Long-lived photoinduced charge separation in carbazole–pyrene–viologen system incorporated in Langmuir–Blodgett films of substituted diazacrown ethers

Abstract

Diaza-18-crown-6 ethers appending two pyrenyl (Py) or two carbazolyl (Cz) groups were synthesized. These macrocyclic compounds form 1:1 host–guest complexes with methyl viologen chloride (MV2+), and these complexes were assembled into monolayers by Langmuir–Blodgett technique. The generated assembly involves the general structure of donor–sensitizer–acceptor (Cz–Py–MV2+) in space, although any of the photo- and redox-active components are not covalently bonded. Photoirradiation of the pyrenyl group resulted in the charge-separated pair Cz+–Py–MV+ which survived up to hours in a well anaerobic atmosphere. An electrode was fabricated by transferring the L–B film on an ITO glass. The photoinduced voltage of this electrode was measured with a saturated calomel reference electrode in hydroquinone (H2Q) solution to be ca. 168mV when the light intensity was 218mW/cm2. This electrode was also used as the light electrode to construct a photogalvanic cell with a platinum electrode as the dark electrode. Irradiation of the light electrode with visible light results in anodic photocurrent, and there is no net chemical change associated with the function of the cell which converts light to electricity.