Hierarchical self-assembly of crown ether based metal-carbene cages into multiple stimuli-responsive cross-linked supramolecular metallogel

The hierarchical self-assembly (HSA) strategy widely utilized in biological systems has been applied in artificial systems to orchestrate small building blocks into complex functional architectures. The non-interfering interactions glue various building blocks together and produce new species with attractive properties. Herein, we functionalized NHC-based assemblies with orthogonal host-guest interaction to fabricate metal-carbene based supramolecular polymer gel. A series of unique crown ether-appended cylinder-like trinuclear Au I hexacarbene assemblies [Au 3 ( L ) 2 ](PF 6 ) 3 ( L=D1–D4, A1–A4 ) were synthesized from the corresponding trisimidazolium salts H 3 - L (PF 6 ) 3 ( L=D1–D4, A1–A4 ) in which the N-wingtip of the imidazole moieties were substituted with three identical crown ether groups of different sizes (B15C5, B18C6, B21C7, DB24C8). The gold carbene assembly is able to complex six ammonium salts without disrupting the underlying metal-carbene cylinders. In addition, the supramolecular polymer metallogel featuring a multiple-responsiveness can be formed by using [Au 3 ( A4 ) 2 ](PF 6 ) 3 appended with DB24C8 as the core and bisammonium salt as the cross-linker. The case of introducing orthogonal interaction to NHC moiety by N-wingtip substitution demonstrates the feasibility and the power of such strategy to expand the NHC-based supramolecular system and endow them with novel properties.