Deep-blue luminescent [{Ir(C^N)2}3(L)2]3+ coordination cages with structurally integral pyridyl-azo-phenyl groups can be reversibly photo-isomerised with no compositional change.

The racemic ligands (±)‐tris(isonicotinoyl)‐cyclotriguaiacylene (L1), or (±)‐tris(4‐pyridyl‐methyl)‐cyclotriguaiacylene (L2) assemble with racemic (Λ,Δ)‐[Ir(ppy)2(MeCN)2]+, in which ppy=2‐phenylpyridinato, to form [{Ir(ppy)2}3(L)2]3+ metallo‐cryptophane cages. The crystal structure of [{Ir(ppy)2}3(L1)2]⋅3BF4 has MM‐ΛΛΛ and PP‐ΔΔΔ isomers, and homochiral self‐sorting occurs in solution, a process accelerated by a chiral guest. Self‐recognition between L1 and L2 within cages does not occur, and cages show very slow ligand exchange. Both cages are phosphorescent, with [{Ir(ppy)2}3(L2)2]3+ having enhanced and blue‐shifted emission when compared with [{Ir(ppy)2}3(L1)2]3+.

Molecular recognition has been widely investigated under equilibrium conditions, but little is known about such processes when perturbed by external forces. Here, we investigate the influence of electric fields on complexes formed between metallosupramolecular cages and a protein nanopore at the single-molecule level. Association rates were dominated by the applied voltage, while local electrostatic interactions between the cage and the nanopore more greatly influenced the dissociation kinetics. Exploiting these principles, it was shown that the externally applied voltage could be used to selectively bind a specific cage from a mixture containing a large excess of other cages. Moreover, the applied voltage could also be used to drive supramolecular enantio-inversion of the chiral cages, or occasionally, the nonequilibrium capture and disassembly of cages deep within the nanopore. Similar principles might be exploited in the design of other molecular devices that operate within externally applied electric fields or biogenic transmembrane potentials.

2D M3L2 coordination polymers (M = Re(i), Cu(ii), Co(ii), Ni(ii)) feature metal-linked M6L2-cages, and the Re(i) material absorbs iodine.

Tris-N-alkylpyridinium-functionalised cyclotriguaiacylene hosts as axles in branched [4]pseudorotaxane formationA series of [4]pseudorotaxanes composed of three-way axle threads based on the cyclotriguaiacylene family of crown-shaped cavitands and three threaded macrocyclic components has been achieved. These exploit the strong affinity for electron-poor alkyl-pyridinium units to reside within the electron-rich cavity of macrocycles, in this case dimethoxypillar