Aromatic Cation-Capped Oligoynes: Stabilisation and Trion Formation

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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.