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Title: Effect of Cation-π Interaction on Macroionic Self-Assembly

Here, a series of rod–shaped polyoxometalates (POMs) [Bu 4N] 7[Mo 6O 18NC(CH 2O) 3MnMo 6O 18(OCH 2) 3CNMo 6O 18] and [Bu 4N] 7[ArNMo 6O 17NC(CH 2O) 3MnMo 6O 18(OCH 2) 3CNMo 6O 17NAr] (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.
Authors:
ORCiD logo [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. Univ. of Akron, Akron, OH (United States)
  2. Tsinghua Univ., Beijing (People's Republic of China)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Northern Illinois Univ., DeKalb, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 15; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Science Foundation (NSF); National Natural Science Foundation of China (NNSFC); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; binding affinity; cation-pi interaction; macroionic self-assembly; polyoxometalates; self-recognition
OSTI Identifier:
1461310
Alternate Identifier(s):
OSTI ID: 1423707

Luo, Jiancheng, Chen, Kun, Yin, Panchao, Li, Tao, Wan, Gang, Zhang, Jin, Ye, Songtao, Bi, Xiaoman, Pang, Yi, Wei, Yongge, and Liu, Tianbo. Effect of Cation-π Interaction on Macroionic Self-Assembly. United States: N. p., Web. doi:10.1002/anie.201800409.
Luo, Jiancheng, Chen, Kun, Yin, Panchao, Li, Tao, Wan, Gang, Zhang, Jin, Ye, Songtao, Bi, Xiaoman, Pang, Yi, Wei, Yongge, & Liu, Tianbo. Effect of Cation-π Interaction on Macroionic Self-Assembly. United States. doi:10.1002/anie.201800409.
Luo, Jiancheng, Chen, Kun, Yin, Panchao, Li, Tao, Wan, Gang, Zhang, Jin, Ye, Songtao, Bi, Xiaoman, Pang, Yi, Wei, Yongge, and Liu, Tianbo. 2018. "Effect of Cation-π Interaction on Macroionic Self-Assembly". United States. doi:10.1002/anie.201800409.
@article{osti_1461310,
title = {Effect of Cation-π Interaction on Macroionic Self-Assembly},
author = {Luo, Jiancheng and Chen, Kun and Yin, Panchao and Li, Tao and Wan, Gang and Zhang, Jin and Ye, Songtao and Bi, Xiaoman and Pang, Yi and Wei, Yongge and Liu, Tianbo},
abstractNote = {Here, a series of rod–shaped polyoxometalates (POMs) [Bu4N]7[Mo6O18NC(CH2O)3MnMo6O18(OCH2)3CNMo6O18] and [Bu4N]7[ArNMo6O17NC(CH2O)3MnMo6O18(OCH2)3CNMo6O17NAr] (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 Zn2+ ions is enhanced significantly after grafting aromatic groups onto the clusters, leading to the effective replacement of tetrabutylammonium counterions (TBAs) upon the addition of ZnCl2. 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 Zn2+ ions is amplified after combining with the clusters, which consequently triggers the self–recognition behavior between two highly similar macroanions.},
doi = {10.1002/anie.201800409},
journal = {Angewandte Chemie (International Edition)},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}