Chemistry of High-Energy Content Reagents

离子的光化学、物理和光谱性质 将研究由阳离子染料和阴离子硼酸盐形成的染料对。的 首先要考虑的问题是硼烷基是否 由硼酸盐的单电子氧化形成的自由基是结合物质。 这将通过应用时间分辨光谱技术来解决。 皮秒和飞秒时间尺度上的方法。自从 硼烷基过短，无法测量氧化 电位的电化学手段，动力学方法的基础上， 应用Weller方程估计了它们的势能。一 将制备一系列硼酸盐以研究空间位阻效应 在氧化电位上硼酸盐的拥挤。穿透离子对 将准备有不同的遭遇距离，方向， 以及光引发的电子转移反应的自由能变化。 有了这些不同的渗透离子对，控制向前和向前的因素就不一样了。 将分析背电子转移。 有机动力学项目的资助支持了 加里教授的B。舒斯特在伊利诺伊大学。离子对 将由带正电荷的染料和带负电荷的 硼酸盐。硼酸盐总共含有四种其它含碳化合物， 键合到硼原子上的基团（烷基或芳基）。这些离子对 将被染料吸收的光照射。电子 将从染料转移到硼酸盐，这反过来又会导致 烷基以自由基（a）的形式与硼解离 具有一个未配对电子的碳物质）。这种方法的效率 反应，这部分取决于电子的反向转移， 给定起始离子对，将作为 离子对的结构这些离子对具有实际重要性， 因为它们可以在用可见光照射时引发聚合， 红外线聚合物的广泛商业应用使得这些 具有商业价值的离子对。

The photochemical, photophysical, and spectroscopic properties of ion pairs formed from cationic dyes and anionic borates will be studied. The first question to be considered will be whether or not the boranyl radicals formed by one electron oxidation of borates are bound species. This will be addressed by application of time-resolved spectroscopic methods on picosecond and femtosecond time-scales. Since the lifetime of boranyl radicals is too short to permit measurement of the oxidation potential by electrochemical means, a kinetic method based on the Rehm-Weller equation will be applied to estimate their potentials. A series of borates will be prepared to investigate the effect of steric crowding in the borate upon the oxidation potential. Penetrated ion pairs will be prepared that have different encounter distances, orientation, and free energy changes for photoinitiated electron transfer reactions. With these various penetrated ion pairs, factors that control forward and back electron transfer will be analyzed. This grant from the Organic Dynamics Program supports the continuing work of Professor Gary B. Schuster at the University of Illinois. Ion pairs will be formed from positively charged dyes and negatively charged borates. The borates contain a total of four other carbon containing groups ( alkyl or aryl groups) bonded to the boron atom. These ion pairs will be irradiated with light which is absorb by the dye. An electron will be transfer from the dye to the borate, which will in turn cause an alkyl group to dissociate from boron in the form of a free radical (a carbon species with one unpaired electron). The efficiency of this reaction, which depends in part on the back-transfer of an electron to give the starting ion pair, will be studied as a function of the structure of the ion pair. These ion pairs have practical importance, since they can initiate polymerization upon irradiation with visible and infrared light. The wide co mmercial application of polymers makes these ion pairs of commercial interest.