The role of molecular oxygen (O2) and UV light in the anion radical formation and stability of TCNQ and its fluorinated derivatives

Abstract

Abstract We report the electronic absorption spectroscopy of 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its fluorinated derivatives (F2TCNQ and F4TCNQ), well-known electron-accepting molecules in common organic solvents (toluene, chlorobenzene, acetonitrile, and ethanol) under controlled exposure to air (O2) and UV light. All compounds (FxTCNQ (x = 0, 2, 4)) were stable in a neutral state (FxTCNQ0) in toluene and chlorobenzene, even under both O2 and UV light. On the other hand, in EtOH, the formation of FxTCNQ·− was monitored upon controlled exposure to O2 or UV light. Especially in air-equilibrated ethanol upon the UV-illumination, efficient α,α-dicyano-p-toluoylcyanide anion (DCTC−) and its fluorinated derivatives were generated evinced by the absorption peak near 480 nm, whereas the reaction was shut off by removing O2 or blocking UV light, thereby keeping FxTCNQ·− stable. However, even in deaerated ethanol, upon the UV-illumination, the anion formation of TCNQ and its fluorinated derivatives (FxTCNQ·−, x = 0, 2, 4) was inevitable, showing the stability of FxTCNQ0 depends on the choice of solvent.

Keywords

• Electron acceptor
• Photochemistry
• Radical anion
• Tetracyanoquinodimethane