Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14⋅+ through post-synthetic oxidation of a redox-active phenothiazine-based Pd2L4-type coordination cage 1. It\'s worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5-di-tert-butyl-4-methoxyphenyl substituent. The generation of 14⋅+ through reversible electrochemical oxidation is investigated by in situ UV/Vis-NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14⋅+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X-ray diffraction analysis of 14⋅+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14⋅+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages.

Understanding the kinetics of interfacial ion speciation could inform battery designs. However, this knowledge gap persists, largely due to the challenge of experimentally interrogating the evolution of ions near electrode interfaces in a sea of bulk signals. We report here the very first kinetically resolved correlation between interfacial ion speciation and lithium-ion storage in a model system, by applying global target analysis to in situ attenuated total reflectance (ATR) Fourier-Transform infrared (FTIR) spectroelectrochemical data. Our results suggest that it may be more kinetically viable for lithium to be extracted from contact ion pairs (CIPs) to contribute to faster electrode charging compared to fully solvated lithium. As the search for fast-charging lithium-ion batteries and supercapacitors wages on, this discovery suggests that manipulating the ion pairing within the electrolyte could be one effective strategy for promoting faster-charging kinetics.

The neuronal calcium sensor protein recoverin is expressed in retinal rod and cone cells and is involved in the calcium-dependent control of receptor (rhodopsin) phosphorylation and receptor inactivation. In its Ca2+-saturated form recoverin is attached to membranes by an exposed myristoyl group and responds to oscillating changes of intracellular Ca2+-concentration by performing a so-called Ca2+-myristoyl switch. In this work we analyze changes in a liquid lipid bilayer interacting with myristoylated and non-myristoylated recoverin by employing polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) with electrochemical control. The lipid bilayer is transferred onto a polycrystalline gold electrode using Langmuir-Blodgett Langmuir-Schaefer transfer at the surface pressure π = 30 mN m-1 which ensures, necessary for the lipid-protein interaction, liquid state of the hydrocarbon chains of phospholipids. The model lipid bilayers are adsorbed directly on the Au electrode surface at transmembrane potentials -0.2 < ∆ϕM|S < 0.25 V. The interaction with recoverin leads to a stabilization of the adsorbed state of the lipid bilayer at positive transmembrane potentials. The interaction leads to a decrease in the surface charge density that accumulates on the membrane covered electrode surface, indicating changes in the lateral interactions in the lipid membrane. In situ spectroelectrochemical studies confirm orientation changes in the hydrophobic environment of the model membrane. Insertion of the myristoyl group of recoverin into the membrane is connected with an increase in the tilt of the hydrocarbon chains with respect to the surface normal and decrease in the bilayer thickness. Potential-induced pore formation and desorption of the lipid bilayer from the membrane surface is accompanied by the removal of the acyl chains of recoverin from the membrane.