Issue 11, 2019

Addressing the properties of “Metallo-DNA” with a Ag(i)-mediated supramolecular duplex

Abstract

The silver-nucleoside complex [Ag(I)-(N3-cytidine)2], 1, self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on 1 show that despite having Ag⋯Ag distances within <5% of the metallic radii, the material is electrically insulating. This is due to the electronic structure which features a filled valence band, an empty conduction band dominated by the ligand, and a band gap of 2.5 eV. Hence, as-prepared, such Ag(I)-DNA systems should not be considered molecular nanowires but, at best, proto-wires. The structural features seen in 1 are essentially retained in the corresponding organogel which exhibits thixotropic self-healing that can be attributed to the reversible nature of the intermolecular interactions. Photo-reduced samples of the gel exhibit luminescence confirming that these poly-cytidine sequences appropriately pre-configure silver ions for the formation of quantum-confined metal clusters in line with contemporary views on DNA-templated clusters. Microscopy data reveals the resulting metal cluster/particles are approximately spherical and crystalline with lattice spacing (111) similar to bulk Ag.

Graphical abstract: Addressing the properties of “Metallo-DNA” with a Ag(i)-mediated supramolecular duplex

Supplementary files

Article information

Article type
Edge Article
Submitted
15 Nov 2018
Accepted
08 Feb 2019
First published
08 Feb 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 3186-3195

Addressing the properties of “Metallo-DNA” with a Ag(I)-mediated supramolecular duplex

L. Mistry, O. El-Zubir, G. Dura, W. Clegg, P. G. Waddell, T. Pope, W. A. Hofer, N. G. Wright, B. R. Horrocks and A. Houlton, Chem. Sci., 2019, 10, 3186 DOI: 10.1039/C8SC05103H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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