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Title: Cation Translocation around Single Polyoxometalate-Organic Hybrid Cluster Regulated by Electrostatic and Cation-π Interactions

Journal Article · · Angewandte Chemie (International Edition)
ORCiD logo [1];  [2];  [3];  [2];  [2];  [2];  [4];  [4];  [2];  [3];  [2]
  1. Univ. of Akron, OH (United States); DOE/OSTI
  2. Univ. of Akron, OH (United States)
  3. Emory Univ., Atlanta, GA (United States)
  4. Lehigh Univ., Bethlehem, PA (United States)
+ Show Author Affiliations

We report herein an interesting dynamic translocation process of countercations around one polyoxometalate(POM)–organic hybrid anionic cluster at various concentrations and temperatures. It was found that both electrostatic interactions and cation–π interactions regulate the position of small countercations around single clusters. The dynamic geometry and the symmetry of the hybrid macroions are largely affected by the type of counterions, as shown by nuclear magnetic resonance (NMR) spectroscopy studies and all-atom molecular dynamics simulation. It is also shown that electrostatic interactions dominate over cation–π interactions in determining the locations of the counterions in the current system.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0001089
OSTI ID:
1533095
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 12 Vol. 56; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

Three polyoxometalates-based organic–inorganic hybrids decorated with Cu–terpyridine complexes exhibiting dual functional electro-catalytic behaviors journal January 2019
Polyoxometalate encapsulation into metal–organic frameworks: the way towards functional nanomaterials for water splitting journal January 2018
Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry journal January 2020
A universal strategy for fabrication and morphology control of polyoxometalate-based metal–organic frameworks journal January 2020
Jenseits von Ladungsausgleich: Gegenkationen in der Polyoxometallat‐Chemie journal October 2019
A Nonclassical Polyoxoanion [P 3 W 6 (O 2 ) 6 (OH) 2 O 22 ] 7- Constructed by Two {PW 3 (O 2 ) 3 (OH)O 9 } Subunits and a {PO 4 } Group : A Nonclassical Polyoxoanion [P journal August 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry
cation–pi interactions
electrostatic interactions
polyoxometalates
MD simulations
NMR spectroscopy