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Title: Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction

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 [MO8Pd12(SeO3)8]6- (M = Zn2+ or Ni2+) and monovalent cations (Na+, K+, Rb+, Cs+), leaving their hydration shells intact (solvent-separated ion-pairs); strong binding between macroanions and divalent cations (Sr2+, Ba2+) to form solvent-shared ion-pairs with partial dehydration; very strong electrostatic attraction between macroanions and Y3+ ion with contact ion-pairs formation by severely breaking their original hydration shells and forming new ones. Additionally, 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.

Authors:
 [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)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
University of Akron; National Science Foundation (NSF); German Research Foundation (DFG); Jacobs University Bremen gGmbH; USDOE
OSTI Identifier:
1471520
Alternate Identifier(s):
OSTI ID: 1418418
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 12; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydration shell; ion pair; macroion; polypalladate; thermodynamics

Citation Formats

He, Jiazhi, Li, Hui, Yang, Peng, Haso, Fadi, Wu, Jiayingzi, Li, Tao, Kortz, Ulrich, and Liu, Tianbo. Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction. United States: N. p., 2017. Web. doi:10.1002/chem.201705873.
He, Jiazhi, Li, Hui, Yang, Peng, Haso, Fadi, Wu, Jiayingzi, Li, Tao, Kortz, Ulrich, & Liu, Tianbo. Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction. United States. doi:10.1002/chem.201705873.
He, Jiazhi, Li, Hui, Yang, Peng, Haso, Fadi, Wu, Jiayingzi, Li, Tao, Kortz, Ulrich, and Liu, Tianbo. Sat . "Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction". United States. doi:10.1002/chem.201705873. https://www.osti.gov/servlets/purl/1471520.
@article{osti_1471520,
title = {Tuning of Polyoxopalladate Macroanionic Hydration Shell via Countercation Interaction},
author = {He, Jiazhi and Li, Hui and Yang, Peng and Haso, Fadi and Wu, Jiayingzi and Li, Tao and Kortz, Ulrich and Liu, Tianbo},
abstractNote = {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 [MO8Pd12(SeO3)8]6- (M = Zn2+ or Ni2+) and monovalent cations (Na+, K+, Rb+, Cs+), leaving their hydration shells intact (solvent-separated ion-pairs); strong binding between macroanions and divalent cations (Sr2+, Ba2+) to form solvent-shared ion-pairs with partial dehydration; very strong electrostatic attraction between macroanions and Y3+ ion with contact ion-pairs formation by severely breaking their original hydration shells and forming new ones. Additionally, 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.},
doi = {10.1002/chem.201705873},
journal = {Chemistry - A European Journal},
number = 12,
volume = 24,
place = {United States},
year = {2017},
month = {12}
}

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    Works referencing / citing this record:

    pH-induced phase transition and crystallization of soft-oxometalates (SOMs) into polyoxometalates (POMs): a study on crystallization from colloids
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