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Homochiral Self‐Sorted and Emissive Ir III Metallo‐Cryptophanes
Author(s) -
Pritchard Victoria E.,
Rota Martir Diego,
Oldknow Samuel,
Kai Shumpei,
Hiraoka Shuichi,
Cookson Nikki J.,
ZysmanColman Eli,
Hardie Michaele J.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701348
Subject(s) - phosphorescence , chemistry , ligand (biochemistry) , tris , crystallography , iridium , crystal structure , stereochemistry , photochemistry , medicinal chemistry , catalysis , organic chemistry , fluorescence , biochemistry , physics , receptor , quantum mechanics
Abstract 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 ]⋅3BF 4 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+ .