Unveiling the Photoinduced Electron-Donating Character of MoS₂ in Covalently Linked Hybrids Featuring Perylenediimide

The covalent functionalization of MoS₂ with a perylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS₂ -PDI hybrid material. Covalently functionalized MoS₂ interfacing organic photoactive species has shown electron and/or energy accepting, energy reflecting or bi-directional electron accepting features. Herein, a rationally designed PDI, unsubstituted at the perylene core to act as electron acceptor, forces MoS₂ to fully demonstrate for the first time its electron donor capabilities. The photophysical response of MoS₂ -PDI is visualized in an energy-level diagram, while femtosecond transient absorption studies disclose the formation of MoS₂ ^.+ -PDI^.- charge separated state. The tunable electronic properties of MoS₂ , as a result of covalently linking photoactive organic species with precise characteristics, unlock their potentiality and enable their application in light-harvesting and optoelectronic devices.