Pasquini Chiara, Fratoddi Ilaria, Capitani Donatella, Mannina Luisa, Bassetti Mauro
CNR, Istituto di Metodologie Chimiche, Sezione Meccanismi di Reazione, and Dipartimento di Chimica, Università degli Studi di Roma La Sapienza, Roma, Italy.
J Org Chem. 2008 May 16;73(10):3892-9. doi: 10.1021/jo800471p. Epub 2008 Apr 15.
pi-Conjugated low molecular weight polymers characterized by regio- and stereoregular alternation of phenylene and ( E)-1-en-3-yne moieties have been synthesized by polyaddition of 1,4-diethynylbenzene or of 2,5-diethynyl-1,4-alkoxybenzene monomers, employing the commercially available di-micro-chlorobis[( p-cymene)chlororuthenium(II)] complex as the metal catalyst source, under homogeneous, atom-economical, amine- and phosphine-free conditions. Bulk materials of poly( p-phenyleneethynylenevinylene) derivatives are obtained with yields larger than 80%, from which polymers readily soluble in chlorinated solvents and in tetrahydrofuran are extracted in 60-75% yields. The polymers with average degrees of polymerization in the range n AV = 4-8 display optical properties in solution similar to those of the higher molecular weights analogues.
通过1,4 - 二乙炔基苯或2,5 - 二乙炔基 - 1,4 - 烷氧基苯单体的加成聚合反应，以市售的二 - 微氯双[（对异丙基苯）氯钌（II）]配合物作为金属催化剂源，在均相、原子经济、无胺和无膦的条件下，合成了以亚苯基和（E）-1 - 烯 - 3 - 炔部分的区域和立体规整交替为特征的π共轭低分子量聚合物。聚（对苯撑乙炔基亚乙烯基）衍生物的块状材料产率大于80%，从中以60 - 75%的产率提取出易溶于氯化溶剂和四氢呋喃的聚合物。平均聚合度在nAV = 4 - 8范围内的聚合物在溶液中的光学性质与较高分子量类似物的光学性质相似。
