Aromatic Cation-Capped Oligoynes: Stabilisation and Trion Formation

我建议开发芳香族阳离子端基低聚炔类化合物(I)以提高溶液状态处理的稳定性，以及(II)研究它们的带电激子(三子)。此外，我还将(Iii)在单分子电导、电荷(空穴)迁移率和光电子学应用的背景下研究这些材料的寡炔-异丁烯失真。对激发芳香族阳离子末端低聚炔链所产生的三重离子的实验研究将加深我们对激发态载流子动力学的理解。这种类型的空穴掺杂在寡炔领域还没有被探索过。因此，这个项目将为三体电荷复合体的形成，沿共轭链的空穴迁移率，寡炔-累积烯的扭曲，以及端联吡喃的自组装，光电性质，以及氧化还原化学提供新的基本见解。我们的假设是，使用TP亚基在寡炔的两端放置持久的以碳为中心的正电荷将(A)在整个碳链中产生极端的空穴迁移率，并且(B)能够容易地产生正电子。这一建议的主要目的是(1)开发可扩展的合成路线，用于TP末端的奇/偶寡炔链，(2)使用瞬时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-积木烯扭曲，(4)使用Pd-夹心金属团簇化学来调制三电子的潜在衰变动力学，以及(5)应用密度泛函计算来帮助我们的观察合理。为了充分理解和利用寡炔三元物种的可标记潜力，对其形成和退化的动力学和机制的基本见解是至关重要的。

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.