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

0555987 - ÚOCHB 2023 RIV US eng J - Journal Article
Melendrez, C. - Lopez-Rosas, J. A. - Stokes, C. X. - Cheung, T. C. - Lee, S. J. - Titus, C. J. - Valenzuela, J. - Jeanpierre, G. - Muhammad, H. - Tran, P. - Sandoval, P. J. - Supreme, T. - Altoe, V. - Vávra, Jan - Raabová, Helena - Vaněk, Václav - Sainio, S. - Doriese, W. B. - O'Neil, G. C. - Swetz, D. S. - Ullom, J. N. - Irwin, K. - Nordlund, D. - Cígler, Petr - Wolcott, A.
Metastable Brominated Nanodiamond Surface Enables Room Temperature and Catalysis-Free Amine Chemistry.
Journal of Physical Chemistry Letters. Roč. 13, č. 4 (2022), s. 1147-1158. ISSN 1948-7185
R&D Projects: GA ČR(CZ) GA18-17071S; GA MŠMT 8C18004; GA MŠMT(CZ) EF16_019/0000729; GA MŠMT EF16_026/0008382
Institutional support: RVO:61388963
Keywords : X-ray absorption * diamond 111 * fluorescent nanodiamonds
OECD category: Nano-materials (production and properties)
Impact factor: 5.7, year: 2022
Method of publishing: Limited access
https://doi.org/10.1021/acs.jpclett.1c04090

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 similar to 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.
Permanent Link: http://hdl.handle.net/11104/0331091