This study reports the first Co₂(CO)₈‐catalyzed [2+2+2] polycyclotrimerization by the transformation of internal ethynyl groups of aromatic diyne monomers. The reaction yields polycyclotrimers of polyphenylene‐type with either hyperbranched or partly crosslinked architecture. The homopolycyclotrimerization of the monomers with two ethynyl groups per one molecule, namely 1,4‐bis(phenylethynyl)benzene, 4,4′‐bis(phenylethynyl)biphenyl, and 4‐(phenylethynyl)phenylacetylene, gives partly crosslinked, insoluble polyphenylenes. The soluble, hyperbranched polyphenylenes are generated via copolycyclotrimerization of 1,4‐bis(phenylethynyl)benzene with 1,2‐diphenylacetylene (average number of ethynyl groups per monomer molecule < 2). This one‐step polycyclotrimerization path to hyperbranched or partly crosslinked polyphenylenes is an alternative to the synthesis of these polymers by Diels–Alder transformation of substituted cyclopentadienones. All polyphenylenes prepared exhibit photoluminescence with emission maxima ranging from 381 to 495 nm. Polyphenylenes with a less compact packing of segments are microporous (specific surface area up to 159 m² g⁻¹), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.

中文翻译：

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Co2（CO）8催化的芳族内二炔的均相和共聚三聚：一种超支化或交联结构的微孔光致发光亚苯基的简便途径

这项研究报告了第一个Co ₂（CO）₈芳族二炔单体内部乙炔基的转化催化[2 + 2 + 2]聚环三聚。该反应产生具有超支链或部分交联结构的聚亚苯基型多环三聚体。每个分子具有两个乙炔基的单体的均聚环三聚，即1,4-双（苯基乙炔基）苯，4,4'-双（苯基乙炔基）联苯和4-（苯基乙炔基）苯乙炔，得到部分交联的不溶性聚苯撑。可溶的超支化聚亚苯基是通过1,4-双（苯基乙炔基）苯与1,2-二苯基乙炔的共聚环三聚反应生成的（每个单体分子的乙炔基平均数<2）。通过一步到多支链或部分交联的聚亚苯基的多环三聚途径，是通过取代的环戊二烯酮的Diels-Alder转化合成这些聚合物的替代方法。制备的所有聚苯撑均表现出光致发光，最大发射范围为381至495 nm。链段堆积不太紧密的聚苯是微孔的（比表面积最大为159 m² g ^-1），这在可溶性聚亚苯基的情况下尤其重要，因为它们可以潜在地用于制备微孔层。