Phthalocyanines have remarkable chemical and thermal stability and offer tremendous architectural flexibility in their structure, facilitating the tailoring of physical, optoelectronic, and chemical parameters. In this paper, we summarize experimental measurements of nonlinear optical absorption in a comprehensive representative series of modified phthalocyanines substituted with various central metals and peripheral functional groups. Rate equations are used to analytically solve the static‐state conditions that simulate the excited‐state dynamics that result from the nonlinear excited‐state absorption, and this solution is fitted to the experimental data. General molecular engineering trends relating the optical limiting performance of these compounds to their structural characteristics are also explored and discussed.
Due to their ease of fabrication and monodisperse, metallic nature, molybdenum-sulfur-iodine nanowires are an interesting alternative to carbon nanotubes for some applications. However very little is known about the solubility of these materials. In this work we have investigated the solubility of Mo(6)S(4.5)I(4.5) nanowire soot in a range of common solvents by performing sedimentation studies and microscopic and spectroscopic characterization. A sedimentation equation was derived showing that the concentration of any insoluble dispersed phase decreases exponentially with time. We find that in all solvents, Mo(6)S(4.5)I(4.5) nanowire soot contains three phases, two of which are insoluble with one stable phase. Microscopy and spectroscopy show that the first insoluble phase is associated mainly with spherical impurities and sediments rapidly out of solution resulting in purification. The second phase appears to consist of insoluble nanowire bundles and sediments more slowly, eventually leaving a stable dispersion of nanowire bundles. The stably dispersed bundles tend to be smaller than their insoluble counterparts. The best solvents studied were 2-propanol and dimethylformamide. Microscopy studies showed that, in the case of 2-propanol, sonication significantly reduced the bundle size relative to the unsonicated bulk. However, during sedimentation, large quantities of bundles were observed to reaggregate to form larger bundles which subsequently sedimented out of solution. In general, the sedimentation properties of the various phases did not vary significantly with concentration indicating that the insoluble nanowires are intrinsically insoluble. However, the diameter of the stably dispersed bundles decreased with concentration, until very small bundles consisting of only two or three nanowires were observed at concentrations below 0.003 mg/mL. In addition, stable composite dispersions were produced by mixing the nanowires with poly(vinylpyrrolidone) in 2-propanol opening the way for the formation of polymer/inorganic nanowire composites.
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