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Title: Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction

Journal Article · · Chemistry - A European Journal
 [1]; ORCiD logo [1];  [2];  [1];  [1];  [3];  [2]; ORCiD logo [1]
  1. The Univ. of Akron, Akron, OH (United States)
  2. Jacobs Univ., Bremen (Germany)
  3. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

Abstract Three types of macroanion–countercation interactions in dilute solution, decided by the strength of electrostatic attraction and the change of hydration shells are reported: minor interaction between macroanions [MO 8 Pd 12 (SeO 3 ) 8 ] 6− (M=Zn 2+ or Ni 2+ ) and monovalent cations (Na + , K + , Rb + , Cs + ), leaving their hydration shells intact (solvent‐separated ion‐pairs); strong binding between macroanions and divalent cations (Sr 2+ , Ba 2+ ) to form solvent‐shared ion‐pairs with partial dehydration; very strong electrostatic attraction between macroanions and Y 3+ ion with contact ion‐pairs formation by severely breaking their original hydration shells and forming new ones. In addition, divalent cations can help the macroanions self‐assemble into hollow spherical blackberry structures through counterion‐mediated attraction, whereas macroanions with mono‐ or trivalent cations only stay as discrete ions due to either weak interaction or a small number of bound countercations.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
University of Akron; National Science Foundation (NSF); German Research Foundation (DFG); Jacobs University Bremen gGmbH; USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1471520
Alternate ID(s):
OSTI ID: 1418418
Journal Information:
Chemistry - A European Journal, Vol. 24, Issue 12; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

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Cited By (8)

Tuning the Intercage Distance in Charge‐Regulated Blackberry‐Type Assemblies through Host–Guest Chemistry journal March 2019
Polyoxometalates as components of supramolecular assemblies journal January 2019
Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry journal January 2020
Comment on “Photochemical reduction of carbon dioxide coupled with water oxidation using various soft-oxometalate (SOM) based catalytic systems” ( J. Mater. Chem. A , 2016, 4 , 8875–8887) journal January 2019
Isotope and Hydrogen‐Bond Effects on the Self‐Assembly of Macroions in Dilute Solution journal November 2019
pH-induced phase transition and crystallization of soft-oxometalates (SOMs) into polyoxometalates (POMs): a study on crystallization from colloids journal October 2018
Jenseits von Ladungsausgleich: Gegenkationen in der Polyoxometallat‐Chemie journal October 2019
Polyoxometalates as components of supramolecular assemblies text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hydration shell
ion pair
macroion
polypalladate
thermodynamics