Alkyne metathesis with simple catalyst systems: Efficient synthesis of conjugated polymers containing vinyl groups in main or side chain
Alkyne metathesis with simple catalyst systems: Efficient synthesis of conjugated polymers containing vinyl groups in main or side chain
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DOI：
10.1021/ja0010251
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发表时间：
2000-12-20
影响因子：
15
通讯作者：
Bunz, UHF
中科院分区：
文献类型：
--
作者：
Brizius, G;Pschirer, NG;Bunz, UHF
报道了无环二炔复分解反应（ADIMET）合成新型共轭聚合物。这些聚合物是聚（对亚苯基亚乙烯基）和聚（对亚苯基亚乙炔基）（PPE）之间的杂化物。它们含有亚苯基、亚乙炔基和亚乙烯基（-=-Ph-=-Ph-，PPVE）。由Mo（CO）（6）和4-氯苯酚形成的简单原位催化剂用于复分解二丙炔基（四烷基）二苯乙烯单体。单体通过Horner反应和Heck型偶联的组合制备。PPVE以高产率形成，并且结构明确。它们显示出30 - 220个重复单元（即60 - 450个苯环）的聚合度（P-n），表明双键的存在不干扰炔复分解。用XRD和电子显微镜对PPVE的结构进行了表征。它们显示出纤维状和网络型的形态，这应该使它们在分子电子学中的应用感兴趣。固体样品的PPVE显示粉末XRD图谱几乎相同的PPE。因此，PPV呈现出与PPE类似的双层结构。研究了PPVE的聚集行为。此外，ADIMET到一个聚（2，7-芴亚乙炔基）携带不饱和侧链的报告。在这种情况下，不饱和度的存在既不干扰有效的炔复分解。
The synthesis of novel conjugated polymers by acyclic diyne metathesis (ADIMET) is reported. These polymers are hybrids between poly(p-phenylenevinylene) and poly(p-phenyleneneethynylene) (PPE). They contain phenylene, ethynylene, and vinylene groups (-=-Ph-=-Ph-, PPVE). Simple in situ catalysts formed from Mo(CO)(6) and 4-chlorophenol were used to metathesize the dipropynyl(tetraalkyl)stilbene monomers. The monomers are made by a combination of Horner reactions and Heck-type couplings. The PPVEs form in high yields and are structurally defined. They show degrees of polymerization (P-n) of 30-220 repeating units (i.e. 60-450 benzene rings), demonstrating that the presence of the double bonds does not interfere with alkyne metathesis. The PPVEs were structurally characterized by XRD and electron microscopy. They show fibrillar and network-type morphologies, which should make them interesting for applications in molecular electronics. Solid samples of PPVEs display powder XRD patterns almost identical to those of the PPEs. PPVEs thus assume similar doubly lamellar structures as the PPEs. The aggregation behavior of PPVEs was studied. In addition, ADIMET to a poly(2,7-fluorenyleneethynylene) carrying unsaturated side chains is reported. In this case the presence of unsaturation does neither interfer with efficient alkyne metathesis.