Adhesion of gold and silver nanoparticles onto urea-alkylamine inclusion compounds

Abstract

We report the synthesis and characterization of a new series of urea inclusion compounds containing primary alkylamine (octyl, decyl and dodecyl) as guests, as well as the deposition of gold and silver nanoparticles onto the crystalline surface of these complexes. X-ray diffraction confirms the inclusion process of the amine in the urea cavities. The structures determined for the three complexes correspond to a hexagonal channel structure with space group P6(1)22. Alkylamine-urea stoichiometric ratios in all cases satisfy the relationship 1:3n (n = 2 for octylamine and 3 for decylamine and dodecylamine), determined by elemental analysis. The deposition of gold and silver nanoparticles by the magnetron sputtering technique onto microcrystals of the complexes was analyzed by Diffuse Reflectance Spectroscopy, showing characteristic surface plasmon resonance for metal nanoparticles. Transmission electron microscopy demonstrates the presence of metal nanoparticles (MNPs) in a size range between 5 and 60 nm for gold and between 5 and 20 nm for silver, and furthermore, in some cases it shows vestiges of a hexagonal arrangement of the MNPs. X-ray diffraction and IR measurements demonstrate that the basic structure of the matrix remains unchanged after the MNPs adhesion. IR also shows increased broadening and intensity of the characteristic NH2 bending frequencies (1,597 cm(-1)) when the MNPs interact with the inclusion compounds. We conclude that the interactions between the inclusion compounds and metal nanoparticles occurs mainly through the amino groups of the guest molecules that can emerge from the entrance of the inclusion compound cavities attracted by the metallic nanoparticles, in opposition to the restoring van der Waals interactions present inside channels, which increase with increasing chain length of the guest molecules.

Schematic representation of urea inclusion compounds containing primary alkylamine (octyl, decyl and dodecyl) as guests and the deposition of gold and silver nanoparticles onto the crystalline surface of these complexes.