Abstract

Spin-active dopants offer a powerful yet largely unexplored route for controlling interfacial redox chemistry in quantum-confined semiconductors. Here we show that manganese doping in cadmium selenide quantum dots enables an ultrafast spin-exchange-mediated electron-transfer pathway that allows methyl viologen reduction even when conventional band-edge energetics are unfavorable for charge transfer. Femtosecond transient absorption spectroscopy reveals that manganese dopants accelerate electron-transfer dynamics by more than an order of magnitude while opening a hot-exciton reduction channel in which a manganese ion captures a photoexcited exciton prior to phonon-assisted cooling. Subsequent spin-flip relaxation of the excited manganese ion drives charge separation and reduction of a molecular acceptor. This mechanism operates efficiently across resonant and off-resonant (energy-uphill and downhill) regimes, identifying spin-exchange coupling—rather than band alignment—as the dominant factor governing electron-transfer rates and efficiencies. These findings establish magnetic doping as a viable strategy for harvesting hot carriers and enabling energetically demanding photocatalytic transformations.

For decades, researchers have understood electron transfer in photocalysis through one guiding principle. Electrons move most readily when the energy levels of a semiconductor and a reacting molecule are well matched. Researchers at UNIST and Los Alamos National Laboratory (LANL) have demonstrated that spin interactions can provide an alternative pathway, allowing electron transfer even when conventional energy-level alignment is unfavorable. 

Professor Ho Jin of the Department of Chemistry at UNIST, in collaboration with Dr. Victor I. Klimov of LANL, showed that manganese ions inside semiconductor quantum dots (QDs) create an ultrafast spin-exchange pathway that channels hot-electron energy into photoreduction reactions. The findings offer a new way to design photocatalysts that make better use of sunlight for hydrogen production and carbon dioxide conversion.

QDs readily transfer photoexcited electrons to nearby molecules, making them attractive materials for photocatalysis. Their most energetic electrons, however, lose excess energy almost immediately, leaving little time for useful chemical reactions to occur. 

The team addressed this challenge by introducing magnetic manganese ions into cadmium selenide (CdSe) QDs. Before hot electrons could cool, the manganese ions captured their excess energy through ultrafast spin exchange. As the ions returned to their original spin state, that energy drove electrons into nearby molecules, triggering photoreduction reactions that would otherwise be difficult to achieve.

Using femtosecond transient absorption spectroscopy, the researchers followed the electron transfer process in real time. Compared with undoped QDs, manganese-doped particles transferred electrons to methyl viologen more than ten times faster, demonstrating that spin exchange provides an efficient pathway for charge transfer.

The team then asked whether the mechanism truly depended on hot-electron energy. When larger QDs were illuminated with higher-energy light, photoreduction readily occurred. Under lower-energy illumination, the reaction largely disappeared. Together, these experiments showed that manganese captures the excess energy of hot electrons before it is lost as heat.

“We have traditionally thought of energy-level alignment as the deciding factor in electron transfer,” said Professor Jin. “Our results show that spin exchange can provide an alternative pathway, giving us a new way to harness the energy of hot electrons for photocatalysis.”

Professor Ho Jin served as the first author of the study. Their findings were published in Nature Communications  on June 26, 2026.

Journal Reference

Ho Jin, Valerio Pinchetti, Connor Orrison,  et al., “Ultrafast photoreduction driven by interfacial spin exchange in manganese-doped quantum dots,”  Nat. Commun.,  (2026).