Copper clusters are nanoscale materials comprised of a metal core or frame enclosed by a mantle of stabilizing ligands; their exploration offers progress in diverse fields, such as medicine, electronics, and fundamental chemistry as catalysts, reducing agents, corrosion inhibitors, and petroleum sweeteners. When stabilized with dithiocarbamate (DTC) ligands (L), copper clusters show a propensity for reversible hydrogen uptake and a remarkable versatility in size and shape as demonstrated by the facile substitution of the protecting groups and multitude of species attainable. The purpose of this report is to demonstrate the versatility of the Cu-DTC system by the novel use of an aromatic dibenzyl DTC ligand (L’) to generate clusters of previously known composition (i.e., Cu8HL’6 PF6). As demonstrated herein, the new materials are air stable and amenable to characterization by high-resolution electrospray ionization mass spectrometry, 1H-nuclear magnetic resonance spectrometry, powder X-ray diffraction, Fourier Transform Infrared Spectroscopy, Ultraviolet-Visible spectroscopy, and Inductively Coupled Plasma Spectrometry. The subject ‑ hydrogen-rich caged cluster materials have potential applications as hydrogen storage sponges to great benefit to material science, energy, and other chemical fields.
Authors:   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Tellechea Jonathan O. , Lima Carlos ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Choi Duke ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Salazar Dennis ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Samiei Marjan ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Keoseyan Angie ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Vinogradova Ekaterina ,   Department of Physics & Astronomy, University of Texas, San Antonio, TX 78249, Yan Fangzhi ,   Department of Chemistry, University of Texas, San Antonio, TX 78249, Wherritt Daniel ,   Department of Chemistry, University of Texas, San Antonio, TX 78249, Alvarez Marcos M. ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Baghdasarian Glen ,   Department of Chemistry, Los Angeles City College, Los Angeles, CA 90029, Whetten Robert L. ,   Department of Physics & Astronomy, University of Texas, San Antonio, TX 78249, Department of Applied Physics & Materials Science, Northern Arizona University, Flagstaff, AZ 86011, Department of Chemistry and Biochemistry, Northern Arizona University, Flagstaff, AZ 86011, Center for Materials Interfaces in Research & Applications ¡MIRA!, Northern Arizona University, Flagstaff, AZ 86011
Published: July 2020

Copper clusters are nanoscale materials comprised of a metal core or frame enclosed by a mantle of stabilizing ligands; their exploration offers progress in diverse fields, such as medicine, electronics, and fundamental chemistry as catalysts, reducing agents, corrosion inhibitors, and petroleum sweeteners. When stabilized with dithiocarbamate (DTC) ligands (L), copper clusters show a propensity for reversible hydrogen uptake and a remarkable versatility in size and shape as demonstrated by the facile substitution of the protecting groups and multitude of species attainable. The purpose of this report is to demonstrate the versatility of the Cu-DTC system by the novel use of an aromatic dibenzyl DTC ligand (L’) to generate clusters of previously known composition (i.e., Cu8HL’6 PF6). As demonstrated herein, the new materials are air stable and amenable to characterization by high-resolution electrospray ionization mass spectrometry, 1H-nuclear magnetic resonance spectrometry, powder X-ray diffraction, Fourier Transform Infrared Spectroscopy, Ultraviolet-Visible spectroscopy, and Inductively Coupled Plasma Spectrometry. The subject ‑ hydrogen-rich caged cluster materials have potential applications as hydrogen storage sponges to great benefit to material science, energy, and other chemical fields.