Functional group engineering in naphthalimides: a conceptual insight to fine-tune the supramolecular self-assembly and condensed state luminescence

Engineering well-defined supramolecular fluorescent nano-architectures based on organic conjugated small molecules has been an essential scientific challenge. Herein, a library of sixteen naphthalimide congeners (1-15 and HNI) has been strategically designed that unveils a conceptual insight into the functional group controlled condensed state emission and aggregation-induced enhanced emission (AIEE) in conventional strong aggregation-caused quenching (ACQ) active fluorophores. Along with the regulation of ACQ-to-AIEE transformation and tailoring of the condensed state emission, a simple yet potential design strategy of functional group engineering has been established for the first time to spontaneously generate and systematically tailor the supramolecular self-assembly of organic small molecules into highly defined nano-architectures. Single-crystal XRD analysis of six congeners revealed that, unlike the well-established electronic contribution of the functional groups in the molecularly dispersed state, the condensed state photophysical and morphological properties are dictated by the distinct intermolecular pi-pi stacking interaction of the planar aromatic core. This work demonstrates an unconventional influence of the functional motif in the condensed state that could emerge as a promising route to build a fluorescent supramolecular nanoassembly from non-fluorescent conjugated molecules for a variety of future applications.