Chiral Self‐Discrimination and Guest Recognition in Helicene‐Based Coordination Cages

Chiral nanosized confinements play a major role for enantioselective recognition and reaction control in biological systems. Supramolecular self‐assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2L4] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis‐monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self‐discrimination to an achiral meso cage, cis‐[Pd2L1P2L1M2]. Enantiopure L1 forms homochiral cages [Pd2L1P/M4]. A longer derivative L2 forms chiral cages [Pd2L2P/M4] with larger cavities, which bind optical isomers of chiral guests with different affinities. Owing to its distinct chiroptical properties, this cage can distinguish non‐chiral guests of different lengths, as they were found to squeeze or elongate the cavity under modulation of the helical pitch of the helicenes. The CD spectroscopic results were supported by ion mobility mass spectrometry. Chirale [6]Helicene dienen als Bausteine für die Assemblierung von [Pd2L4]‐Koordinationskäfigen und verflochtenen [Pd4L8]‐Dimeren. Die Länge der Liganden bestimmt die chirale Selbstunterscheidung und die Erkennung enantiomerer Gäste. Eine Veränderung der Helicen‐Ganghöhe ermöglicht die Unterscheidung nicht‐chiraler Gäste durch eine Kombination aus CD‐Spektroskopie und Ionenmobilitätsmassenspektrometrie.