Morphology controlled surface-assisted self-assembled microtube junctions and dendrites of metal free porphyrin-based...

Solution-vapor annealing of drop-cast thin films of meso-5,10,15,20-tetra-n-decylporphyrin H(2)T(C(10)H(21))(4)P deposited on SiO(2) substrate and quartz leads to the formation of well-defined self-assemblies. Their self-assembling properties in n-hexane vapor and chloroform vapor were comparatively investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) technique, and IR and UV-vis spectroscopy. Intermolecular pi-pi interaction in cooperation with the van der Waals interaction of metal free porphyrin and solvent-solute interaction leads to the formation of microleaves and microtube dendrites in n-hexane vapor and chloroform vapor, respectively. Electronic absorption spectroscopic data on the self-assembled microstructures reveal the J-aggregate nature in both the microleaves and microtube dendrites. However, the difference in the shift of the Soret and Q bands for the two kinds of aggregates relative to corresponding solution absorption bands indicates the dependence of the solvent-porphyrin molecular interaction during the annealing self-assembly process, which counterbalances the intermolecular interactions, particularly the hydrophobic interaction between side chains. IR and XRD results clearly reveal the higher molecular ordering nature of microtube dendrites than that of microleaves, further confirming the effect of the solvent on tuning the intermolecular interaction and in turn the molecular packing mode in aggregates of porphryin compounds. The present results appear to represent the first example of orderly micrometer-sized tube junctions and dendrites of porphyrin prepared through a self-assembly process, providing an effective and new method toward the synthesis of complicated nanotubular structures. In addition, micrometer-sized leaves and tube dendrites were revealed to show good semiconductor features. Highly reproducible and sensitive gas response characteristics have also been observed in these microstructures.