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Self‐Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate
Author(s) -
Schreiber Roy E.,
Avram Liat,
Neumann Ronny
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704287
Subject(s) - chemistry , supramolecular chemistry , two dimensional nuclear magnetic resonance spectroscopy , nuclear magnetic resonance spectroscopy , non covalent interactions , self assembly , spectroscopy , crystallography , molecule , chemical physics , crystallization , supramolecular assembly , computational chemistry , stereochemistry , crystal structure , organic chemistry , physics , hydrogen bond , quantum mechanics
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 [H 2 F 6 NaW 18 O 56 ] 7− from simple tungstate Na 2 WO 2 F 4 was demonstrated by using 2D 19 F– 19 F NOESY, 2D 19 F– 19 F COSY NMR spectroscopy, a new 2D 19 F{ 183 W} 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.