The first calixarenequinhydrone: syntheses, self‐organized films and solvatochromism

Di(methoxy‐ p‐tert ‐butyl)calix[4]arenediquinone ( 2 ) was prepared from di(methoxy‐ p‐tert ‐butyl)calix[4]arene. Reduction of 2 led to its calix[4]arenedihydroquinone analog 3 . Partial reduction of 2 by 0.5 equiv. of a reducing agent led to the calix[4]arenequinhydrone charge‐transfer complex 4 , which exhibits an intense solvatochromic absorption band in the visible region. Thus, λ max varies from 627 nm in CHCl 3 to 677 nm in Et 2 O. The association between two moieties of calix[4]arenequinonehydroquinone disodium salt was evidenced by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The optical absorptions of 4 and a quinhydrone‐containing polymer were compared. A calix[4]arenequinonecyclohexadienone derivative was also obtained and characterized by X‐ray diffraction. Copyright © 2005 John Wiley & Sons, Ltd.