Light-responsive three-dimensional microstructures composed of azobenzene-based palladium complexes.

We describe not only fleeting assembly of photoisomerizable azobenzene-based palladium complexes into microstructured crystalline architectures but also their light-responsive functions. A transformation in the crystalline morphology from two-dimensional (2D) parallelogram-like sheets to three-dimensional (3D) cuboid- or rhombus-like structures was achieved by changing the solvent from tetrahydrofuran (THF) to acetone and N,N-dimethylformamide (DMF). The sizes of the structures, ranging from a few hundred nanometers to several hundred micrometers, were also modified by varying the complex concentration. In stark contrast to the very stable 2D sheets in the THF-H2O suspensions, exposure of 3D structures in polar DMF-H2O suspensions to ultraviolet (UV) light led to fast disassembly of the structures into isolated metal complexes and further dissociation of free azobenzene ligands from the complexes. In acetone-H2O suspensions, interestingly, disassembly of 3D cuboid-like structures into isolated complex components occurred upon exposure to UV light without further dissociation of azobenzene ligands from the palladium complexes. Considering the photoisomerization ability of the azobenzene-based palladium complex in common organic solvents, the π-stacking interactions that support 3D structures are likely to be sufficiently weak that they might be broken by the UV-induced trans-to-cis isomerization in more polar solvent mixtures. As a consequence, disassembly proceeded under UV light irradiation. Moreover, the effect of solvent polarity on the UV-assisted dissociation (in DMF-H2O) may be associated with the coordination ability of solvent molecules with the metal center.