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Construction of π‐Surface‐Metalated Pillar[5]arenes which Bind Anions via Anion–π Interactions
Author(s) -
Jiang Bo,
Wang Wei,
Zhang Ying,
Lu Ye,
Zhang ChangWei,
Yin GuangQiang,
Zhao XiaoLi,
Xu Lin,
Tan Hongwei,
Li Xiaopeng,
Jin GuoXin,
Yang HaiBo
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707209
Subject(s) - trifluoromethanesulfonate , cationic polymerization , chemistry , pillar , transition metal , molecule , metal , ligand (biochemistry) , crystallography , polymer chemistry , organic chemistry , catalysis , biochemistry , receptor , structural engineering , engineering
By simple ligand exchange of the cationic transition‐metal complexes [(Cp*)M(acetone) 3 ](OTf) 2 (Cp*=pentamethylcyclopentadienyl and M=Ir or Rh) with pillar[5]arene, mono‐ and polynuclear pillar[5]arenes, a new class of metalated host molecules, is prepared. Single‐crystal X‐ray analysis shows that the charged transition‐metal cations are directly bound to the outer π‐surface of aromatic rings of pillar[5]arene. One of the triflate anions is deeply embedded within the cavity of the trinuclear pillar[5]arenes, which is different to the host–guest behavior of most pillar[5]arenes. DFT calculation of the electrostatic potential revealed that the metalated pillar[5]arenes featured an electron‐deficient cavity due to the presence of the electron‐withdrawing transition metals, thus allowing encapsulation of electron‐rich guests mainly driven by anion–π interactions.