We have conducted a new comparison of gold nanoparticles functionalized by primary- and secondary amine with the same chain length. Our hypothesis suggests that the adaptive steric conformation of the secondary amine molecular branches makes a marked additional contribution to the well-established role of the ligand chain length. We characterize the importance of this factor based on diOctadecylamine (diODA) and Octadecylamine (ODA) passivated gold nanoparticles by using high-resolution transmission electron microscopy (HR-TEM) and selective area electron diffraction (SAED). The results evidenced that the diODA coordination to the inorganic core forms a more efficient and impenetrable protective coating. The SAED patterns show a more homogeneous distribution of the small crystalline domains in the gold core. TEM images show a smooth spherical shape of the diODA nanoparticles and a lack of interparticle coalescence cases. The diODA-passivation provides nanoparticles with nearly twice the effective ligand length than its ODA equivalent. This results in their spontaneous arrangement in domains with expressed crystal-like order despite the relatively large size-dispersity before passivation. The surface free energy of coatings, formed by diODA passivated gold nanoparticles, is twice as small as measured on the ODA-nanoparticle-coated surfaces.
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