Morphology Control in AgCu Nanoalloy Synthesis by Molecular Cu(I) Precursors

As nanoparticle preparation methods employing bottom-up procedures rely on the use of molecular precursors, the chemical composition and bonding of these precursors have a decisive effect on nanoparticle formation and their resulting morphology and properties. We synthesized the Cu(I) complexes [Cu(PPh₃)₂(bea)] (1, bea = benzoate) and [Cu(PPh₃)₃(Hphta)] (2, phta = phthalate) by reducing the corresponding Cu(II) mono- and dicarboxylates with triphenylphosphine. We characterized 1 and 2 by single-crystal X-ray diffraction analysis, elemental analyses, infrared and nuclear magnetic resonance spectroscopy, and mass spectrometry and obtained complete information about their structures in the solid state and in solution. Also, we examined their thermal stability in oleylamine and determined their decomposition temperatures to be used as the minimal reaction temperature in metal nanoparticle synthesis. The complexes 1 and 2 differ in the number of reducing PPh₃ ligands and the strength of carboxylate bonding to the Cu(I) center. Therefore, we employed them in combination with [Ag(NH₂C₁₂H₂₅)₂]NO₃ as molecular precursors in the solvothermal hot injection synthesis of AgCu nanoalloys in oleylamine and demonstrated their influence on the elemental distribution, phase composition, particle size distribution, shape, morphology, and optical properties of the resulting nanoparticles. The nanoalloy particles from the benzoate complex 1 were oblate and polydisperse and exhibited two surface plasmons at 393 and 569 nm, which is caused by their Janus-type structure. The nanoparticles prepared from the phthalate complex 2 were round and monodisperse and exhibited one plasmon at 413 nm, as they formed an AgCu solid solution with a random distribution of the elements in a particle.