Isolation of mixed valence charge-neutral Ag12, and dicationic Ag10 nano-clusters stabilized by carbene-phosphaalkenides

Maria Francis; Asutosh Patra; Farsana Abdul Salam; Siriyara Jagannatha Prathapa; Sudipta Roy

doi:10.1039/d4cc05628k

Isolation of mixed valence charge-neutral Ag₁₂, and dicationic Ag₁₀ nano-clusters stabilized by carbene-phosphaalkenides

Chem Commun (Camb). 2024 Dec 18. doi: 10.1039/d4cc05628k. Online ahead of print.

Authors

Maria Francis¹, Asutosh Patra¹, Farsana Abdul Salam¹, Siriyara Jagannatha Prathapa², Sudipta Roy¹

Affiliations

¹ Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517619, India. [email protected].
² Bruker India Scientific Pvt. Ltd, India.

PMID: 39692629
DOI: 10.1039/d4cc05628k

Abstract

Cyclic alkyl(amino) carbene (cAAC)-supported phosphaalkenides (cAACP)^- have been employed as ligands for the isolation of two atomically precise mixed valence paramagnetic AgI/012Cl₃, and AgI/010, nano-clusters [(Me₂-cAACP)₆Ag₁₂Cl₃] (2), and [(Me₂-cAACP)₆Ag₁₀](NTf₂)₂ (4). 2 and 4 have been structurally characterized by single-crystal X-ray diffraction revealing the presence of three Ag⁰ atoms, nine Ag^I ions (2); and two Ag⁰ atoms, eight Ag^I ions (4), respectively. The clustering inorganic unit Ag₁₂Cl₃ in 2 has been found to be surrounded by six mono-anionic μ₃-cAACP moieties having 3-bar symmetry. 2 and 4 have been studied by cyclic voltammetry, UV-vis, ESI-MS, XPS, EPR spectroscopy, and DFT calculations.