%0 Journal Article
%T Efficient Self-Sorting Behaviours of Metallacages with Subtle Structural Differences.
%A Jin T
%A Zeng K
%A Zhang X
%A Dou WT
%A Hu L
%A Zhang D
%A Zhu W
%A Qian X
%A Yang HB
%A Xu L
%J Angew Chem Int Ed Engl
%V 0
%N 0
%D 2024 Jul 25
%M 39051526
%F 16.823
%R 10.1002/anie.202409878
%X Investigating the self-sorting behaviour of assemblies with subtle structural differences is a captivating yet challenging endeavour. Herein, we elucidate the unusual self-sorting behaviour of metallacages with subtle structural differences in batch reactors and microdroplets. Narcissistic self-sorting of metallacages has been observed for two ligands with identical sizes, shapes, and symmetries, with only minor differences in the substituted groups. In particular, the self-sorting process in microdroplets occurs within 1 min at room temperature, in stark contrast to batch reactors, which require equilibration for 30 min. To reveal the mechanism of self-sorting and the role of microdroplets, we conducted a series of experiments and theoretical calculations, including competitive self-assembly, cage-to-cage transformation, control experiments involving model metallacages with larger cavities, noncovalent interaction analysis, and root mean square deviation (RMSD) analysis. This research demonstrates an unusual case of self-sorting of very similar assemblies and provides a new strategy for facilitating the self-sorting efficiency of supramolecular systems.