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Reduced dimensionality and quantum confinement in conjugated organic and polymer structures enhance the effects of electron correlation on virtual electronic excitation processes and nonlinear-optical responses. A microscopic many-electron description of the third-order susceptibilities Yijkl(-W4; w1, 2, c3) of conjugated structures is reviewed for one-dimensional chains and extended to two-dimensional conjugated cyclic structures. Electron correlation effects in effectively reduced dimensions result in highly correlated 7-electron virtual excitations that lead to large, ultrafast nonresonant nonlinear-optical responses. The increase of dimensionality from linear to cyclic chains is found to reduce the nonresonant isotropic third-order susceptibility yg. Resonant experimental studies of saturable absorption and optical bistability in ultrathin films of quasi-two-dimensional naphthalocyanine oligomers are also presented. In the saturable-absorption studies, the resonant nonlinear refractive index n was measured to be 1 X 10-4 cm2/kW in the wavelength range of operating laser diodes. Based on this result, electronic absorptive optical bistability is observed on a nanosecond time scale in a nonlinear Fabry-Perot interferometer employing the saturably absorbing naphthalocyanine film as the nonlinear-optical medium.

The third-order nonlinear optical properties of several porphyrin derivatives incorporated in thin films of polymethylmethacrylate have been measured by degenerate four-wave mixing at 598 nm with 1 ps pulses. Both the magnitude and dynamics of the nonlinear response are measured, with each system exhibiting both a subpicosecond response and a more slowly decaying response (10 ps–1 ns) owing to excited-state population. A copolymer of silicon phthalocyanine and methyl methacrylate exhibits a fast recovery time (15 ps) and no observable long-time (∼ns) component of its nonlinear response, as well as an absorption band twice as narrow as that of guest/host samples of the same material.

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The photosensitive, alkyl- and alkylsiloxy-ligated silicon phthalocyanine, SiPc[(CH2)3SH][OSi(CH3)2(CH2)3N(CH3)2], Pc 227, has been prepared and characterized. This phthalocyanine yields the experimental photodynamic therapy (PDT) drug Pc 4, SiPc[OH][OSi(CH3)2(CH2)3N(CH3)2], when irradiated with red light. To provide an understanding of the process by which Pc 227 and other alkyl-alkylsiloxysilicon phthalocyanines such as Pc 227 are photolyzed, bond dissociation energy, natural bond orbital (NBO) charge distribution, spin density distribution, nucleus-independent chemical shift (NICS), and electron localization function (ELF) calculations have been carried out on two models related to it. These show that the lowest energy pathway for the photolysis of Pc 227 is a homolysis involving a phthalocyanine π radical having a low SiPc-C bond dissociation energy. The promise of the results of this study for synthetic chemistry and drug development is discussed.