Acetylenic scaffolding on solid support: poly(triacetylene)- derived oligomers by Sonogashira and Cadiot–Chodkiewicz-type cross-coupling reactionsElectronic supplementary information (ESI) available: typical procedures for the reactions on solid phase and physical as well as spectral data of compound 2. See http://www.rsc.org/suppdata/ob/b2/b210184j/

Abstract

We report the first synthesis of poly(triacetylene)-derived oligomers by Pd(0)-catalysed Sonogashira and Cadiot-Chodkiewicz-type cross-coupling reactions on solid support. Oligo(phenylene triacetylene)s, members of a new class of linearly pi-conjugated oligomers with all-carbon backbones, feature very high fluorescence intensities.

Synthesis of Conjugated Oligomers Having Aromatic and Enediyne Units Alternately in the Backbone that Show Intense Fluorescence Emission

“…The electronic absorption and fluorescence spectra of the oligo(arylene enediyne)s 5 − 7 thus prepared are summarized in Table . It can be seen from Table that, in all cases, the longest-wavelength absorption maxima λ max are bathochromically shifted with increasing conjugation length as expected . While the position of the λ max differs little between the oligomer having a phenyl or pyridyl group as the arylene unit, it shifts about 30 nm to lower energy for the thiophene-containing oligomers 7 in comparison with 5 and 6 , presumably due to the electron-rich character of the thiophene ring.…”

“…Most recently, they prepared (phenylene enediyne)-monomer, -dimer, -trimer, and -tetramer of type 1 ( n = 1−4) shown in Figure using Sonogashira coupling on solid support as a key reaction. Interestingly, the dimer and, in particular, the trimer and tetramer display intense fluorescence emission, with the highest quantum yield, Φ F = 0.69, being measured for the trimer. , We therefore were interested in the fluorescence property of oligo(arylene enediyne)s that have an aromatic group other than a phenyl group. The synthetic method of Diederich, however, only allowed access to oligo(phenylene enediyne), and thus, a new synthetic method was needed.…”

Recent Progress in the Design of Monodisperse, Sequence-Defined Macromolecules

“…Diederich and co‐workers published a route to monodisperse oligo(triacetylene‐ alt ‐phenylene)s ( 5a ) in 2003 . The synthesis of the hexenediyne/diethynylethene starting molecule, with one triple bond protected with a TMS group, has been reported before .…”

Synthesis of 1,4-Cyclohexadiene-Based Acetylenic Macrocycles with Cadiot−Chodkiewicz Coupling. Structure of a Tub-Shaped Tetrameric Container

“…Among the haloacetylenes bromoacetylene has optimal reactivity and gives good yields of the diacetylenes. Cadiot-Chodkiewicz coupling has been widely used in the synthesis of acetyenic cyclophanes, natural and unnatural polyacetylenes . To develop a more efficient method for the synthesis of 1,4-cyclohexadiene-based acetylenic macrocycles, in particular the larger macrocycles, we explored the utility of Cadiot−Chodkiewicz coupling.…”