Sub-10 nm Scale Lamellar Structures with a High Degree of Long-Range Order Fabricated by Orthogonal Self-Assembly of Crown Ether/Secondary Dialkylammonium Recognition and Metal···Metal/π-π Interactions.

We here present an orthogonal self-assembly strategy to fabricate a series of metallosupramolecular polymers by coupling planar platinum(II) complexes and starlike poly(ε-caprolactone), through Pt···Pt/π-π interactions and host-guest recognition between secondary dialkylammonium salts and crown ether groups. The solid metallosupramolecular polymers exhibit sub-10 nm scale lamellar structures and one of them occupies an extraordinary degree of long-range order. The platinum(II) complexes can be regarded as an individual supramolecular block to microphase segregate the polymeric segment. Moreover, the metallosupramolecular polymers show intense luminescence and appreciable proton conductivity, originating from these two supramolecular connection modes, respectively. This work paves the way for fabricating metallosupramolecular polymers showing both highly ordered nanostructures and multifunctional properties.