Aromatic Cation-Capped Oligoynes: Stabilisation and Trion Formation

芳香族阳离子封端寡炔：稳定化和 Trion 形成

• 批准号: EP/Y015657/1
• 负责人: Paul McGonigal
• 金额: $ 23.84万
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FY015657%2F1
• 关键词: Aromatic; Cation; Capped; Oligoynes; Stabilisation

I propose the development of aromatic cation-terminated oligoynes (i) to improve the stability of oligoynes for solution-stateprocessing and (ii) to investigate their charged excitons (trions). In addition, I will (iii) investigate the oligoyne-cumulene distortion ofthese materials in the context of single molecular conductance, charge (hole) mobility and optoelectronics applications. Thisexperimental study of trions created by exciting aromatic cation-terminated oligoyne chains will enhance our understanding ofexcited-state charge carrier dynamics. This type of hole doping has not yet been explored in the oligoyne field. Therefore, this projectwill give new fundamental insights into the formation of three-body charge complexes, hole mobility along conjugated chains, andthe oligoyne-cumulene distortion, as well as the self-assembly, optoelectronic properties, and the redox chemistry of tropylium (TP)-terminated oligoynes.Our hypothesis is that using TP subunits to place persistent, carbon-centred positive charges at both ends of an oligoyne will (a)generate extreme hole mobility throughout the carbon chain and (b) enable facile positive-trion generation. The primary objectivesof this proposal are (1) to develop scalable synthetic routes for TP-terminated odd/even oligoyne chains, (2) to investigate andcharacterise their excitons and trions using transient absorption spectroscopy and time-resolved luminescence measurements, (3) toshed light on their oligoyne-cumulene distortion, (4) to modulate the potential decay dynamics of the trions using Pd-sandwichmetal cluster chemistry, and (5) to apply DFT calculations to help rationalise our observations. To fully comprehend and harness theremarkable potential of oligoyne trion species, fundamental insights into the dynamics and mechanisms that characterize theirformation and degradation are critical.

我建议开发芳香族阳离子封端的oligoynes（i）以提高oligoynes的稳定性，用于溶液状态加工和（ii）调查他们的带电激子（trions）。此外，我将（iii）调查oligoyne-cumulene畸变ofthese材料的背景下，单分子电导，电荷（空穴）迁移率和光电子应用。本实验研究了芳香族阳离子封端的低聚炔链激发产生的三电子，将增强我们对激发态载流子动力学的理解。在低聚炔领域中尚未探索这种类型的空穴掺杂。因此，本项目为研究三体电荷复合物的形成、空穴沿沿着共轭链的迁移率、寡炔-累积烯畸变、托吡酯（TP）封端的寡炔的自组装、光电性质和氧化还原化学提供了新的基础性认识。在低聚炔两端的碳中心正电荷将（a）在整个碳链中产生极端的空穴迁移率和（B）能够容易地产生正三电子。本研究的主要目的是：（1）开发TP封端的奇/偶寡炔链的可扩展的合成路线，（2）使用瞬态吸收光谱和时间分辨发光测量来研究和表征它们的激子和三电子，（3）揭示它们的寡炔-累积多烯畸变，（4）使用Pd-Pd金属簇化学来调节三电子的潜在衰变动力学，（5）应用DFT计算来合理化我们的观测。为了充分理解和利用低聚炔三离子物种的显着潜力，对其形成和降解的动力学和机制的基本见解是至关重要的。