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Effect of Cation–π Interaction on Macroionic Self‐Assembly
Author(s) -
Luo Jiancheng,
Chen Kun,
Yin Panchao,
Li Tao,
Wan Gang,
Zhang Jin,
Ye Songtao,
Bi Xiaoman,
Pang Yi,
Wei Yongge,
Liu Tianbo
Publication year - 2018
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.201800409
Subject(s) - isothermal titration calorimetry , counterion , chemistry , titration , ion , crystallography , aromaticity , ionic bonding , stereochemistry , inorganic chemistry , organic chemistry , molecule
A series of rod‐shaped polyoxometalates (POMs) [Bu 4 N] 7 [Mo 6 O 18 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 18 ] and [Bu 4 N] 7 [ArNMo 6 O 17 NC(CH 2 O) 3 MnMo 6 O 18 (OCH 2 ) 3 CNMo 6 O 17 NAr] (Ar=2,6‐dimethylphenyl, naphthyl and 1‐methylnaphthyl) were chosen to study the effects of cation–π interaction on macroionic self‐assembly. Diffusion ordered spectroscopy (DOSY) and isothermal titration calorimetry (ITC) techniques show that the binding affinity between the POMs and Zn 2+ ions is enhanced significantly after grafting aromatic groups onto the clusters, leading to the effective replacement of tetrabutylammonium counterions (TBAs) upon the addition of ZnCl 2 . The incorporation of aromatic groups results in the significant contribution of cation–π interaction to the self‐assembly, as confirmed by the opposite trend of assembly size vs. ionic strength when compared with those without aromatic groups. The small difference between two aromatic groups toward the Zn 2+ ions is amplified after combining with the clusters, which consequently triggers the self‐recognition behavior between two highly similar macroanions.