Solid‐Phase Synthesis of Oligo(triacetylene)s and Oligo(phenylenetriacetylene)s Employing Sonogashira and CadiotChodkiewicz ‐Type Cross‐Coupling Reactions

We describe the first polymer‐supported synthesis of poly(triacetylene)‐derived monodisperse oligomers, utilizing Pd 0 ‐catalyzed Sonogashira and CadiotChodkiewicz ‐type cross‐couplings as the key steps in the construction of the acetylenic scaffolds. For our investigations, Merrifield resin functionalized with a 1‐(4‐iodoaryl)triazene linker was chosen as the polymeric support ( R2 ; Figure and Scheme 3 ). The linker selection was made based on the results of several model studies in the liquid phase ( Schemes 1 and 2 ). For the solid‐support synthesis of the oligo(phenylene triacetylene)s 7b – 7d , a set of only three reactions was required: i ) Pd 0 ‐catalyzed Sonogashira cross‐coupling, ii ) Me 3 Sialkyne deprotection by protodesilylation, and iii ) cleavage of the linker with liberation of the generated oligomers ( Scheme 5 ). The longest‐wavelength absorption maxima of the oligo(phenylene triacetylene)s 7a – 7d shift bathochromically with increasing oligomeric length, from λ max 337 nm (monomer 7a ) to 384 nm (tetramer 7d ; Table 2 ). Based on the electronic absorption data, the effective conjugation length (ECL) of the oligo(phenylene triacetylene)s is estimated to involve at least four monomer units and 40 C‐atoms. π ‐Electron conjugation in these oligomers is less efficient than in the known oligo(triacetylene)s 14a – 14d ( Table 2 ) due to poor transmittance of π ‐electron delocalization by the phenyl rings inserted into the oligomeric backbone. Similar conclusions were drawn from the electrochemical properties of the two oligomeric series as determined by cyclic (CV) and rotating‐disk voltammetry (RDV; Table 3 ). In sharp contrast to 14b – 14d , the oligo(phenylene triacetylene)s 7b – 7d are strongly fluorescent, with the highest quantum yield Φ F =0.69 measured for trimer 7c ( Table 2 ). Whereas the Sonogashira cross‐coupling on solid support proceeded smoothly, optimal conditions for alkynealkyne cross‐coupling reactions employing Pd 0 ‐catalyzed CadiotChodkiewicz conditions still remain to be developed, despite extensive experimentation ( Scheme 7 and Table 1 ).