Cotterill Erin L, Jaberi Yasmeen, Dhindsa Jasveer S, Boyle Paul D, Gilroy Joe B
Department of Chemistry, The University of Western Ontario, 1151 Richmond St. N., London, ON, N6A 5B7, Canada.
Macromol Rapid Commun. 2025 Feb;46(4):e2400786. doi: 10.1002/marc.202400786. Epub 2024 Oct 27.
𝜋-Conjugated polymers, including those based on acetylenic repeating units, are an exciting class of materials that offer narrow optical band gaps and tunable frontier orbital energies that lead to their use in organic electronics. This work expands the knowledge of structure-property relationships of acetylenic polymers through the synthesis and characterization of a series of Glaser-Hay-coupled model compounds and random copolymers comprised of BF formazanate, fluorene, and/or bis(alkoxy)benzene units. The model compounds and copolymers synthesized exhibit redox activity associated with the reversible reduction of the BF formazanate units and the irreversible reduction of the fluorene and bis(alkoxy)benzene units. The copolymers exhibit absorption profiles characteristic or intermediate of their respective models and homopolymers, leading to broad absorption of UV-vis light. The alkyne linkages of the model compounds and copolymers are reacted with [Co(CO)] to convert the alkyne functional groups into cobalt carbonyl clusters. This transformation leads to blue-shifted absorption profiles due to a decrease in π-conjugation, demonstrating the ability to tune the properties of these materials through post-polymerization functionalization. The redox activity and broad absorption bands of the polymers reported make them excellent candidates for use in photovoltaics and other light-harvesting applications.
π共轭聚合物，包括那些基于炔属重复单元的聚合物，是一类令人兴奋的材料，它们具有窄的光学带隙和可调的前沿轨道能量，这使得它们可用于有机电子学。这项工作通过一系列由BF甲臜、芴和/或双（烷氧基）苯单元组成的Glaser-Hay偶联模型化合物和无规共聚物的合成与表征，扩展了炔属聚合物结构-性质关系的知识。合成的模型化合物和共聚物表现出与BF甲臜单元的可逆还原以及芴和双（烷氧基）苯单元的不可逆还原相关的氧化还原活性。共聚物表现出各自模型和均聚物的特征性或中间的吸收谱，导致紫外-可见光的广泛吸收。模型化合物和共聚物的炔键与[Co(CO)]反应，将炔官能团转化为羰基钴簇。由于π共轭的减少，这种转变导致吸收谱蓝移，证明了通过聚合后功能化来调节这些材料性质的能力。所报道的聚合物的氧化还原活性和宽吸收带使其成为用于光伏和其他光捕获应用的优秀候选材料。
