Surfactant-Enhanced Photoisomerization and Photomechanical Response in Molecular Crystal Nanowires.

Dimethyl-2(3-anthracen-9-yl)allylidene)malonate (DMAAM) is a divinylanthracene derivative that photoisomerizes between its (E) and (Z) conformations. Crystalline nanowires composed of this molecule undergo a rapid coiling motion when exposed to visible light. In this paper, a variety of experimental techniques are used to investigate the mechanism of this transformation, including powder X-ray diffraction, polarized light microscopy, 1H NMR, and absorption spectroscopy. The results show that the presence of a surfactant like cetyltrimethylammonium bromide (CTAB) accelerates the photochemical reaction rate by at least a factor of 10 within the nanowire and is required to observe the photoinduced coiling. The accelerated reaction facilitates the transition to an amorphous phase composed of reactant and photoproduct, which leads to the rapid, large-scale shape changes that the nanowires undergo. Disruption of the highly packed crystal structure by photoisomerization also enhances the dissolution rate by a factor of about 30. The fact that the nanowires have a nominal diameter of 200 nm suggests that the presence of surface species can influence the reaction dynamics deep inside the crystal. These results show that the reaction dynamics and photomechanical motions of nanoscale molecular crystals can be extremely sensitive to surface species.