Search

Redox–active components are highly valuable in the construction of molecular devices. We combined two p‐phenylenediamines (p‐PDA) with a biphenyl (BiPhe) unit to prepare a supramolecular guest 4 consisting of three binding sites for cucurbit[7/8]uril (CBn) and/or cyclodextrins (CD). Supramolecular properties of 4 were investigated using NMR, UV‐vis, mass spectrometry and isothermal titration calorimetry. Our analysis revealed that 4 forms higher–order host–guest complexes, wherein a CD unit occupies the central BiPhe site, secured by two CBn units at the terminal p‐PDA sites. Additionally, 1 : 1 complexes with α‐CD and β‐CD, a 1 : 2 complex with γ‐CD and 2 : 1 complexes with CB7 and CB8 were identified. Through UV‐vis and cyclic voltammetry, redox processes leading to the formation of a stable, deep blue dication diradical of 4 are elucidated. Furthermore, it is demonstrated that CB7 selectively protects oxidised 4 from reduction in the presence of a reducing agent. The supramolecular and redox properties of the structural motif represented by 4 render it an interesting candidate for the construction of supramolecular devices. [ABSTRACT FROM AUTHOR]

Inorganic selenium, the most common form of harmful selenium in the environment, can be determined using electrochemical sensors, which are compact, fast, reliable and easy-to-operate devices. Despite progress in this area, there is still significant room for developing high-performance selenium electrochemical sensors. To achieve this, one should take into account (i) the electrochemical process that selenium undergoes on the electrode; (ii) the valence state of selenium species in the sample and (iii) modification of the sensor surface by a material with high affinity to selenium. The goal of this review is to provide a knowledge base for these issues. After the Introduction section, mechanisms and principles of the electrochemical reduction of selenium are introduced, followed by a section introducing the modification of electrodes with materials interacting with selenium and a section dedicated to speciation methods, including the reduction of non-detectable Se(VI) to detectable Se(IV). In the following sections, the main types of materials (metallic, polymers, hybrid (nano)materials...) interacting with inorganic selenium (mostly absorbents) are reviewed to show the diversity of properties that may be endowed to sensors if the materials were to be used for the modification of electrodes. These features for the main material categories are outlined in the conclusion section, where it is stated that the engineered polymers may be the most promising modifiers. [ABSTRACT FROM AUTHOR]

Redox-active components are highly valuable in the construction of molecular devices. We combined two p-phenylenediamines (p-PDA) with a biphenyl (BiPhe) unit to prepare a supramolecular guest 4 consisting of three binding sites for cucurbit[7/8]uril (CBn) and/or cyclodextrins (CD). Supramolecular properties of 4 were investigated using NMR, UV-vis, mass spectrometry and isothermal titration calorimetry. Our analysis revealed that 4 forms higher-order host-guest complexes, wherein a CD unit occupies the central BiPhe site, secured by two CBn units at the terminal p-PDA sites. Additionally, 1 : 1 complexes with α-CD and β-CD, a 1 : 2 complex with γ-CD and 2 : 1 complexes with CB7 and CB8 were identified. Through UV-vis and cyclic voltammetry, redox processes leading to the formation of a stable, deep blue dication diradical of 4 are elucidated. Furthermore, it is demonstrated that CB7 selectively protects oxidised 4 from reduction in the presence of a reducing agent. The supramolecular and redox properties of the structural motif represented by 4 render it an interesting candidate for the construction of supramolecular devices., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)