Synthesis and Photophysics of Silsequioxane Macromonomers and Polymers

在这个由化学系高分子、超分子和纳米化学计划资助的项目中，密歇根大学高分子科学与工程计划的理查德·M·莱恩和西奥多·古德森三世教授正在探索基于硅和氧的三维、结构精密的笼子的合成和性质。这些笼子具有独特的光学特性，研究小组正在研究将它们不对称地功能化的方法。该项目的成果可用于开发应用范围从有机发光二极管组件、有机太阳能电池和混合激光材料到新型半导体薄膜的新材料。Laine教授和Goodson教授正在为未被充分代表的少数群体提供培训的教育环境，并为K-12学生提供推广活动，以研究结构上精确的[(RSiO1.5)8]、[(RSiO1.5)10]和[(RSiO1.5)12]类型的硅氧烷(SQS)，以制备不对称分子。在通过共轭有机系链连接SQ笼时，这些系统还表现出通过笼的三维激发态共轭，这是由离域导致的通常与扩展共轭相关的发射红移。此外，这些相同的大分子表现出巨大的和意想不到的双光子吸收(TPA)截面，这与三维离域和电荷从外围有机官能团到笼芯的转移有关。莱恩教授和古德森教授正在绘制不对称性和Rr‘SiO引入对SQ大分子单体新家族的光物理和化学性质的影响图。正在研究的两种方法包括“顺序组装”，其中两个RR‘SiO基团作为简单单元添加到随后将被官能化的“双层”配方中，以及氟离子催化将预制的RR’SiO和R‘SiO 1.5单元并入到现有的SQS中。与密歇根大学和国外这两个小组的合作正被用来评估这些化合物在各种光子应用中的效用，包括激光和光磁应用，并绘制它们作为单独化合物和组装后的光物理和电子性质图。每年，这两个团体都接待和培训4-8名本科生和2-4名高中暑期学生研究人员，这些研究人员来自当地高中，包括代表人数不足的少数民族，其中大约一半是女性学者。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professors Richard M. Laine and Theodore Goodson III of the Macromolecular Science and Engineering Program at the University of Michigan are exploring the synthesis and properties of three-dimensional, structurally precise cages based on silicon and oxygen. These cages offer unique optical properties, and the team is studying methods to functionalize them asymmetrically. The results of this project could be used to develop new materials for applications ranging from components for organic light-emitting diodes, organic solar cells, and hybrid laser materials to novel semiconducting thin films. Professors Laine and Goodson are providing an educational environment targeting the training of under-represented minorities as well as outreach activities for K-12 students Structurally precise silsequioxanes (SQs) of the types [(RSiO1.5)8], [(RSiO1.5)10] and [(RSiO1.5)12] are being investigated to prepare asymmetric molecules. On linking SQ cages via conjugated organic tethers, these systems also exhibit three-dimensional excited state conjugation through the cages as witnessed by delocalization leading to emission red-shifts normally associated with extended conjugation. Furthermore, these same macromolecules exhibit large and unexpected two-photon absorption (TPA) cross-sections that are associated with both three-dimensional delocalization and charge transfer from peripheral organic functionality to the cage cores. Professors Laine and Goodson are mapping the effects of asymmetry and RR'SiO introduction on the photophysics and chemical properties of new families of SQ macromonomers. Two approaches being studied include "sequential assembly" wherein two RR'SiO groups are added as simply units in "double decker" formulations that will be followed by functionalization, as well as the fluoride anion catalyzed incorporation of preformed RR'SiO and R'SiO1.5 units to existing SQs. Collaborations with both groups at the University of Michigan and abroad are being used to assess the utility of these compounds for various photonic applications including lasing and photo-magnetism applications and to map their photophysical and electronic properties as individual compounds and after assembly. Annually, both groups are hosting and training 4-8 undergraduates and 2-4 high school summer student researchers from local high schools including under-represented minorities, with approximately half of these being women scholars.