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Geometrically Restricted Intermediates in the Self‐Assembly of an M 12 L 24 Cuboctahedral Complex
Author(s) -
Fujita Daishi,
Yokoyama Hiroyuki,
Ueda Yoshihiro,
Sato Sota,
Fujita Makoto
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409216
Subject(s) - metastability , spectroscopy , nuclear magnetic resonance spectroscopy , crystallography , chemistry , self assembly , mass spectrometry , ligand (biochemistry) , topology (electrical circuits) , chemical physics , physics , stereochemistry , biochemistry , receptor , mathematics , organic chemistry , chromatography , quantum mechanics , combinatorics
The self‐assembly of a cuboctahedral M 12 L 24 complex is traced by time‐dependent NMR spectroscopy and mass spectrometry. The metastable intermediate structures that exist during the self‐assembly process are not a chaotic mixture of numerous species, but instead are geometrically restricted. Short‐lived M 8 L 16 (D 4d ) and relatively long‐lived M 9 L 18 (D 3h ) are fully characterized as major intermediates. Employing a ligand with a smaller bend angle (112°) allows these two species to be kinetically trapped and more clearly observed by NMR spectroscopy. X‐ray crystallography shows that M 9 L 18 has the framework topology predicted by geometric discussion.