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.

有机双重自由主义者的反应性研究受到溶液中的高反应性和短寿命的阻碍。例如，关于控制许多以碳为中心的自由基的化学特性的因素，知之甚少，并且对相关三重自由基的化学特性一无所知。但是，关于控制这些物种化学性质的因素的信息非常可取，因为它可能会使人们通过改变结构细节，从而设计具有量身定制特性的多层质量来“调整”其反应性。这样做的能力有望影响许多领域，包括有机合成，材料科学（例如有机磁铁）和药物开发。过去，PI和她的学生通过使用傅立叶转换离子环状共振质谱仪（FT-ICR）（一种流动的余辉Quadrupole-octapapole-octapapole-quadrupole applatus），研究了气体单和观点的反应性。这些研究揭示了几个重要的反应性控制因子，这些因素可用于“调整”这些物种的反应性。该项目将将这些研究扩展到类似的三自动和反应性几乎完全未经探索的三立自由基。通过实验研究以及对其几何形状和电子结构的计算研究，将探索几种异构体和不同替代的三个自由基的特性。 超过20位毕业生和至少五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。约有一半的参与学生是女性和/或属于代表性不足的少数民族。此外，将向普渡大学的科学货车介绍质谱法，该学院将向印第安纳州中部的高中和中学提供研究级工具。拟议的研究将导致培训大量种族多样的，高素质的科学博士学位。