Role of Sterically Bulky Azobenzenes in the Molecular Assembly of Pyrene Derivatives: Rectangular Sheet-like Structures and Their Emission Characteristics

The development of pyrene-based fluorescent assembled systems with desirable emission characteristics by reducing conventional concentration quenching and/or aggregation-induced quenching (ACQ) is highly desirable. In this investigation, we designed a new azobenzene-functionalized pyrene derivative (AzPy) in which sterically bulky azobenzene is linked to pyrene. Absorption and fluorescence spectroscopic results before and after molecular assembly indicate that even in a dilute N,N-dimethylformamide (DMF) solution (~10 μM), AzPy molecules experienced significant concentration quenching, whereas the emission intensities of AzPy DMF-H O turbid suspensions containing self-assembled aggregates were slightly enhanced and showed similar values regardless of the concentration. The shape and size of sheet-like structures, from incomplete flakes less than one micrometer in size to well-completed rectangular microstructures, could be adjusted by changing the concentration. Importantly, such sheet-like structures exhibit concentration dependence of their emission wavelength from blue to yellow-orange. Comparison with the precursor (PyOH) demonstrates that the introduction of a sterically twisted azobenzene moiety plays an important role in converting the spatial molecular arrangements from H- to J-type aggregation mode. Thus, AzPy chromophores grow into anisotropic microstructures through inclined J-type aggregation and high crystallinity, which are responsible for their unexpected emission characteristics. Our findings provide useful insight into the rational design of fluorescent assembled systems.