Circularly polarised luminescence in an RNA-based homochiral, self-repairing, coordination polymer hydrogel

El-Zubir, Osama and Rojas Martinez, Pablo and Dura, Gema and Al-Mahamad, Lamia L.G. and Pope, Thomas and Penfold, Thomas J. and MacKenzie, Lewis E. and Pal, Robert and Mosely, Jackie A. and Cucinotta, Fabio and McGarry, Liam F. and Horrocks, Benjamin R. and Houlton, Andrew (2022) Circularly polarised luminescence in an RNA-based homochiral, self-repairing, coordination polymer hydrogel. Journal of Materials Chemistry. C, 10 (18). pp. 7329-7335. ISSN 2050-7526 (https://doi.org/10.1039/D2TC00366J)

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Abstract

The aqueous equimolar reaction of Ag(I) ions with the thionucleoside enantiomer (−)6-thioguanosine, ((−)6tGH), yields a one-dimensional coordination polymer {Ag(−)tG}n, the self-assembly of which generates left-handed helical chains. The resulting helicity induces an enhanced chiro-optical response compared to the parent ligand. DFT calculations indicate that this enhancement is due to delocalisation of the excited state along the helical chains, with 7 units being required to converge the calculated CD spectra. At concentrations ≥15 mmol l−1 reactions form a sample-spanning hydrogel which shows self-repair capabilities with instantaneous recovery in which the dynamic reversibility of the coordination chains appears to play a role. The resulting gel exhibits circularly polarised luminescence (CPL) with a large dissymmetry factor of −0.07 ± 0.01 at 735 nm, a phenomenon not previously observed for this class of coordination polymer.