Photochemically and Thermally Programmed Optical Multi-States from a Single Diacetylene-Functionalized Cyanostilbene Luminogen.

To develop advanced optical systems, many scientists have endeavored to create smart optical materials which can tune their photophysical properties by changing molecular states. However, optical multi-states are obtained usually by mixing many dyes or stacking multi-layered structures. Here, multiple molecular states are tried to be generated with a single dye. In order to achieve the goal, a diacetylene-functionalized cyanostilbene luminogen (DACSM) is newly synthesized by covalently connecting diacetylene and cyanostilbene molecular functions. Photochemical reaction of cyanostilbene and topochemical polymerization of diacetylene can change the molecular state of DACSM. By thermal stimulations and the photochemical reaction, the conformation of polymerized DACSM is further tuned. The synergetic molecular cooperation of cyanostilbene and diacetylene generates multiple molecular states of DACSM. Utilizing the optical multi-states achieved from the newly developed DACSM, switchable optical patterns and smart secret codes are successfully demonstrated.

Self-Assembled and Polymerized Hierarchical Nanostructure Films of Cyanostilbene-Based Reactive AIEgens for Smart Chemosensors.

For the development of acid-responsive advanced fluorescent films with a 2D nanostructure, a pyridyl cyanostilbene-based AIEgen (PCRM) is newly synthesized. The synthesized PCRM exhibits aggregation-induced emission (AIE) and responds reversibly to acid and base stimuli. To fabricate the nanoporous polymer-stabilized film, PCRM and 4-(octyloxy)benzoic acid (8OB) are complexed in a 1:1 ratio through hydrogen bonding. The PCRM-8OB complex with a smectic mesophase is uniaxially oriented at first and photopolymerized with a crosslinker. By subsequently removing 8OB in an alkaline solution, nanopores are generated in the self-assembled and polymerized hierarchical 2D nanostructure film. The prepared nanoporous fluorescent films exhibit not only the reversible response to acid and base stimuli but also mechanical and chemical robustness. Since the nanoporous fluorescent films have different sensitivities to trifluoroacetic acid (TFA) depending on the molecular orientation in the film, advanced acid vapor sensors that can display the risk level according to the concentration of TFA are demonstrated. Reactive AIEgens-based hierarchical nanostructure films with nanopores fabricated by a subsequent process of self-assembly, polymerization, and etching can open a new door for the development of advanced chemosensors.