4.6 Article

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

Journal

JOURNAL OF MATERIALS CHEMISTRY C
Volume 10, Issue 18, Pages 7329-7335

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2tc00366j

Keywords

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Funding

  1. EPSRC [EP/P015395/1]
  2. Newcastle University
  3. EU [H2020-MSCA-ITN-2016-INDEED 722176, SBPLY/19/180501/000191]
  4. Junta de Comunidades de Castilla la Mancha
  5. Royal Society University Research Fellowship [URF\R\191002, H2020-MSCA-ITN-859752 HEL4CHIROLED]
  6. BBSRC [BB/S017615/1]
  7. BBSRC Discovery Fellowship [BB/S017615/1, BB/T009268/1]
  8. Iraqi Ministry of Higher Education and Scientific Research
  9. Mustansiriyah University
  10. BBSRC [BB/T009268/1, BB/S017615/1] Funding Source: UKRI

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This article discusses the properties of a one-dimensional coordination polymer formed by the reaction of Ag(i) ions with the thionucleoside enantiomer. The study found that the resulting polymer has a left-handed helical chain structure and exhibits enhanced chiro-optical response compared to the parent ligand. Experimental results also show that at higher concentrations, the reaction forms a self-repairing hydrogel that exhibits circularly polarised luminescence.
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.

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