Atomically resolved single-molecule triplet quenching

• Published in: Science (American Association for the Advancement of Science) 2021-07, Vol.373 (6553), p.452-456
• Main Authors: Peng, Jinbo, Sokolov, Sophia, Hernangómez-Pérez, Daniel, Evers, Ferdinand, Gross, Leo, Lupton, John M., Repp, Jascha
• Format: Article
• Language: English
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.abh1155

Little is known about the atomistic mechanism that nature uses to mitigate the destructive interaction of triplet-excited pigment chromophores with omnipresent oxygen. Peng et al. tackled this challenge by developing a technique based on conducting atomic force microscopy to populate and track triplets in a single pentacene molecule, a model ϖ-conjugated system, placed on a sodium chloride surface (see the Perspective by Li and Jiang). The authors show how the triplet-state lifetime can be quenched in controllable manner by atomic-scale manipulations with oxygen co-adsorbed in close vicinity. The presented single-molecule spectroscopy paves the way for further atomically resolved studies of triplet excited states that play an important role in many other fields, such as organic electronics, photocatalysis, and photodynamic therapy. Science , abh1155, this issue p. 452 ; see also abj5860, p. 392 Single-molecule triplet states and their interactions with O 2 molecules can be tracked with real-space atomic resolution. The nonequilibrium triplet state of molecules plays an important role in photocatalysis, organic photovoltaics, and photodynamic therapy. We report the direct measurement of the triplet lifetime of an individual pentacene molecule on an insulating surface with atomic resolution by introducing an electronic pump-probe method in atomic force microscopy. Strong quenching of the triplet lifetime is observed if oxygen molecules are coadsorbed in close proximity. By means of single-molecule manipulation techniques, different arrangements with oxygen molecules were created and characterized with atomic precision, allowing for the direct correlation of molecular arrangements with the lifetime of the quenched triplet. Such electrical addressing of long-lived triplets of single molecules, combined with atomic-scale manipulation, offers previously unexplored routes to control and study local spin-spin interactions.