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A series of rim-differentiated Co-pillar[4+1]arenes featuring penta-substituted “upper” rims and mono-functionalisable “lower” rims was successfully synthesised and fully characterised. These novel pillar[5]arene-based scaffolds with clickable moieties and extra synthetic handles are versatile platforms for self-assembled molecular architectures and biological applications.

Graphical abstract: Rim-differentiated Co-pillar[4+1]arenes

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