Pillararene‐Based Fluorescent Supramolecular Systems: The Key Role of Chain Length in Gelation

Four supramolecular assemblies are fabricated from two pillararene tetramers with aggregation‐induced emission properties (SH and LH) and two different lengths of neutral guests with three binding sites (arms) for pillararene cavities (SG and LG) through host–guest interactions, and their fluorescent behaviors in organic solvent are investigated. SG⊂SH exhibits the largest fluorescent enhancement in chloroform due to supramolecular assembly‐induced emission enhancement, while only LG⊂LH turns into supramolecular gel with stimuli responsiveness owing to their most flexible arms. A series of supramolecular assemblies is fabricated from two pillararene tetramers with aggregation‐induced emission properties and two different lengths of neutral guests with three binding arms for pillararene cavities through host–guest interactions, and the supramolecular assembly‐induced emission enhancement of the supramolecular polymers in organic solvent and gel state is investigated.