Alkaline-earth metal cations as structure building blocks for molecular cages with entrapment and controlled release of quintuple ionic aggregates

Chi Tsang Wang, Ler Chun Shiu, Kom Bei Shiu

研究成果: Article

4 引文 (Scopus)

摘要

Currently, main-group metal cations are totally neglected as the structure-building blocks for the self-assembly of supramolecular coordination metallocages due to the lack of directional bonding. However, here we show that a common Arrhenius acid-base neutralization allows the alkaline-earth metal cations to act as charged binders, easily connecting two or more highly directional anionic transition-metal-based metalloligands to coordination polymers. With a metal salt such as K+PF6- added during the neutralization, the main-group metal-connected skeleton can be templated by the largest yet reported ionic-aggregate anion, K2(PF6)3-, formed from KPF6 in solution, into molecular metallocages, encapsulating the ion. Crystal-structure details, DFT-calculation results, and controlled-release behavior support the presence of K2(PF6)3- as a guest in the cage. Upon removal of PF6- ions, the cage stays intact. Other ions like BF4- can be put back in.

原文English
頁(從 - 到)7026-7029
頁數4
期刊Chemistry - A European Journal
21
發行號19
DOIs
出版狀態Published - 2015 五月 4

指紋

Alkaline Earth Metals
Alkaline earth metals
Cations
Positive ions
Metals
Ions
Discrete Fourier transforms
Self assembly
Binders
Transition metals
Anions
Polymers
Negative ions
Salts
Crystal structure
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

引用此文

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abstract = "Currently, main-group metal cations are totally neglected as the structure-building blocks for the self-assembly of supramolecular coordination metallocages due to the lack of directional bonding. However, here we show that a common Arrhenius acid-base neutralization allows the alkaline-earth metal cations to act as charged binders, easily connecting two or more highly directional anionic transition-metal-based metalloligands to coordination polymers. With a metal salt such as K+PF6- added during the neutralization, the main-group metal-connected skeleton can be templated by the largest yet reported ionic-aggregate anion, K2(PF6)3-, formed from KPF6 in solution, into molecular metallocages, encapsulating the ion. Crystal-structure details, DFT-calculation results, and controlled-release behavior support the presence of K2(PF6)3- as a guest in the cage. Upon removal of PF6- ions, the cage stays intact. Other ions like BF4- can be put back in.",
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AU - Wang, Chi Tsang

AU - Shiu, Ler Chun

AU - Shiu, Kom Bei

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Y1 - 2015/5/4

N2 - Currently, main-group metal cations are totally neglected as the structure-building blocks for the self-assembly of supramolecular coordination metallocages due to the lack of directional bonding. However, here we show that a common Arrhenius acid-base neutralization allows the alkaline-earth metal cations to act as charged binders, easily connecting two or more highly directional anionic transition-metal-based metalloligands to coordination polymers. With a metal salt such as K+PF6- added during the neutralization, the main-group metal-connected skeleton can be templated by the largest yet reported ionic-aggregate anion, K2(PF6)3-, formed from KPF6 in solution, into molecular metallocages, encapsulating the ion. Crystal-structure details, DFT-calculation results, and controlled-release behavior support the presence of K2(PF6)3- as a guest in the cage. Upon removal of PF6- ions, the cage stays intact. Other ions like BF4- can be put back in.

AB - Currently, main-group metal cations are totally neglected as the structure-building blocks for the self-assembly of supramolecular coordination metallocages due to the lack of directional bonding. However, here we show that a common Arrhenius acid-base neutralization allows the alkaline-earth metal cations to act as charged binders, easily connecting two or more highly directional anionic transition-metal-based metalloligands to coordination polymers. With a metal salt such as K+PF6- added during the neutralization, the main-group metal-connected skeleton can be templated by the largest yet reported ionic-aggregate anion, K2(PF6)3-, formed from KPF6 in solution, into molecular metallocages, encapsulating the ion. Crystal-structure details, DFT-calculation results, and controlled-release behavior support the presence of K2(PF6)3- as a guest in the cage. Upon removal of PF6- ions, the cage stays intact. Other ions like BF4- can be put back in.

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