title: Interrogating near-infrared electrogenerated chemiluminescence of Au25(SC2H4Ph)18(+) clusters.
abstract: The electrochemistry, near-infrared photoluminescence (NIR-PL) spectroscopy, and electrogenerated chemiluminescence (ECL) of Au(25)(SC(2)H(4)Ph)(18)(+)C(6)F(5)CO(2)(-) (Au(25)(+)) clusters were investigated. For the first time, NIR-ECL emission was observed in both annihilation and coreactant paths. Our newly developed spooling spectroscopy was employed during the ECL evolution and devolution processes along with explicit NIR-PL spectroscopy to elucidate light generation mechanisms. It was discovered that the electronic relaxation of the Au(25)(-) excited state to the ground state plays a key role in giving off ECL at 893 nm, while intermediate, strong, and weak NIR-PL emissions at 719/820, 857, and 1080 nm can be attributed to the excited states higher than the HOMO-LUMO gap, across the HOMO-LUMO gap, and of semi-rings, respectively.
authors.affiliation: Department of Chemistry and Centre for Advanced Materials and Biomaterials, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
authors.forename: Kalen N
authors.initials: KN
authors.lastname: Swanick
authors.forename: Mahdi
authors.initials: M
authors.lastname: Hesari
authors.forename: Mark S
authors.initials: MS
authors.lastname: Workentin
authors.forename: Zhifeng
authors.initials: Z
authors.lastname: Ding