Photoswitchable Nanomaterials Based on Hierarchically Organized Siloxane Oligomers

Materials with highly ordered molecular arrangements have the capacity to display unique properties derived from their nanoscale structure. Here, the synthesis and characterization of azobenzene (AZO)‐functionalized siloxane oligomers of discrete length that form photoswitchable supramolecular materials are described. Specifically, synergy between phase segregation and azobenzene crystallization leads to the self‐assembly of an exfoliated 2D crystal that becomes isotropic upon photoisomerization with UV light. Consequently, the material undergoes a rapid athermal solid‐to‐liquid transition which can be reversed using blue light due to the unexpectedly fast 2D crystallization that is facilitated by phase segregation. In contrast, enabling telechelic supramolecular polymerization through hydrogen bonding inhibits azobenzene crystallization, and nanostructured pastes with well‐ordered morphologies are obtained based on phase segregation alone, thus demonstrating block copolymer‐like behavior. Therefore, by tailoring the balance of self‐assembly forces in the azobenzene‐functionalized siloxane oligomers, fast and reversible phase‐changing materials can be engineered with various mechanical properties for applications in photolithography or switchable adhesion to lubricant properties. Azobenzene‐functionalized siloxane oligomers self‐assemble into supramolecular materials with well‐ordered nanostructure and highly organized molecular arrangement. Photoisomerization with UV and visible wavelengths alter molecular organization, resulting in materials with rapid and reversible athermal phase transitions. Furthermore, by varying the synergy between phase segregation and azobenzene crystallization, material properties can be tailored for applications in photoswitchable adhesion and photolithography.