A key limitation of supramolecular force-driven molecular
assembly
in aggregation-induced emission (AIE) materials is the need to precisely
regulate molecular interactions within the assembly. Achieving such
assemblies with in situ manipulable molecular arrangements could provide
valuable insights into the role of molecular forces in AIE. Herein,
by using glutathione-protected gold nanoclusters (AuNCs) as a model
AIE material and a naturally occurring polyphenol, tannic acid (TA),
as the assembling agent, we demonstrate that assemblies dominated
by covalent bonds and hydrogen bonding show enhanced AIE, while those
dominated by π–π stacking promote charge transfer,
resulting in significant photoluminescence (PL) quenching. This phenomenon
primarily stems from the oxidation of TA into smaller aromatic ring
structures, leading to an increase in π–π interactions.
The complete in situ oxidation of TA within the assembly induces a
morphological transition from 3-D spherical to 2-D sheet-like structures
due to the dominance of π–π interactions, consequently
resulting in complete PL quenching of AuNCs. These findings highlight
the critical role of molecular packing in modulating the AIE properties
of AuNCs.