CAREER: Living Ring-Opening Polymerization: A New Route to Emissive Materials

本提案的目的是利用我们最近开发的基于paracylophan -1-ene的PPV-poly（对苯基乙烯）方法来解决技术重要性问题。重点将放在新的大分子方法，提高共轭聚合物的环境稳定性，同时保持感兴趣的光光学特性。我们也有兴趣研究多色团的立体规则性问题，它们对二级结构的影响，以及最终的体性质。在资助期间，具体目标是：(1)将我们的温和和活性聚合途径的范围扩大到无缺陷PPV，从而可以用这种方法制备电差版本的PPV。(2)利用分子模型研究聚副环磷酰胺-1-烯的二级结构如何促进发色团聚集。(3)研究光生成酸是否能够催化固态脱水反应形成PPV，从而允许使用微光刻工艺进行图案化。(4)考察链长和聚合度对新工艺制备的PPV的发射量子产率和耐久性的影响，以期对这些性能进行优化。(5)开始研究含PPV片段嵌段共聚物的微非均相性质。(6)利用标准溶液法表征PPV链与供体和受体分子形成激发态二聚体（准分子）的能力。导电聚合物作为一门科学领域正在走向成熟。合成方法的基本进步，主要是由化学家带来的，已经允许物理学家和工程师使用它们作为电子和电光设备的组件，如发光二极管、电子照相光感受器、太阳能转换系统、聚合物电容器和光电探测器。将聚合物应用于这些功能器件的兴趣源于其优越的可加工性和低密度，相对于无机材料，以及它们固有的无定形性质。然而，导致小带隙的结构和键合特征不仅显着降低了材料的溶解度和可加工性，而且不可避免地使这类材料易于化学氧化。这种反应性严重限制了它们的环境稳定性和一般的长期耐久性。因此，这些基于分子的电子和电活性器件的成功实施将在很大程度上取决于我们设计和合成新一代环境稳定的共轭聚合物的能力。在此资助期间，初级水平的高级无机/有机方法和仪器课程将继续创新，首次包括x射线结构测定。本课程将结合严格的化学操作和最新仪器的介绍。购买计算机设备的资金已经筹集。＊＊＊

9500627 Bazan The aim of this proposal is to take advantage of our recently developed paracyclophan-1-ene based PPV-poly(para phenylenevinylene) methodology to resolve issues of technical importance. Emphasis will be placed on new macromolecular approaches that improve the environmental stability of conjugated polymers while maintaining photo optical features of interest. We are also interested in investigating stereoregularity issues on polychromophores, their influence on secondary structure and, ultimately, bulk properties. During the grant period, specific aims are: (1) To expand the scope of our mild and living polymerization route to defect-free PPV so that electronpoor versions of PPV can be prepared in this way. (2) To study, by use of molecular modeling, how the secondary structure in poly(paracyclophan-1-ene)s enforces chromophore aggregation. (3) To investigate whether photogenerated acids are capable of catalyzing a solid state dehydration reaction to form PPV so as to permit patterning using microlithographic processes. (4) To examine the effect of chain length and degree of aggregation on the emission quantum yield and durability of PPV prepared via our new route, in the hope of optimizing these properties. (5) To begin an investigation into the microheterogeneous properties of block copolymers containing PPV fragments. (6) To characterize, using standard solution methods, the ability of PPV chains to form excited state dimers (excimers) with both donor and acceptor molecules. %%% Conducting polymers are reaching maturity as a scientific field. Fundamental advances in synthetic methodology, primarily brought about by chemists, have permitted their use by physicists and engineers as components in electronic and electro-optic devices such as light emitting diodes, electrophotographic photoreceptors, solar energy conversion systems, polymer based capacitors and photodetectors. The interest in applying polymers to these functional de vices stems from their superior processability and low density, relative to inorganic materials, as well as their intrinsic amorphous nature. However, the structural and bonding features that lead to a small band gap not only reduce significantly the solubility and processability of the material but inevitably make chemical oxidation of this class of materials facile. This reactivity places severe limits on their environmental stability and general longterm durability. Successful implementation of these molecular- based electronic and electro-active devices will therefore depend to a large extent on our ability to design and synthesize a new generation of conjugated polymers that are environmentally stable. During this grant period, the junior-level advanced inorganic/organic methods and instrumentation course will continue to be innovated to include for the first time x-ray structure determination. This course will combine rigorous chemical manipulations with an introduction to stae-of-the art instrumentation. Funds for the purchase of computer equipment have already been raised. ***