Collaborative Research: Semiconducting Behavior in Silsesquioxane Macromonomers and Polymers

合作研究：倍半硅氧烷大分子单体和聚合物的半导体行为

• 批准号: 2103628
• 负责人: Aleksander Rebane
• 金额: $ 10.12万
• 依托单位: Montana State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-15 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2103628&HistoricalAwards=false
• 关键词: Collaborative; Research; Semiconducting; Behavior; Silsesquioxane

With support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professors Richard Laine and John Kieffer of the University of Michigan-Ann Arbor, and Professor Aleks Rebane of Montana State University will develop new families of silicone-based polymers. Silicone oils and rubbers are hydrophobic, colorless, and electrically insulating materials and as such find wide uses. Recently, two families of silicon-containing polymers were developed wherein silicon-containing building blocks alternate with fluorescent ones. Unlike most known silicon-based materials, these polymers are intensely colored, brightly fluorescent, and behave as semiconductors. Importantly, they still retain key properties of traditional silicones, such as water and flame resistance. Semiconducting polymers, such as, organic light-emitting diodes (OLEDs) are found in flat panel displays and in some instances can be used to convert sunlight into electricity. Hence the study of these new polymer families could lead to unexpected and potentially useful properties, bringing new, low-cost and more robust materials to many everyday societal applications. This research project will facilitate the training of graduate and undergraduate students to expand knowledge of these materials and their behavior. Silsesquioxanes (SQs) are unique, regularly symmetric 3D macromolecules that resemble single silica crystals in being extremely robust, some remaining air-stable up to 600 °C. The phenyl derivatives of SQs can also be selectively functionalized by using electrophilic substitution reactions. The cage centers interact with appended moieties in the excited state providing 3D conjugation (cage centered LUMOs) and semiconducting behavior. There is potential to develop new families of polymers with semiconducting properties wherein siloxane bridges offer potential value for photonic applications, for example for displays, hybrid lasers and photovoltaics. These avenues of scientific inquiry, which constitute the basis for the broad collaboration, aim at expanding the number of cage architectures that form the presumed cage centered LUMOs, detailing the substitution patterns required to promote onset of such properties, and optimizing one- and two-photon quantum efficiencies for display, white light and laser applications. These goals will be pursued through detailed photophysical measurements, theoretical modeling, and electrochemical probing with the aim of improving fundamental understanding of structure-property relationships in this polymer family. The potential exists to make available important new sets of semiconducting polymers for chemists, physicists and materials scientists and engineers.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在大分子，超分子和计划的支持下，蒙大拿州的Aleks Rebane的化学措施将开发新的基于有机硅油的家族。 。在平面显示器中发现的材料可用于电力。独特的，对称的3D大分子，在SQS的600°C中，二氧化硅晶体也可以是静态的，也可以是静态的替代反应。 Siloxane Bridges提供光子应用，例如显示，混合激光器和TAIC，旨在扩大笼子架构帽子的数量这些属性和优化一个和二个量子ies以进行显示，这些目标将被追求详细的光物理测量g，并进行电化学探测，以改善对聚合物家族的结构 - 培训关系的理解。化学家，物理学家，材料和工程师的聚合物。该奖项反映了NSF'SF'SF的误差，并通过使用基金会的知识分子优点和更广泛的影响评估标准进行评估，被认为值得支持。

项目成果

On‐off‐on Control of Molecular Inversion Symmetry via Multi‐stage Protonation: Elucidating Vibronic Laporte Rule

通过多级质子化控制分子反转对称性：阐明电子拉波尔特规则

• DOI: 10.1002/anie.202212581
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Stark, Charles W.;Rammo, Matt;Trummal, Aleksander;Uudsemaa, Merle;Pahapill, Juri;Sildoja, Meelis‐Mait;Tshepelevitsh, Sofja;Leito, Ivo;Young, David C.;Szymański, Bartosz
• 通讯作者: Szymański, Bartosz