High-pressure high-temperature nanoscale diamond is the most common host of the nitrogen vacancy center (NVC) for magnetometry and electric field sensing applications. Limiting advancements in NVC charge state control and atomic/molecular control of the diamond surface are the limited routes to chemically removing C-O bonds after aerobic oxidation protocols. Previous discoveries about the highly labile C-Br bond on the diamond surface revealed that catalysis-free C-N bond formation was possible at 25<sup>o</sup>C and was largely understood as a consequence of the high energy state of the alkyl-bromide and long-lived carbocation intermediate. Here we expand the available bond formation chemistry using the reactive C-Br intermediate to generate new C-C bonds with carbenes. Atomic and molecular details of the diamond surface is confirmed with vibrational spectroscopy and synchrotron-based X-ray spectroscopies. The removal of the highly stable C-O bond now allows tunablility of the surface dipole moment with carbon-carbon and carbon-heteroatom bonding environments. The modulation of the surface dipole moment will changes the depletion and accumulation layer properties of the diamond host and was confirmed with work function measurements This work is applicable to researchers investigating the charge dynamics of NVCs (or other colour center) in diamond and their use as a biolabeling and quantum sensor nanoprobe.

Brominated nanodiamond allows for C-C bond formation without a catalyst at room temperature

ACS Spring 2022

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