Stepwise Self‐Assembly and Dynamic Exchange of Supramolecular Snowflakes

Abstract Snowflake, a highly symmetrical hexagram figure, is challenging to be expressed by chemistry/supramolecular chemistry due to the complex structure. Herein, we have constructed super snowflake supramolecules using terpyridine (tpy)‐based metal‐organic building blocks with tpy‐Ru(II)‐tpy and tpy‐Zn(II)‐tpy connectivities through stepwise strategies in high yield. The structures were characterized by multi‐dimensional mass spectrometry and multi‐dimensional NMR spectrometry. In order to address the stability/tolerance of our designed super snowflake structures, ligand exchange behaviors between different supramolecules with various arm length were fully investigated by mass spectrometry. The study revealed that three modes could exist in such binary systems, including full exchange, partial exchange and self‐sorting (no exchange) depending on the length difference of ligands.