The enhancement of the third order susceptibilities (chi) (3) and second order molecular hyperpolarizabilites < (gamma) > in a series of covanlently stacked dimer and trimer macrocycles (SiPc and SiNc) was observed throught he phase conjugated signals from DFWM measurements at both 1064 and 532 nm. The FWHM of the phase conjugated signals at 532 nm is much smaller than those at 1064 nm and those of the reference compound CS2. The < (gamma) > values at both wavelengths as a function of number of the monomer units (n) have an approximate n3 dependence, differing only in the scaling constant. The origin of such enhancement is discussed and compared to those in 1D (pi) -conjugated systems.
A series of new silicon phthalocyanine monomers containing two or more hydroxyl groups has been synthesized by axial etherification of [PcSi(OH)2] with various polyfunctional alcohols, where R is a residue generated from an appropriate alcohol namely, ethylene glycol, glycerol, triethanolamine, triethylene glycol, 1,4-bis(2- hydroxyethyl)piperazine and N,N-bis(2-hydroxyethyl) isonicotinamide. All derivatives are soluble in common organic solvents such as chloroform and dioxane, and exhibit low absorptions in the visible spectral region. The dimer [RO(SiPcO)2R] and trimer [RO(SiPcO)3R] of triethanolamine have also been synthesized to investigate structure-property relationships. The above derivatives can be processes into thin polymeric films either by reacting with a diisocyanate compound or with a reactive polysiloxane. Third- order nonlinear optical properties of the above derivatives are described.
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