Immobilizing Tetraphenylethylene into Fused Metallacycles: Shape Effects on Fluorescence Emission

Herein, we describe the selective formation of a discrete fused metallarhomboid and a triangle by the careful control of the shape and stoichiometry of the building blocks. A tetraphenylethylene (TPE)-based tetrapyridyl donor is exploited as the bridging component, and coordination immobilization of the TPE unit within the rigid metallacyclic frameworks efficiently suppresses its intramolecular rotational motions. As a result, the fused polygons are innately emissive in dilute solution, representing an alternative to aggregation-induced emission. Upon further molecular aggregation, these metallacycles display aggregation-induced enhanced emissions. Interestingly, the fused rhomboid 7 shows a weaker fluorescence in dilute solutions relative to that of the fused triangle 8, while a reversal of emission intensities was observed in the aggregated state. These markedly different fluorescence efficiencies are likely due to the differences in the shapes of the fused polygons. Thus, this work shows that the properties of supramolecular coordination complexes can be affected by subtle structural factors, which can be controlled easily and precisely at the molecular level.