Cotterill Erin L, Gomes Tiago C, Teare Amélie C P, Jaberi Yasmeen, Dhindsa Jasveer S, Boyle Paul D, Rondeau-Gagné Simon, Gilroy Joe B
Department of Chemistry, The University of Western Ontario, 1151 Richmond St. N., London, ON, N6A 3K7, Canada.
Department of Chemistry and Biochemistry, University of Windsor, 401 Sunset Ave., Windsor, ON, N9B 3P4, Canada.
Chemistry. 2024 Dec 13;30(70):e202403458. doi: 10.1002/chem.202403458. Epub 2024 Nov 7.
Since the Nobel prize winning discovery that polyacetylene could act as a semiconductor, there has been tremendous efforts dedicated to understanding and harnessing the unusual properties of π-conjugated polymers. Much of this research has focused on the preparation of oligoynes and polyynes with well-defined numbers of repeating alkyne units as models for carbyne. These studies are usually hampered by a structure-property relationship where the stability of the resulting materials decrease with the incorporation of additional alkyne units. Here, we describe a series of oligoynes, with up to 12 alkyne units, where electron-rich [Pt(PBu)] units are incorporated at the center of the oligoyne backbones which are capped by electron-poor BF formazanate dyes. These compounds exhibit excellent stability and solubility, panchromatic absorption, and redox activity characteristic of their structural components. These traits facilitated thin-film studies of extended oligoyne materials, where it is shown that incorporating [Pt(PBu)] units leads to smoother films, decreased conductivity on the microscale, and increased conductivity on the nanoscale when compared to metal-free analogs. Remarkably, our oligoynes have superior conductivity compared to the ubiquitous poly(3-hexylthiophene) semiconductor.
自从因发现聚乙炔可作为半导体而获得诺贝尔奖以来，人们付出了巨大努力来理解和利用π共轭聚合物的特殊性质。这项研究的大部分集中在制备具有明确重复炔单元数量的低聚炔和聚炔，作为卡宾的模型。这些研究通常受到结构 - 性能关系的阻碍，即所得材料的稳定性会随着额外炔单元的引入而降低。在此，我们描述了一系列含有多达12个炔单元的低聚炔，其中富电子的[Pt(PBu)]单元被引入到低聚炔主链的中心，并用贫电子的BF甲脒染料封端。这些化合物表现出优异的稳定性和溶解性、全色吸收以及其结构组分所特有的氧化还原活性。这些特性有助于对扩展的低聚炔材料进行薄膜研究，结果表明，与无金属类似物相比，引入[Pt(PBu)]单元会导致薄膜更光滑，微观尺度上导电性降低，而纳米尺度上导电性增加。值得注意的是，我们的低聚炔与普遍存在的聚(3 - 己基噻吩)半导体相比具有更高的导电性。
