RESUMO
Functionalization of diamond surfaces with TEMPO and other surface paramagnetic species represents one approach to the implementation of novel chemical detection schemes that make use of shallow quantum color defects such as silicon-vacancy (SiV) and nitrogen-vacancy (NV) centers. Yet, prior approaches to quantum-based chemical sensing have been hampered by the absence of high-quality surface functionalization schemes for linking radicals to diamond surfaces. Here, we demonstrate a highly controlled approach to the functionalization of diamond surfaces with carboxylic acid groups via all-carbon tethers of different lengths, followed by covalent chemistry to yield high-quality, TEMPO-modified surfaces. Our studies yield estimated surface densities of 4-amino-TEMPO of approximately 1.4 molecules nm-2 on nanodiamond (varying with molecular linker length) and 3.3 molecules nm-2 on planar diamond. These values are higher than those reported previously using other functionalization methods. The ζ-potential of nanodiamonds was used to track reaction progress and elucidate the regioselectivity of the reaction between ethenyl and carboxylate groups and surface radicals.