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.

Department of Chemistry San José State University San José California 95192 United States

Department of Physics Stanford University Palo Alto California 94025 United States

Institute of Organic Chemistry and Biochemistry Academy of Sciences of the Czech Republic Flemingovo nam 2 166 10 Prague 6 Czech Republic

Microelectronics Research Unit Faculty of Information Technology and Electrical Engineering University of Oulu Oulu Finland 90014

Quantum Electromagnetics Division National Institute of Standards and Technology Boulder Colorado 80305 United States

Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Menlo Park California 94025 United States

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

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