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Doris SE, Lynch JJ, Li C, et al. Mechanistic insight into the formation of cationic naked nanocrystals generated under equilibrium control. J Am Chem Soc. 2014;136(44):15702-10doi: 10.1021/ja508675t.
Doris, S. E., Lynch, J. J., Li, C., Wills, A. W., Urban, J. J., & Helms, B. A. (2014). Mechanistic insight into the formation of cationic naked nanocrystals generated under equilibrium control. Journal of the American Chemical Society, 136(44), 15702-10. https://doi.org/10.1021/ja508675t
Doris, Sean E, et al. "Mechanistic insight into the formation of cationic naked nanocrystals generated under equilibrium control." Journal of the American Chemical Society vol. 136,44 (2014): 15702-10. doi: https://doi.org/10.1021/ja508675t
Doris SE, Lynch JJ, Li C, Wills AW, Urban JJ, Helms BA. Mechanistic insight into the formation of cationic naked nanocrystals generated under equilibrium control. J Am Chem Soc. 2014 Nov 05;136(44):15702-10. doi: 10.1021/ja508675t. Epub 2014 Oct 24. PMID: 25302526.
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J Am Chem Soc. 2014 Nov 05;136(44):15702-10. doi: 10.1021/ja508675t. Epub 2014 Oct 24.

Mechanistic insight into the formation of cationic naked nanocrystals generated under equilibrium control.

Journal of the American Chemical Society

Sean E Doris, Jared J Lynch, Changyi Li, Andrew W Wills, Jeffrey J Urban, Brett A Helms

Affiliations

  1. The Molecular Foundry, Lawrence Berkeley National Laboratory , One Cyclotron Road, Berkeley, California 94720, United States.

PMID: 25302526 DOI: 10.1021/ja508675t

Abstract

Cationic naked nanocrystals (NCs) are useful building units for assembling hierarchical mesostructured materials. Until now, their preparation required strongly electrophilic reagents that irreversibly sever bonds between native organic ligands and the NC surface. Colloidal instabilities can occur during ligand stripping if exposed metal cations desorb from the surface. We hypothesized that cation desorption could be avoided were we able to stabilize the surface during ligand stripping via ion pairing. We were successful in this regard by carrying out ligand stripping under equilibrium control with Lewis acid-base adducts of BF3. To better understand the microscopic processes involved, we studied the reaction pathway in detail using in situ NMR experiments and electrospray ionization mass spectrometry. As predicted, we found that cationic NC surfaces are transiently stabilized post-stripping by physisorbed anionic species that arise from the reaction of BF3 with native ligands. This stabilization allows polar dispersants to reach the NC surface before cation desorption can occur. The mechanistic insights gained in this work provide a much-needed framework for understanding the interplay between NC surface chemistry and colloidal stability. These insights enabled the preparation of stable naked NC inks of desorption-susceptible NC compositions such as PbSe, which were easily assembled into new mesostructured films and polymer-nanocrystal composites with wide-ranging technological applications.

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