Gas-Phase Studies of Organic Sigma-type Polyradicals

有机西格玛型多自由基的气相研究

• 批准号: 0910466
• 负责人: Hilkka Kenttamaa
• 金额: $ 45.5万
• 依托单位: Purdue University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-08-01 至 2012-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0910466&HistoricalAwards=false
• 关键词: Gas; Phase; Studies; Organic; Sigma

Reactivity studies on organic bi- and polyradicals are hindered by their high reactivity and short lifetime in solution. Only little is known, for example, about the factors that control the chemical properties of many carbon-centered radicals, and nothing is known about the chemical properties of related tri- and tetraradicals. However, information on the factors that control the chemical properties of these species is highly desirable since it may allow one to "tune" their reactivity by varying structural details and hence design polyradicals with tailored properties. The ability to do this is expected to impact many fields, including organic synthesis, materials science (e.g., organic magnets), and drug development. In the past, PI and her students have studied the reactivity of gaseous mono- and biradicals by using Fourier-transform ion cyclotron resonance mass spectrometers (FT-ICR), a flowing afterglow quadrupole-octapole-quadrupole apparatus, and most recently, a linear quadrupole ion trap. These studies have revealed several important reactivity controlling factors that can be used to "tune" the reactivity of these species. This project will extend these studies to analogous tri- and tetraradicals whose reactivity is nearly entirely unexplored. The properties of several isomeric and differently substituted tri- and tetraradicals will be explored by experimental studies on their reactivity and by computational studies on their geometries and electronic structures. More than 20 graduate and at least five undergraduate students will carry out all aspects of the research, and disseminate the results under the PI's supervision. About half of the participating students are female and/or belong to underrepresented minorities. Further, mass spectrometry will be introduced to Purdue's College of Science Van that delivers research grade instruments to high and middle schools throughout central Indiana. The proposed research will lead to the training of a large number of ethnically diverse, highly qualified science Ph.D.'s.

有机双自由基和多自由基在溶液中的高反应性和短寿命阻碍了它们的反应性研究。例如，我们对控制许多碳中心自由基化学性质的因素知之甚少，对相关的三自由基和四自由基的化学性质也一无所知。然而，控制这些物种的化学性质的因素的信息是非常可取的，因为它可以让一个“调整”他们的反应性通过改变结构的细节，从而设计与定制的性能polyradicals。这样做的能力预计将影响许多领域，包括有机合成、材料科学（例如，有机磁体）和药物开发。在过去，PI和她的学生已经研究了气态单和双自由基的反应性，通过使用傅里叶变换离子回旋共振质谱仪（FT-ICR），一个流动的余辉四极-八极-四极装置，最近，一个线性四极离子阱。这些研究揭示了几个重要的反应性控制因素，可用于“调整”这些物种的反应性。这个项目将把这些研究扩展到类似的三和四自由基，其反应性几乎完全未被探索。几个异构体和不同取代的三-和四自由基的性质将探讨其反应性的实验研究，并通过计算研究其几何形状和电子结构。 超过20名研究生和至少5名本科生将进行研究的各个方面，并在PI的监督下传播结果。大约一半的参与学生是女性和/或属于代表性不足的少数群体。此外，质谱法将被引入普渡大学的科学学院货车，提供研究级仪器，高中和中学整个印第安纳州。拟议的研究将导致大量种族多元化，高素质的科学博士的培训。's.