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

Abstract

The covalent functionalization of MoS 2 with ap erylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS 2-PDI hybrid material. Covalently functionalizedM oS 2 interfacing organic photoactive species has shown electron and/or energy accepting,energy reflecting or bi-directional electron accepting features.H erein, ar ationally designed PDI, unsubstituted at the perylene core to act as electron acceptor,f orces MoS 2 to fully demonstrate for the first time its electron donor capabilities.The photophysical response of MoS 2-PDI is visualized in an energy-level diagram, while femtosecond transient absorption studies disclose the formation of MoS 2 C +-PDIC À charge separated state.T he tunable electronic properties of MoS 2 ,a saresult of covalently linking photoactive organic species with precise characteristics,u nlock their potentiality and enable their application in light-harvesting and optoelectronic devices.

Brand-New Method toward Widely Regulating Polymer Dispersity by Two-Dimensional Confining Radical Polymerization

“…During polymerization in TDCRP, the PL emission gradually produces a red shift (Figure a,b). It is known that the strong interactions between the polymer segment and two-dimensional plane could promote the transfer or energy dissipation of excitons, which thus results in the excitons coming back to the ground state with a longer PL emission (Figure c,d). − Therefore, the PL result of the red shift proves the increased interactions between the polymer segment and two-dimensional plane during polymerization in TDCRP. In addition, the different polymer segments would produce different interactions with the two-dimensional plane, thereby leading to different degrees of the red shift.…”

Noncovalent Liquid Phase Functionalization of 2H-WS2 with PDI: An Energy Conversion Platform with Long-Lived Charge Separation

“…a Please note that covalently linked MoS 2 -PDI conjugates fail to exhibit similar CT bands or any evidence for intercomponent ground-state electronic coupling. 22 A likely rationale is centered around the noncovalent nature of WS 2 −PDI. Here, PDIs are accommodated at positions, where the electronic interactions with WS 2 are maximized.…”

“…Similar conclusions were drawn for a previously reported covalent MoS 2 −PDI conjugate. 22 It signifies that the degree of functionalization is insufficient to significantly alter Coulomb interactions between electrons and holes within WS 2 via dielectric screening. 24 Concerning the polydispersity of the WS 2 nanosheets in lateral size and thickness, it has recently been shown that absorption spectra allow for the simultaneous quantification of the nanosheets dimensions in dispersion.…”

“…Importantly, it has been demonstrated that TMDs are complementary electron donors, which were integrated into covalently linked MoS 2 -PDI conjugates. 22 As a consequence, we expected a robust photoenergy conversion platform. Our WS 2 −PDI hybrid was comprehensively characterized by spectroscopic methods, and inter alia we gathered insights into the electronic interactions between WS 2 and PDI upon photoexcitation on the femto-to nanosecond timescales.…”

One-step covalent hydrophobic/hydrophilic functionalization of chemically exfoliated molybdenum disulfide nanosheets with RAFT derived polymers

“…Molecular functionalization of exfoliated MoS 2 nanosheets has gained increased interest. [1][2][3][4][5][6] In particular, chemically exfoliated MoS 2 nanosheets (ce-MoS 2 ) derived by treating the bulk semiconducting MoS 2 powder with organolithium compounds 7 are a proven candidate towards stable covalently modified nanosheets with small molecules. 6,[8][9][10] However, covalent functionalization of ce-MoS 2 nanosheets with polymers remains in its infancy.…”