University of Otago, New Zealand


Te Tari Hua-Ruanuku

Georgina Shillito

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Georgina Shillito
Supervisor: Prof. Keith C. Gordon
Tel: (03) 479 7599
Location: Science II, 5c1

Georgina Shillito

Excited state structures and dynamics of transition metal polypyridyl complexes

Project Summary


Transition metal polypyridyl systems are strong candidates as the photoactive component of dye sensitised solar cells (DSSCs). These aim to artificially replicate photosynthesis, thereby providing a potential means of clean and renewable energy generation. A thorough understanding of the excited states and photophysical processes of these systems is essential in order to develop efficient and applicable materials.


The specifics of the chemical design of the metal polypyridyl has a significant impact on the energies, dynamics and nature of the excited states formed. This project involves utilisation of a range of spectroscopic and computational techniques in order to study the changes to the photophysical properties of the complex as a result of systematic chemical modification to its structure. This can be achieved in a number of ways, from alteration of the type or number of metal centres, to ancillary ligand modulation. Our focus is placed on the inclusion of ligands containing electron donating substituents, introducing intra-ligand charge transfer (ILCT) states alongside metal-to-ligand charge transfer (MLCT) states. The energies of these states can be tuned relative to one another, allowing exploration into their interaction and dynamics.


Electronic and vibrational spectroscopic methods are used in combination with theoretical calculations utilising density functional theory (DFT) and time-dependent DFT. These techniques allow study of the ground and excited state structures of these systems and the processes involved from original excitation, to relaxation back to the ground state.


·         Shillito, G. E.; Larsen, C. B.; McLay, J. R. W.; Lucas, N. T.; Gordon, K. C., Effect of Bridge Alteration on Ground- and Excited-State Properties of Ruthenium(II) Complexes with Electron-Donor-Substituted Dipyrido[3,2-a:2′,3′-c]phenazine Ligands. Inorg. Chem. 2016, 55 (21), 11170-11184.

·         Barnsley, J. E.; Shillito, G. E.; Larsen, C. B.; van der Salm, H.; Wang, L. E.; Lucas, N. T.; Gordon, K. C., Benzo[c][1,2,5]thiadiazole Donor-Acceptor Dyes: A Synthetic, Spectroscopic, and Computational Study. J. Phys. Chem. A 2016, 120 (11), 1853-66.


·         Larsen, C. B.; van der Salm, H.; Shillito, G. E.; Lucas, N. T.; Gordon, K. C., Tuning the Rainbow: Systematic Modulation of Donor–Acceptor Systems through Donor Substituents and Solvent. Inorg. Chem. 2016, 55 (17), 8446-8458.