Synthesis of Soluble Bis-terpyridine Ligands Bearing Ethynylene−Phenylene Spacers

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Abstract
Soluble and rigid terpyridine-based ditopic ligands bearing one to five phenylene/ethynylene modules have been synthesized by way of a stepwise procedure. Each module is attached to the terpyridine unit via an ethynylene fragment and functionalized at the 4-position with an additional ethynylene connector and in the 2,5-positions with two flexible dodecyloxy chains. The synthetic protocol is based on sequential Pd(0)-catalyzed cross-coupling reactions between a terpyridine subunit grafted with the necessary diethynyl/phenyl or ethynylphenyl/bromide appendage. For ditopic ligands displaying an even number of phenyl/ethynylene modules, the final step involves a single cross-coupling reaction between 4‘-ethynylene-2,2‘:6‘,6‘ ‘-terpyridine and the appropriate bromo derivative. In the case of the ligands having an odd number of phenylene/ethynylene fragments, a double cross-coupling reaction between an extended dibromopolyphenylene intermediate and 4‘-ethynylene-2,2‘:6‘,6‘ ‘-terpyridine or 1-(4‘-ethynylene-2,2‘:6‘,2‘ ‘-terpyridine)-4-ethynylene-2,5-didodecyloxy-benzene is required. For ligands I−V, optimal preparative conditions were found with [Pd0(PPh3)4] (6 mol %) in n-propylamine at 70 °C. Oxidative dimerization of the 1-(4‘-ethynylene-2,2‘:6‘,2‘ ‘-terpyridine)-4-ethynylene-2,5-didodecyloxybenzene derivative in the presence of cupric salts and oxygen gives the corresponding homoditopic ligand II 2 bearing a central diphenyldiacetylene spacer. Spectroscopic data for the new oligomers are discussed in terms of the extent of π-electron conjugation. Upon increasing the number of phenylene/ethynylene modules, there is a progressive lowering in energy of absorption and fluorescence transitions.