Homochiral Self-Sorted and Emissive IrIII Metallo-Cryptophanes.
Victoria E PritchardDiego Rota MartirSamuel OldknowShumpei KaiShuichi HiraokaNikki J CooksonEli Zysman-ColmanMichaele J HardiePublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2017)
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+ .