Chiral Metallosupramolecular Polyhedra

Diastereomer Resolution of M4L6 Coordination Cages by Ultra‐High‐Resolution Ion‐Mobility Mass Spectrometry

“…Self‐assembled cages often exist as interconverting diastereomers due to unsymmetrical pairing of their constituent components, such as ligands or weak structural coupling between the stereogenic metal centres (Figure 1b). [2d, 3] While diastereomers can be amplified and/or isolated through ligand design, [4] guest binding [5] or crystallisation, [5, 6] the efficient separation of all diastereomers is necessary for the investigation of their individual properties [7]…”

Remote stereocentres do not disrupt the stereochemical coupling in homochiral [M2L3] helicates and [M4L6] tetrahedra

“…In general, rigid bridging ligands with suitable substituents that lead to atropisomers result in strong positive communication between stereocentres, while longer more flexible ligands or those with configurations that disfavour atropisomerism, result in weaker (or negligible) stereochemical communication. [11][12][13] Similarly, the presence of various substituents on a bridging ligand can dramatically influence the course of a self-assembly reaction leading to products that have vastly different geometries, complexity or function. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Recently, we have shown that we can control the equilibrium formed between mixtures of [Fe 2 L 3 ] 4+ helicates and [Fe 4 L 6 ] 8+ tetrahedra through the incorporation of different degrees of steric bulk on the central ring of the bridging ligand using quaterpyridines 33-40 L 1 and L 2 .…”

“…In general, rigid bridging ligands with suitable substituents that lead to atropisomers result in strong positive communication between stereocentres, while longer more flexible ligands or those with configurations that disfavour atropisomerism, result in weaker (or negligible) stereochemical communication. 11–13 Similarly, the presence of various substituents on a bridging ligand can dramatically influence the course of a self-assembly reaction leading to products that have vastly different geometries, complexity or function. 14–32…”