Synthesis, Reactions, and Applications of Organic "Super" Photoacids

这项研究的重点是新型超级光酸的合成和光化学，包括它们在生物和光刻胶系统中的应用。质子转移代表了自然界中两个最基本的过程之一，但研究该过程动力学的技术依赖于相对低效的商用材料。这与电子转移形成鲜明对比，电子转移经历了压倒性的合成、机械和动态努力。尽管两者之间存在许多相似之处，包括通过马库斯理论合理化的溶剂依赖性动力学，但光激发产生电化学驱动力，这很容易通过氧化/还原电位的分析合理化。如果可以理解激发态的电子结构，那么激发态下质子转移的发生为使用超快时间分辨技术研究这一基本过程的化学和动力学提供了独特的机会。该项目涉及新基底的设计和合成，以测试结构、驱动力和熵的概念，并允许与理论建立关联。这种方法利用酸激发态电子结构的知识来设计具有增强激发态酸性的分子。其中一些被称为“超级”光酸，是已知的最强的可逆光酸。将开发合成方法以获得可以定制光致酸性的分子，从而为质子转移反应和新型聚合催化剂的研究提供新方法。该研究向研究生和博士后介绍了酸碱化学和动力学的新概念，以及检查这些瞬态效应的方法。有机和高分子化学项目通过该奖项支持佐治亚理工学院化学与生物化学学院 Laren Tolbert 教授的研究。托尔伯特教授的研究重点是光酸分子的合成和激发态化学，其酸碱性质会在光激发下发生变化。这些分子可以表现出巨大但短暂的酸碱性质变化，为研究酸碱化学提供了新方法，也为光活化聚合催化剂提供了新方法。托尔伯特教授正在通过与他系的罗伯特·迪克森教授、弗里堡大学的于尔根·鲁赫教授和特拉维夫大学的梅纳希姆·古特曼教授的合作扩大他的研究工作。通过托尔伯特教授的研究，研究生和博士后学生将接触到酸碱化学的新概念，以及检查这些瞬态效应的方法。

This research focuses on the synthesis and photochemistry of new super photoacids, including their application to biological and photoresist systems. Proton transfer represents one of the two most fundamental processes in nature, yet techniques for studying the dynamics of this process have relied on relatively inefficient, commercially-available materials. This is in contrast to electron transfer, which has seen an overwhelming synthetic, mechanistic, and dynamic effort. Although many similarities exist between the two, including solvent-dependent kinetics rationalized through Marcus theory, photoexcitation creates electrochemical driving forces, which are readily rationalized by an analysis of oxidation/reduction potentials. The occurrence of proton transfer in the excited state presents unique opportunities to study the chemistry and dynamics of this fundamental process using ultrafast time-resolved techniques, if the electronic structure of the excited state can be understood. This project involves the design and synthesis of new substrates that test concepts of structure, driving force, and entropy and that allow correlations to be made with theory. This approach uses a knowledge of the electronic structure of excited-states of acids to design molecules which exhibit enhanced excited-state acidity. Some of these, which are termed "super" photoacids, are the strongest reversible photoacids known. Synthetic methodologies will be developed to achieve molecules whose photoacidity can be tailored thereby providing new methods for studies of proton transfer reactions and novel polymerization catalysts. The research introduces graduate and postdoctoral students to new concepts in acid-base chemistry and kinetics, and to the methodologies to examine these transient effects.With this award, the Organic and Macromolecular Chemistry Program supports the research of Professor Laren Tolbert of the School of Chemistry and Biochemistry at Georgia Institute of Technology. Professor Tolbert will focus his research efforts on the synthesis and excited state chemistry of molecules, called photoacids, whose acid-base properties change on optical excitation. These molecules, which can exhibit immense, but transient, changes in acid-base properties, provide new methods to study acid-base chemistry, and novel approaches to photoactivated, polymerization catalysts. Professor Tolbert is expanding his research efforts through collaborations with Professors Robert Dickson in his Department, Juergen Ruehe of Frieburg University and Menachim Gutman at the University of Tel Aviv. Through Professor Tolbert's research, graduate and postdoctoral students will be exposed to new concepts in acid-base chemistry, and the methodology to examine these transient effects.