Abstract
High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2F6NaW18O56]7− from simple tungstate Na2WO2F4 was demonstrated by using 2D 19F–19F NOESY, 2D 19F–19F COSY NMR spectroscopy, a new 2D 19F{183W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 369-379 |
| Number of pages | 11 |
| Journal | Chemistry - A European Journal |
| Volume | 24 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - Jan 9 2018 |
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Keywords
- mass spectrometry
- NMR spectroscopy
- polyoxometalates
- self-assembly
- tungsten
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Self-Assembly through Noncovalent Preorganization of Reactants : Explaining the Formation of a Polyfluoroxometalate. / Schreiber, Roy E.; Avram, Liat; Neumann, Ronny.
In: Chemistry - A European Journal, Vol. 24, No. 2, 09.01.2018, p. 369-379.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Self-Assembly through Noncovalent Preorganization of Reactants
T2 - Explaining the Formation of a Polyfluoroxometalate
AU - Schreiber, Roy E.
AU - Avram, Liat
AU - Neumann, Ronny
PY - 2018/1/9
Y1 - 2018/1/9
N2 - High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2F6NaW18O56]7− from simple tungstate Na2WO2F4 was demonstrated by using 2D 19F–19F NOESY, 2D 19F–19F COSY NMR spectroscopy, a new 2D 19F{183W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions.
AB - High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2F6NaW18O56]7− from simple tungstate Na2WO2F4 was demonstrated by using 2D 19F–19F NOESY, 2D 19F–19F COSY NMR spectroscopy, a new 2D 19F{183W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions.
KW - mass spectrometry
KW - NMR spectroscopy
KW - polyoxometalates
KW - self-assembly
KW - tungsten
UR - http://www.scopus.com/inward/record.url?scp=85040323401&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85040323401&partnerID=8YFLogxK
U2 - 10.1002/chem.201704287
DO - 10.1002/chem.201704287
M3 - Article
AN - SCOPUS:85040323401
VL - 24
SP - 369
EP - 379
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 2
ER -