Identifying Highly Photoelectrochemical Active Sites of Two Au21 Nanocluster Isomers toward Bright Near-Infrared Electrochemiluminescence.

Thus far, no correlation between nanocluster structures and their electrochemiluminescence (ECL) has been identified. Herein, we report how face-centered-cubic and hexagonal close-packed structures of two Au21(SR)15 nanocluster isomers determine their chemical reactivity. The relationships were explored by means of ECL and photoluminescence spectroscopy. Both isomers reveal unprecedented ECL efficiencies in the near-infrared region, which are >10- and 270-fold higher than that of standard Ru(bpy)32+, respectively. Photoelectrochemical reactivity as well as ECL mechanisms were elucidated based on electrochemistry, spooling photoluminescence, and ECL spectroscopy, unfolding the three emission enhancement origins: (i) effectively exposed reactive facets available to undergo electron transfer reactions; (ii) individual excited-state regeneration loops; (iii) cascade generations of various exited states. Indeed, these discoveries will have immediate impacts on various applications including but not limited to single molecular detection as well as photochemistry and electrocatalysis toward clean photon-electron conversion processes such as light-harvesting and light-emitting technologies.