Abstract
Porphyrin-based molecules play an important role in natural biological systems such as photosynthetic antennae and haemoglobin. Recent organic chemistry provides artificial porphyrin-based molecules having unique electronic and optical properties, which leads to wide applications in material science. Here, we successfully produced many macroscopically anisotropic structures consisting of porphyrin dimers by light-induced solvothermal assembly with smooth evaporation in a confined volatile organic solvent. Light-induced fluid flow around a bubble on a gold nanofilm generated a sub-millimetre radial assembly of the tens-micrometre-sized petal-like structures. The optical properties of the petal-like structures depend on the relative angle between their growth direction and light polarisation, as confirmed by UV-visible extinction and the Raman scattering spectroscopy analyses, being dramatically different from those of structures obtained by natural drying. Thus, our findings pave the way to the production of structures and polycrystals with unique characteristics from various organic molecules.
Highlights
Porphyrin-based molecules play an important role in natural biological systems such as photosynthetic antennae and haemoglobin
A toluene solution of diporphyrin was placed on a gold nanofilm and the solution/nanofilm interface was vertically illuminated with an infrared continuous wave (CW) laser to generate fluid flow for transporting and a bubble for the deposition of the transported molecules
A single natural drying-produced structure with rugby-ball-like shape did not exhibit pronounced anisotropic properties(Supplementary Figure S4), and showed weakly polarisation-dependent property, with this anisotropy vanishing in the averaged spectrum (Fig. 3b). These results suggest that light-induced fluid flow would transport constituent molecules around a bubble to result in a directional assembly in the case of Light-induced solvothermal assembly (LSTA), whereas the solution was evaporated uniformly and slowly to result in a directionless growth in the case of natural drying
Summary
Yasuyuki Yamamoto[1,2,3], Yushi Nishimura[1,2,3,5], Shiho Tokonami[2,3], Norihito Fukui[4,6], Takayuki Tanaka[4], Atsuhiro Osuka[4], Hideki Yorimitsu4 & Takuya Iida[1,2]. A single natural drying-produced structure with rugby-ball-like shape did not exhibit pronounced anisotropic properties(Supplementary Figure S4), and showed weakly polarisation-dependent property, with this anisotropy vanishing in the averaged spectrum (Fig. 3b). These results suggest that light-induced fluid flow would transport constituent molecules around a bubble to result in a directional assembly in the case of LSTA, whereas the solution was evaporated uniformly and slowly to result in a directionless growth in the case of natural drying
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