Development of Functionalized Cyclotriveratrylene Analogues: Introduction of Withdrawing and π-Conjugated Groups

Abstract

Cyclotriveratrylene analogues (CTVs) are supramolecular bowl-shaped molecules known for their ability to complex organic and organometallic guests, to form liquid crystals, polymers, or nanostructures. In this Article, we report the synthesis of new cyclotriveratrylene analogues with fluorescence properties in which various electron-withdrawing or π-extended conjugated groups are appended to the wide rim ortho to the methoxy-donating groups. Synthetically, these functionalized CTVs cannot be obtained as CTVs with electron-rich functions by the typical method (i.e., the trimerization of the corresponding benzyl alcohol) but are prepared from a common key intermediate, the C(3)-triiodocyclotriveratrylene (CTV-I(3)), in good yields. Despite the synthetic difficulties encountered due to the presence of three reactive centers, we have demonstrated the possibility of performing Sonogashira coupling and Huisgen cycloaddition reactions directly to the CTV core for the first time. CTVs with π-extended conjugated groups reveal interesting fluorescence profiles. More broadly, this study utilizes CTV-I(3) to introduce novel functionalities into CTVs to keep exploring their potential applications.

The Stereoselective Self‐Assembly of Chiral Metallo‐Organic Cryptophanes

“…[18] We report herein a study of the self-assembly of cryptophanes through palladium-and platinum-carbonitrile coordination bonds, which have been employed previously to construct achiral metallo-organic cages based on resorcin[4]-arene. [19] As CTB components, we compared cyclotricyanotribenzylene 1, which has sterically clear binding sites, and cyclotricyanotrianisylene 2, [20] both in racemic form ( Figure 1). As palladium and platinum complex assembling fragments, we selected [M(dppp)] 2+ (M = Pd or Pt, dppp = 1,3-bisdiphenylphosphinopropane), as the dppp chelate provides the optimal P-M-P angle for a square-planar complex (ca.…”

A new fluorescent hemicryptophane for acetylcholine recognition with an unusual recognition mode

“…Excited at 320 nm, this CTV exhibits a maximum emission at 355 nm. 25 This means that the structure of the capsule does not impact the spectroscopic characteristics of the fluorescent part. The fluorescent quantum yield F and the decay time t were determined (F = 11% using quinine as reference and t = 2.4 ns).…”

Click Chemistry in Materials Science

“…As 1,2,3-triazoles are π-conjugated, Cu(I)-and Ru(II)-catalyzed azide-alkyne cycloadditions have been used to fabricate regioregular polymeric materials with extended π-conjugation of varying chemical and photophysical properties. [ 17,18 ] Owing to the cytotoxicity associated with Cu(I), several groups have endeavored to minimize the copper concentration while maintaining high reaction rates. [ 19 ] Utilizing ring strain and chemical modifi cation of the alkynyl moieties, suffi cient cycloaddition reaction rates at room temperature are achievable without copper catalysis.…”