The redox properties of metallo-base pairs remain to be elucidated. Herein, we report the detailed1H/13C/109Ag NMR spectroscopic and cyclic voltammetric characterisation of the [Ag(cytidine)2]+complex as isolated cytosine-Ag+-cytosine (C-Ag+-C) base pairs. We also performed comparative studies between cytidine/Ag+and other nucleoside/Ag+systems by using cyclic voltammetry measurements. In addition, to evaluate the effect of [Ag(cytidine)2]+formation on the chemical reduction of Ag+to Ag, we utilised the redox reaction between Ag+and tetrathiafulvalene (TTF). We found that Ag+-mediated base pairing lowers the redox potential of the Ag+/Ag couple. In addition, C-Ag+-C base pairing makes it more difficult to reduce captured Ag+ions than in other nucleoside/Ag+systems. Remarkably, the cytidine/Ag+system can be utilised to control the redox potential of the Ag+/Ag couple in DMSO. This feature of the cytidine/Ag+system may be exploited for Ag nanoparticle synthesis by using the redox reaction between Ag+and TTF.
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