Photophysics, Exciton and Charge Transport in Conjugated Organometallic Oligomers and Aggregates

共轭有机金属低聚物和聚集体中的光物理学、激子和电荷传输

• 批准号: 0515066
• 负责人: Kirk Schanze
• 金额: $ 39万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-08-01 至 2012-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0515066&HistoricalAwards=false
• 关键词: Photophysics; Exciton; Charge; Transport; Conjugated

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Kirk S. Schanze of the University of Florida to pursue studies on the "Photophysics, Exciton and Charge Transport in Conjugated Organometallic Oligomers and Aggregates." Excited-state properties along with charge and exciton transport in metal-containing pi-conjugated oligomers and supramolecular assemblies will be examined. The overall objectives are to develop a clear understanding of excited state delocalization, energy, and charge transport within isolated single chains of organometallic pi-conjugated systems (molecular wires) and within supramolecular aggregates produced by self-assembly of pi-conjugated monomers. Several molecular systems will be studied. 1) A family of metal-acetylide oligomers that contain repeat units consisting of trans-(Ar-C=C-)2M(P-P)2 moieties (M = Ru and Os, and P-P is a diphosphine) will be investigated in order to determine the factors that control excited state delocalization in organometallic pi-conjugated systems. 2) The nature of the triplet excited state will be probed in a series of platinum(II)-capped polyynes of the type, trans,trans-Ar(P)2Pt-(C=C)n-Pt(P)2Ar in order to define the relationship between excited state properties and carbon chain length. 3) A series of long-chain, monodisperse Pt-acetylide oligomers will be studied to determine the rates of triplet exciton and negative polaron transport through single organometallic conjugated chains. 4) Photophysical and exciton transport studies will be extended to well-defined supramolecular aggregates formed by self-assembly of a) pi-conjugated rigid-rod Pt-acetylide oligomers capped with one or more long alkyl chains, or b) hexabenzocoronenes functionalized with metal complex chromophores. The objective of this work will be to determine the effect of aggregation on the properties of the triplet state and to study triplet exciton migration in well defined supramolecular aggregates.This investigation is directly relevant to emerging technologies that have a significant potential to benefit society, the economy, and improve the nation's defense capabilities. Specifically, the materials that are the focuses of this work have applications in opto-electronic devices such as visible and near infrared light emitting diodes (novel light sources), photovoltaic cells (light to electrical energy conversion), non-linear optics (laser protection and color shifting) and sensors (chemical- and bio-agent detection). This program also serves as the primary research training conduit for undergraduate and graduate students. The broader impacts of this project are augmented by the Light and Matter Outreach program at the University of Florida, through which PI, graduate students and undergraduate students will bring photochemistry related scientific demonstrations to middle schools in the North Florida region.

该奖项由无机、生物无机和有机金属化学项目颁发，支持佛罗里达大学Kirk S. Schanze教授对“共轭有机金属低聚物和聚集体中的光物理学、激子和电荷输运”的研究。将研究含金属偶联寡聚物和超分子组装中的激发态性质以及电荷和激子输运。总体目标是对有机金属π共轭系统（分子线）的孤立单链以及π共轭单体自组装产生的超分子聚集体中的激发态离域、能量和电荷传输有一个清晰的理解。几个分子系统将被研究。1)为了确定在有机金属偶联体系中控制激发态离域的因素，将研究一类含有由反式（Ar-C=C-）2M(P-P)2 （M = Ru和Os， P-P是二膦）组成的重复单元的金属乙酰基低聚物家族。2)为了确定激发态性质与碳链长度之间的关系，将在一系列反式、反式、反式ar (P)2Pt-(C=C)n-Pt(P)2Ar型铂（II）盖帽多炔中探索三重态激发态的性质。3)研究一系列长链、单分散的pt -乙酰基酯低聚物，以确定通过单个有机金属共轭链的三重态激子和负极化子输运速率。4)光物理和激子输运研究将扩展到定义明确的超分子聚集体，这些超分子聚集体是由以下物质自组装形成的：a) π共轭刚性棒pt -乙酰基低聚物，顶部有一条或多条长烷基链，或b)金属络合物发色团功能化的六苯并冠烯。这项工作的目的将是确定聚集对三重态性质的影响，并研究三重态激子在明确定义的超分子聚集体中的迁移。这项调查与新兴技术直接相关，这些技术对社会、经济和提高国防能力具有重大潜力。具体来说，作为这项工作重点的材料在光电器件中有应用，如可见光和近红外发光二极管（新型光源）、光伏电池（光能转换）、非线性光学（激光保护和色移）和传感器（化学和生物制剂检测）。该项目也是本科生和研究生的主要研究培训渠道。佛罗里达大学的光与物质拓展项目扩大了该项目的广泛影响，通过该项目，PI、研究生和本科生将把光化学相关的科学演示带到北佛罗里达地区的中学。