Assemble–Disassemble–Reassemble Dynamics in Copper Nanocluster-Based Superstructures
Sameeksha Agrawal, Saurabh Rai, Paritosh Mahato, Asif Ali, Saptarshi Mukherjee
Abstract
Assembling metal nanoclusters (MNCs) to form superstructures generates exciting photophysical properties distinct from those of their discrete precursors. Controlling the assembly process of MNCs and understanding the assembly-disassembly dynamics can have implications in achieving the reversible self-assembly of MNCs. The formation of self-assembled copper nanoclusters (CuNCs) as homogeneous superstructures and the underlying mechanisms governing such a process remain unexplored. Smart molecular imprinting of surface ligands can establish the forces necessary for the formation of such superstructures. Herein, we report highly luminescent, ordered superstructures of 4-phenylimidazole-2-thiol (4-PIT)-protected CuNCs with the help of l-ascorbic acid as a secondary ligand. Through a comprehensive spectroscopic analysis, we deciphered the mechanism of the self-assembly process, where the role of interligand H-bonding and C-H-π interactions was established. Notably, efficient reversibility of assembly-disassembly was demonstrated by re-establishing the interligand interactions and regenerating their photophysical and morphological signatures.