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.

The synthesis and characterization of a new kind of cis- and trans-cyclometalated square-planar platinum(II) complexes is reported. Uncharged organometallic compounds carrying one or two of the CN-donor ligand L were prepared. Due to the heterobidentate coordination of the achiral chelate ligand, the formed [PtLCl(SEt)], cis- and trans-[PtL] complexes are chiral with the metal serving as the stereo center. The enantiomers of complex trans-[PtL] could be separated and their absolute configuration was determined by anomalous X-ray diffraction, in accordance with CD spectroscopic results and TD-DFT calculations. All compounds were fully characterized by NMR spectroscopy, mass spectrometry and X-ray structure determination. The photophysical properties of trans-[PtL] have been investigated showing phosphorescence in solution and in the solid state with a moderate quantum yield. For the enantiomers, strong circular dichroism (CD) and circularly polarized luminescence (CPL) effects were observed, rendering this new structural motif suitable for application in chiroptical and luminescent materials.

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.

Most metallo-supramolecular assemblies of low nuclearity adopt simple topologies, with bridging ligands spanning neighboring metal centers in a direct fashion. Here we contribute a new structural motif to the family of host compounds with low metal count (two) that consists of a pair of doubly-interlocked, Figure-eight-shaped subunits, also termed "lemniscates". Each metal is chelated by two chiral bidentate ligands, composed of a peptidic macrocycle that resembles a natural product with two pyridyl-terminated arms. DFT calculation results suggest that dimerization of the mononuclear halves is driven by a combination of 1) Coulomb interaction with a central anion, 2) p-stacking between intertwined ligand arms and 3) dispersive interactions between the structures compact inner core bedded into an outer shell composed of the cavitand-type macrocycles. The resulting cage-like architecture was characterized by NMR, MS and Xray structure analyses. This new mechanically bonded system highlights the scope of structural variety accessible in metalmediated self-assemblies composed of only a few constituents.

The self-assembly of interpenetrated double-cages was examined with respect to various synthetic modifications of the dibenzosuberone backbone.