Redox-active metal−organic nanocages are of interest for many applications, but the development of cages with extensive redox activity is often hindered by their limited stability and solubility across multiple charge states. This report reveals that these properties can be tuned for cages with redox-active walls by incorporating additional redox activity into the linkers. In particular, new +12 charged triangular nanoprisms 1a,b were formed from three electroactive tetrakis(3pyridyl)porphyrin walls linked by six [(TMEDA)Pt] 2+ (for 1a) or [(2,2′-bipy)Pt] 2+ (for 1b) vertices, the latter of which are also electroactive. Thus, 1b exhibits extensive redox activity, consisting of two porphyrin-centered (x3) and two 2,2′-bipy-centered (x6) reductions that provide reversible access to +12, +9, +3, 0, and −6 charge states, whereas 1a undergoes only two, porphyrin-centered (x3) reversible reductions. Comparisons of 1a and 1b (and monomeric control compounds) by cyclic voltammetry and UV−vis−NIR spectroelectrochemistry show that the redox-activity of the linkers in 1b lowers the second reduction potential of the porphyrins by 100 mV and improves the stability and solubility of this structure under highly reducing conditions (e.g., −2.25 V vs Fc +/0 in MeCN). These findings reveal new principles for controlling the properties of highly electroactive molecular nanostructures. Anion exchange rates (≫10 3 s −1 ) were also probed, showing that the narrow apertures (≤3 Å van der Waals width) of 1a,b do not impede the loss/gain of PF 6 − anions during redox processes.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.