Pritchard Victoria E, Rota Martir Diego, Oldknow Samuel, Kai Shumpei, Hiraoka Shuichi, Cookson Nikki J, Zysman-Colman Eli, Hardie Michaele J
School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.
Organic Semiconductor Centre, EaSTCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
Chemistry. 2017 May 5;23(26):6290-6294. doi: 10.1002/chem.201701348. Epub 2017 Apr 20.
The racemic ligands (±)-tris(isonicotinoyl)-cyclotriguaiacylene (L1), or (±)-tris(4-pyridyl-methyl)-cyclotriguaiacylene (L2) assemble with racemic (Λ,Δ)-[Ir(ppy) (MeCN) ] , in which ppy=2-phenylpyridinato, to form [{Ir(ppy) } (L) ] metallo-cryptophane cages. The crystal structure of [{Ir(ppy) } (L1) ]⋅3BF 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) } (L2) ] having enhanced and blue-shifted emission when compared with [{Ir(ppy) } (L1) ] .
外消旋配体（±）-三（异烟酰基）-环三聚愈创木酚（L1）或（±）-三（4-吡啶基甲基）-环三聚愈创木酚（L2）与外消旋（Λ，Δ）-[Ir（ppy）（MeCN）]（其中ppy = 2-苯基吡啶基）组装，形成[{Ir（ppy）}（L）]金属隐藻烷笼。[{Ir（ppy）}（L1）]·3BF的晶体结构具有MM-ΛΛΛ和PP-ΔΔΔ异构体，并且在溶液中发生同手性自分类，这一过程由手性客体加速。笼内L1和L2之间不会发生自识别，并且笼显示出非常缓慢的配体交换。两个笼均具有磷光性，与[{Ir（ppy）}（L1）]相比，[{Ir（ppy）}（L2）]具有增强的蓝移发射。
