Aromatic Cation-Capped Oligoynes: Stabilisation and Trion Formation
Lead Research Organisation:
University of York
Department Name: Chemistry
Abstract
I propose the development of aromatic cation-terminated oligoynes (i) to improve the stability of oligoynes for solution-state
processing and (ii) to investigate their charged excitons (trions). In addition, I will (iii) investigate the oligoyne-cumulene distortion of
these materials in the context of single molecular conductance, charge (hole) mobility and optoelectronics applications. This
experimental study of trions created by exciting aromatic cation-terminated oligoyne chains will enhance our understanding of
excited-state charge carrier dynamics. This type of hole doping has not yet been explored in the oligoyne field. Therefore, this project
will give new fundamental insights into the formation of three-body charge complexes, hole mobility along conjugated chains, and
the 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 objectives
of this proposal are (1) to develop scalable synthetic routes for TP-terminated odd/even oligoyne chains, (2) to investigate and
characterise their excitons and trions using transient absorption spectroscopy and time-resolved luminescence measurements, (3) to
shed light on their oligoyne-cumulene distortion, (4) to modulate the potential decay dynamics of the trions using Pd-sandwich
metal cluster chemistry, and (5) to apply DFT calculations to help rationalise our observations. To fully comprehend and harness the
remarkable potential of oligoyne trion species, fundamental insights into the dynamics and mechanisms that characterize their
formation and degradation are critical.
processing and (ii) to investigate their charged excitons (trions). In addition, I will (iii) investigate the oligoyne-cumulene distortion of
these materials in the context of single molecular conductance, charge (hole) mobility and optoelectronics applications. This
experimental study of trions created by exciting aromatic cation-terminated oligoyne chains will enhance our understanding of
excited-state charge carrier dynamics. This type of hole doping has not yet been explored in the oligoyne field. Therefore, this project
will give new fundamental insights into the formation of three-body charge complexes, hole mobility along conjugated chains, and
the 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 objectives
of this proposal are (1) to develop scalable synthetic routes for TP-terminated odd/even oligoyne chains, (2) to investigate and
characterise their excitons and trions using transient absorption spectroscopy and time-resolved luminescence measurements, (3) to
shed light on their oligoyne-cumulene distortion, (4) to modulate the potential decay dynamics of the trions using Pd-sandwich
metal cluster chemistry, and (5) to apply DFT calculations to help rationalise our observations. To fully comprehend and harness the
remarkable potential of oligoyne trion species, fundamental insights into the dynamics and mechanisms that characterize their
formation and degradation are critical.
