Stimuli‐Responsive Interconversion between Poly‐NHC‐Based Organometallic Assemblies and Their Self‐Aggregated Dimers

Comprehensive Summary Poly‐NHC‐based organometallic assemblies 3‐PF 6 , 3‐SbF 6 and 3‐OTf were obtained and verified by NMR spectroscopy, ESI mass spectrometry and single‐crystal X‐ray diffraction analyses. Controllable structural interconversion was observed between the poly‐NHC‐based organometallic assemblies and their self‐aggregated dimers in solution affected by concentration, solvent and metal ion. 1 H NMR spectra of assembly 3‐PF 6 in CD 3 CN at different concentrations demonstrated controllable structural interconversion, and 19 F NMR spectrum of assembly 3‐PF 6 at high concentration further evidenced the presence of the free hexafluorophosphate anion and encapsulated hexafluorophosphate anion for its two sets of signals. In addition, single‐crystal X‐ray diffraction analysis provided clear evidence that in the solid state, two assemblies 3‐PF 6 were vertically stuck, forming a self‐aggregated dimer with an encapsulated hexafluorophosphate anion. Investigating the reversible structural interconversion is beneficial for revealing the intrinsic nature on the atom level and paving the way to design the stimuli‐responsive functional system.