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A Redox-Switchable, Allosteric Coordination Complex

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journal contribution
posted on 2018-10-26, 18:18 authored by Ho Fung Cheng, Andrea I. d’Aquino, Joaquín Barroso-Flores, Chad A. Mirkin
A redox-regulated molecular tweezer complex was synthesized via the weak-link approach. The PtII complex features a redox-switchable hemilabile ligand (RHL) functionalized with a ferrocenyl moiety, whose oxidation state modulates the opening of a specific coordination site. Allosteric regulation by redox agents gives reversible access to two distinct structural statesa fully closed state and a semi-open statewhose interconversion was studied via multinuclear NMR spectroscopy, cyclic voltammetry, and UV–vis–NIR spectroscopy. Two structures in this four-state system were further characterized via SCXRD, while the others were modeled through DFT calculations. This fully reversible, RHL-based system defines an unusual level of electrochemical control over the occupancy of a specific coordination site, thereby providing access to four distinct coordination states within a single system, each defined and differentiated by structure and oxidation state.