Controlling the growth of porphyrin based nanostructures for tuning third-order NLO properties

A series of porphyrin nanospindles with controlled long axis length distributions of 330, 550, 800 nm, and 4 μm have been successfully fabricated via hierarchical self-assembly of cationic porphyrin (H₆TPyP)(4+) with the help of anionic surfactant sodium dodecyl sulfonate (SDS) due to the effective electrostatic interaction. These newly fabricated nanostructures are characterized by TEM and SEM techniques, powder X-ray diffraction analysis, electronic absorption spectroscopy, and confocal laser scanning microscopy (CLSM). The Z-scan technique with a laser duration of 5 ns at the wavelength of 532 nm reveals unreported size-dependent third-order NLO switching properties: the nonlinear absorption changes from saturation absorption to reversed saturation absorption and the nonlinear refraction from self-defocus to self-focus due to the change of the dominant scattering effect, from Rayleigh scattering for nanostructures with a smaller size than the wavelength of laser light, to Mie scattering for nanostructures with a larger size than the laser wavelength. This result is useful for the development of organic nanostructures with desired NLO properties, in particular the optical limiting properties.