Aromatic Cation-Capped Oligoynes: Stabilisation and Trion Formation

我建议开发芳香阳离子端低聚炔(I)来提高低聚炔在溶液态处理中的稳定性（ii）来研究它们的带电激子（trions）。此外，我将（iii）在单分子电导、电荷（空穴）迁移率和光电子应用的背景下研究这些材料的低聚炔-累积烯畸变。本实验研究激发芳族阳离子端低聚烷链产生的trions，将增强我们对激发态载流子动力学的理解。这种空穴掺杂在低聚炔领域还没有被探索过。因此，该项目将为三体电荷配合物的形成，共轭链上的空穴迁移率，低聚炔-累积烯畸变，以及tropylium （TP）端低聚炔的自组装，光电性质和氧化还原化学提供新的基本见解。我们的假设是，使用TP亚基在低聚烷的两端放置持久的、以碳为中心的正电荷将(a)在整个碳链上产生极端的空穴迁移率，(b)使正离子易于产生。该方案的主要目标是：(1)开发可扩展的端部奇/偶低聚烷链的合成路线，(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trions，(3)阐明它们的低聚烷-累积烯畸变，(4)使用Pd-sandwichmetal团簇化学来调节trions的潜在衰变动力学。(5)应用DFT计算来帮助我们的观测合理化。为了充分理解和利用低聚乙二醇三离子的巨大潜力，对其形成和降解的动力学和机制的基本认识至关重要。

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.