Geometrically restricted intermediates in the self-assembly of an M12L24 cuboctahedral complex

Daishi Fujita; Hiroyuki Yokoyama; Yoshihiro Ueda; Sota Sato; Makoto Fujita

doi:10.1002/anie.201409216

Geometrically restricted intermediates in the self-assembly of an M12L24 cuboctahedral complex

Angew Chem Int Ed Engl. 2015 Jan 2;54(1):155-8. doi: 10.1002/anie.201409216. Epub 2014 Nov 7.

Authors

Daishi Fujita¹, Hiroyuki Yokoyama, Yoshihiro Ueda, Sota Sato, Makoto Fujita

Affiliation

¹ Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan).

PMID: 25381901
DOI: 10.1002/anie.201409216

Abstract

The self-assembly of a cuboctahedral M12 L24 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 M8 L16 (D4d ) and relatively long-lived M9 L18 (D3h ) 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 M9 L18 has the framework topology predicted by geometric discussion.

Keywords: geometrical restriction; metastable intermediates; palladium; self-assembly.