A novel polyaniline containing azo groups has been synthesized using h
orseradish peroxidase catalyzed oxidative free radical coupling of 4,4
'-diaminoazobenzene in the presence of hydrogen peroxide. The spectral
changes observed indicate polymerization accompanied by trans-cia iso
merization, leading to structural constraints in the growing polymer c
hain. This soluble azo polymer consists of azo groups in the main chai
n as well as in the side chain. Upon photoexcitation of the polymer in
solution, the chromophores undergo structural photoisomerization; The
polymer relaxes to a conformation having spectral features identical
to those of the conformation prior to photoexcitation if the excitatio
n is carried out within the trans absorption band. Photoexcitation at
the cis absorption band or thermal kinetic randomization of the chromo
phore conformation in the polymer in solution results in relaxation of
the structural constraints, which leads to a different constrained co
nformation.