Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses

Junfei Xing, Luca Schweighauser, Satoshi Okada, Koji Harano () and Eiichi Nakamura ()
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Junfei Xing: The University of Tokyo
Luca Schweighauser: The University of Tokyo
Satoshi Okada: The University of Tokyo
Koji Harano: The University of Tokyo
Eiichi Nakamura: The University of Tokyo

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: Abstract Chemical reactions in solution almost always take place via a series of minute intermediates that are often in rapid equilibrium with each other, and hence hardly characterizable at the level of atomistic molecular structures. We found that single-molecule atomic-resolution real-time electron microscopic (SMART-EM) video imaging provides a unique methodology for capturing and analyzing the minute reaction intermediates, as illustrated here for single prenucleation clusters (PNCs) in the reaction mixture of metal–organic frameworks (MOFs). Specifically, we found two different types of PNCs are involved in the formation of MOF-2 and MOF-5 from a mixture of zinc nitrate and benzene dicarboxylates at 95 °C and 120 °C, respectively. SMART-EM identified a small amount of 1-nm-sized cube and cube-like PNCs in the MOF-5 synthesis, but not in the MOF-2 synthesis. In the latter, we instead found only linear and square PNCs, suggesting that the MOF-2/-5 bifurcation takes place at the PNC stage.

Date: 2019
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DOI: 10.1038/s41467-019-11564-4

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