Crystal‐to‐Gel Transformation Stimulated by a Solid‐State E→Z Photoisomerization

: The molecule (E)-(5-(3-anthracen-9-yl-allylidene)-2,2-dimethyl-[1,3] dioxane-4,6-dione) (E-AYAD) undergoes E→Z photoisomerization. In the solid state, this photoisomerization process can initiate a physical transformation of the crystal that is accompanied by a large volume expansion (ca. 10 times), loss of crystallinity, and growth of large pores. This physical change requires approximately 10 % conversion of the E isomer to the Z isomer and results in a gel-like solid with decreased stiffness that still retains its mechanical integrity. The induced porosity allows the expanding gel to engulf superparamagnetic nanoparticles from the surrounding liquid. The trapped superparamagnetic nanoparticles impart a magnetic susceptibility to the gel, allowing it to be moved by a magnetic field. The photoinduced phase transition, starting with a compact crystalline solid instead of a dilute solution, provides a new route for in situ production of functional porous materials.