-tetrakis [3-methoxy-4-(N-carbazyl)n-hexyloxyphenyl] porphyrin in water–THF solution

Solutions of meso-tetrakis [3-methoxy-4-(N-carbazyl)n-hexyloxyphenyl] porphyrin (4C6-TPP) in a water–organic mixture (tetrahydrofuran, THF) generate aggregates with absorption spectra characterized by broader red shifts of the Soret band relative to the monomeric porphyrin band. For the aggregated form several phenyl modes enhance and some modes weaken, the ν2, ν3 and ν11 bands in the Raman spectra are slightly downshifted compared with the monomeric form. These data suggest that the phenyl groups of 4C6-TPP in the aggregate rotate to an orientation more coplanar with the porphyrin core. The increased conjugation of the meso-phenyl rings with the porphyrin core brings about the red shift of the Soret band. The circular dichroism (CD) band of the aggregate undergoes some changes with time, as indicated by the transition from a negative band to no signal resulted from the rotation of phenyl groups. All of the results imply that the location of the phenyl groups plays a key role in the determination of the morphology of the aggregate.