Experimental and theoretical results on third-order nonlinear optical
susceptibility chi(3) and molecular hyperpolarizability (gamma) of oli
gomeric and polymeric azines are reported for the first time. Molecula
r hyperpolarizabilities (gamma) of well-defined conjugation length pol
yazines containing terminal electron-donating amino groups were calcul
ated by employing the ab initio Coupled Perturbed Hartee-Fock with the
6-31G basis set. An azine monomer showed a molecular hyperpolarizabil
ity of the order of 14.7x10(-36) esu, which is the largest gamma value
ever reported for such a short pi-electron conjugation length. Molecu
lar hyperpolarizability increases significantly as the length of the p
i-electron delocalization increases. The gamma values for the dimer, t
rimer, tetramer, and pentamer azine derivatives were 79.0x10(-36), 228
.3x10(-36), 575.9x10(-36), and 903.0x10(-36) esu, respectively. Third-
order nonlinear optical susceptibilities chi(3) of polyazine derivativ
es were determined by third-harmonic generation (THG) measurements. Th
e chi(3)(-3omega; omega, omega, omega) values of an azine monomer and
a pentamer were 1.39x10(-13) and 15.3x10(-13) esu, respectively. On th
e other hand, the chi(3) of a polyazine possessing statistically alter
nating methyl and propyl substituents on the carbon atoms along the ch
ain was found to be 8.0x10(-12) esu at 1.5 mum. The interesting third-
order nonlinear properties of polyazines presumably originate from the
multiple quantum-well structure of the main pi-electron conjugated ba
ckbone.