Ligand exchange synthesis of organometallic Rh nanoparticles and application in explosive sensing

Abstract

Alkyne {phenyl acetylene (PA) and 9-ethynylphenanthrene (EPT)}-ligated Rh nanoparticles (1 and 2, respectively) with mean diameter of 1.5 ± 0.2 nm were synthesized via a facile and high-yield biphasic ligand exchange protocol using similar sized ethylene glycol (EG)-stabilized Rh nanoparticles as precursors (EG:Rh). The synthesized organometallic Rh nanoparticles were convincingly characterized using several spectroscopic and microscopic techniques, e.g., Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), optical absorption spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). We propose that the syntheses mechanism relies on catalytic acetylenic (≡C–H, carbon–hydrogen) bond breaking by EG:Rh followed by strong metal–carbon bond formation with a vinyldiene (>C═C═M) motif. The obtained 1 and 2 showed luminescence property, which arises from ligand structure through intraparticle conjugation. Electron-rich phenanthrene-ligated Rh nanoparticles (2) showed good sensing performance for detection of electron deficient nitro-aromatic explosive molecules (NA) in solution phase through luminescence quenching method.

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