Metastable Brominated Nanodiamond Surface Enables Room Temperature and Catalysis-Free Amine Chemistry

Publication Date

2-3-2022

Document Type

Article

Publication Title

Journal of Physical Chemistry Letters

Volume

13

Issue

4

DOI

10.1021/acs.jpclett.1c04090

First Page

1147

Last Page

1158

Abstract

Bromination of high-pressure, high-temperature (HPHT) nanodiamond (ND) surfaces has not been explored and can open new avenues for increased chemical reactivity and diamond lattice covalent bond formation. The large bond dissociation energy of the diamond lattice-oxygen bond is a challenge that prevents new bonds from forming, and most researchers simply use oxygen-terminated NDs (alcohols and acids) as reactive species. In this work, we transformed a tertiary-alcohol-rich ND surface to an amine surface with ∼50% surface coverage and was limited by the initial rate of bromination. We observed that alkyl bromide moieties are highly labile on HPHT NDs and are metastable as previously found using density functional theory. The strong leaving group properties of the alkyl bromide intermediate were found to form diamond-nitrogen bonds at room temperature and without catalysts. This robust pathway to activate a chemically inert ND surface broadens the modalities for surface termination, and the unique surface properties of brominated and aminated NDs are impactful to researchers for chemically tuning diamond for quantum sensing or biolabeling applications.

Comments

Full author list: Cynthia Melendrez, Jorge A. Lopez-Rosas, Camron X. Stokes, Tsz Ching Cheung, Sang-Jun Lee, Charles James Titus, Jocelyn Valenzuela, Grace Jeanpierre, Halim Muhammad, Polo Tran, Perla Jasmine Sandoval, Tyanna Supreme, Virginia Altoe, Jan Vavra, Helena Raabova, Vaclav Vanek, Sami Sainio, William B. Doriese, Galen C. O’Neil, Daniel S. Swetz, Joel N. Ullom, Kent Irwin, Dennis Nordlund, Petr Cigler, and Abraham Wolcott

Department

Chemistry

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