Photoswitchable Intramolecular H-Stacking of Perylenebisimide

• Published in: Journal of the American Chemical Society Vol. 132; no. 12; pp. 4191 - 4196
• Main Authors: Wang, Jiaobing, Kulago, Artem, Browne, Wesley R, Feringa, Ben L
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 31.03.2010; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Electronics; Hydrogen - chemistry; Imides - chemistry; Light; Magnetic Resonance Spectroscopy; Models, Biological; Molecular Structure; Perylene - analogs & derivatives; Perylene - chemistry; Physical Sciences; Science & Technology; Spectrometry, Fluorescence; Stereoisomerism; ORGANIZATION; BISIMIDE DYES; ELECTRON-TRANSFER; FLUORESCENCE; DRIVEN; CHARGE; MOLECULES
• ISSN: 0002-7863; 1520-5126; 1943-2984; 1520-5126
• DOI: 10.1021/ja910829b

Dynamic control over the formation of H- or J-type aggregates of chromophores is of fundamental importance for developing responsive organic optoelectronic materials. In this study, the first example of photoswitching between a nonstacked and an intramolecularly H-stacked arrangement of perylenebisimides (PBI) is demonstrated. The system is composed of a central switching unit (overcrowded alkene) tethered to two PBI chromophores. cis−trans isomerization of the switching unit, induced by alternate irradiation at 312 and 365 nm, can drive two PBI chromophores reversibly between an intramolecularly “aggregated” and “nonaggregated” state. Distinct changes in UV−vis absorption and fluorescence spectra are observed following photoisomerization. This approach allows for efficient control of intramolecular H-stack formation with no significant intermolecular interactions spanning over at least 4 orders of magnitude of concentration (from 10−8 to 10−4 M) and a range of solvents and temperatures.