A Self‐Assemble Supramolecular Film with Humidity Visualization Enabled by Clusteroluminescence

Abstract Clusteroluminescence (CL) has recently gained significant attention due to its unique through‐space interactions associated with a high dependence on the aggregation of subgroups. These distinct features could easily transform the stimuli into visual fluorescence and monitor the fluctuation of the environment but have not received sufficient attention before. In this work, supramolecular films are designed based on the neutralization reaction of anhydride groups and the self‐assembly of dynamic covalent disulfide bonds in NaOH aqueous solution. The self‐assembly of hydrophilic carboxylate chromophores and hydrophobic disulfide‐containing five‐membered rings could be observed by the variation of the aggregation state of carboxylate in CL. Furthermore, the dynamic cross‐linking films obtained with water‐sensitive carboxylate chromophores could alter the aggregation distance stimulated by surrounding water vapor, causing the emission wavelength to change from 534 to 508 nm by varying the relative humidity. This work not only provides an approach to monitor the self‐assembly of clusteroluminogens but also offers new strategies for designing stimuli‐responsive materials that utilize the intrinsic features of CL.