Special Issue to Prof. Doron Aurbach,celebrating his 70th birthday

Journal of Solid State Electrochemistry -     

New Editor-in-Chief,J. Solid State Electrochemistry

Journal of Solid State Electrochemistry -     

Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications

Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science.     

N,N′-Ethylene-Bridged Bis-2-Aryl-Pyrrolinium Cations to E-Diaminoalkenes: Non-Identical Stepwise Reversible Double-Redox Coupled Bond Activation Reactions

This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi-pyrrolinium cation scaffold-based organic redox systems, which constitute decidedly sought-after molecules in contemporary chemistry.     

Electrochemistry and Spin-Crossover Behavior of Fluorinated Terpyridine-Based Co(II) and Fe(II) Complexes

Due to their ability to form stable molecular complexes that have tailor-made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding Co^II and Fe^II complexes were synthesized and characterized by single-crystal X-ray structural analysis, electrochemistry and temperature-dependent SQUID magnetometry. Single crystal X-ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin Co^II and Fe^II centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis-NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction.     

Influence of Solution Volume on the Dissolution Rate of Silicon Dioxide in Hydrofluoric Acid

Experimental data and modeling of the dissolution of various Si/SiO₂ thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO₂‐film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6–1.2 mL) of the HF solution, an effect of SiO₂‐coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO₂ dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF₂^? accumulation in the HF solution, owing to SiO₂ dissolution was identified as the source of the chemical alteration.     

Recent development in the field of ceramics solid-state electrolytes: I—oxide ceramic solid-state electrolytes

Journal of Solid State Electrochemistry - Many elements in the periodic table form ionic compounds; the crystal lattices of such compounds contain cations and anions, which are arranged in the way...     

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3-Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated Au^I species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.     

Aromatic Polynitro Ether Derivatives of Cellulose

The nucleophilic reaction of sodium cellulosate in the form of membrane or cotton fabric with 2, 4-dinitrohalo-benzenes, 2, 4, 6-trinitrochlorobenzene, 2, 4, 6-trinitrobenzyl bromide, and 2, 4, 6-trinitrostyrene was investigated. The degree of substitution attained with the dinitroaryl derivatives was much higher than that with the trinitroaryl derivatives. The reaction proceeded through Meisen-heimer complexes, which in the case of the trinitro derivatives could be isolated. The ability of the polynitro phenyl ether derivatives of the cellulose to form n- and π-complexes was investigated using naphthalene and p-toluidine. No -π- complex was formed with the former, and the latter gave complexes only with the 2, 4, 6-trinitrobenzyl or -phenethyl cellulose derivatives but not with the trinitrophenyl. The results were explained as due to steric hindrance from the polymeric cellulosic backbone.