Oral Presentation 21st International Conference on Biological Inorganic Chemistry 2025

Exploring the Biological Activity of Systematically Designed Polyimine Metal Complexes (122236)

Sylvia M Draper 1 , Amani Al Riyami 1 , Judit Fodor 1 , Claire Condon 1 , Olga Mazuryk 2 , Mary Pyrce 3
  1. Trinity College Dublin, Dublin, DUBLIN, Ireland
  2. Coordination and Bioinorganic Physicochemistry Group, Jagiellonian University, Krakow, Poland
  3. Inorganic Chemistry, Dublin City University, Dublin, Dublin , Ireland

Characteristic of our group’s evolving strategies in the design of metal complexes for tailored biological applications e.g. photodynamic therapy (PDT) [1] we hereby share insights into the unusual photophysics and cytotoxity of two novel complex families. These have in common ligands that are built around a bipyridine-ethynyl-chromophore motif.

The first of the two families was created using an ‘on-the complex’ synthetic approach and involves Nile Red (NR) as an intensely absorbing lipophilic chromophore[2]. Given its desirable photophysical properties (λex 610 nm, ΦΔ 90.4% and possessing a non-emissive triplet state capable of singlet oxygen generation) the Ru(II)-3ENR complex was expected to be a potent photosensitiser (PS) in PDT experiments. It was drammatically out-performed however (approximately 2-fold) by its Ir(III)-ENR analogue which in comparison had a much lower ΦΔ (λex 610 nm, ΦΔ 9.7 %). We present here our collaborative efforts to understand to what extent this is due to better internalisation of the Ir(III) complex by the SKBR-3 cells and/or alternative oxygen-independent mechanisms of action.  

The second family of complexes were accessed using an unusual convergent synthetic route comprises unsymmetrical bipyridine ligands with conventional donor/acceptor moieties. These materials demonstrate solvent-dependent excited state switching and ground state energies that are influenced by the counter-ion. These systems have moderate dark cytotoxicty and preliminary in vitro cell studies show that despite their simplicity they are very efficient at generating Reactive Oxygen Species (ROS).

  1. [1] (a) Lu, Y.; Conway-Kenny, R.; Wang, J.; Cui, X.; Zhao, J. and Draper, S. M. Dalton Trans. 2018, 47 (26), 8585-8589. (b) Cabrera-Gonzalez, J.; Soriano, J.; Conway-Kenny, R.; Wang, J.; Lu, Y.; Zhao, J.; Nogues, C. and Draper, S.M. Biomater. Sci. 2019, 7 (8), 3287-3296. (c) Conway-Kenny, R.; Ferrer-Ugalde, A.; Careta, O.; Cui, X.; Zhao, J.; Nogues, C.; Nunez, R.; Cabrera-Gonzalez, J.; Draper, S.M. Biomater. Sci. 2021, 9 (16), 5691-5702.
  2. [2] Condon, C.; Conway-Kenny, R.; Cui, X.; Hallen, L.J.; Twamley, B.; Zhao, J.; Watson, G.W.; and Draper, S.M., J. Mater. Chem. C, 2021, 9, (41) 14573-14577.
  3. [3] Hallen, L.; Horan, A. M.; Twamley B.; McGarrigle E. M.; Draper, S.M. Chem. Commun. 2023, 59, 330-333.