The Synthesis of Diquinone and Dihydroquinone Derivatives of Calix[4]arene and Electrochemical Characterization on Au(111) surface

Abstract

In the memory of Janez (Janko) Jamnik, my doctoral advisor who taught me that everything can be done and built if there is a vision and a will. AbstractSeveral new electroactive diquinone and dihydroquinone derivatives of calix [4]arene bearing anchor functional groups were designed, synthesized and characterized. A method for selective protection of the hydroquinone -OH groups with trimethylsilyl groups (TMS) either on lower-rim or on upper-rim was developed. Four selected molecules -with sulfide anchor groups and carboxylic anchor groups -were adsorbed onto Au(111) single crystal surface using ex-situ and insitu self-assembly methods. Adsorbed molecules were then electrochemically probed with cyclic voltammetry. All adsorbed molecules showed redox response which changed during cycling. After conditioning CVs stabilized and showed two distinct current peaks for all molecules. Synthesized and electrochemically probed molecules are of interest to: Li-ion batteries (as cathode materials and overcharge protection), beyond Li-ion batteries and redox-flow batteries.

Design Strategies for Promising Organic Positive Electrodes in Lithium-Ion Batteries: Quinones and Carbon Materials

“…Recently, efforts to identify promising high-performance positive electrode materials have been extended to metal-free organic materials with redox-active sites on their surfaces, such as conducting polymers and quinone molecules. − In addition to their potential for kinetic performance, organic materials are attractive because they can reduce the costs of electrochemical energy storage by replacing conventional transition metal oxides with abundant carbon materials. Specifically, the potential of conducting polymers − and redox-active quinone derivatives − ,− as organic positive electrodes in lithium-ion batteries and catholytes in redox-flow batteries has been investigated intensively.…”

“…Recently, efforts to identify promising high-performance positive electrode materials have been extended to metal-free organic materials with redox-active sites on their surfaces, such as conducting polymers and quinone molecules. − In addition to their potential for kinetic performance, organic materials are attractive because they can reduce the costs of electrochemical energy storage by replacing conventional transition metal oxides with abundant carbon materials. Specifically, the potential of conducting polymers − and redox-active quinone derivatives − ,− as organic positive electrodes in lithium-ion batteries and catholytes in redox-flow batteries has been investigated intensively. For instance, composites of conducting polymers (e.g., polypyrrole and polyaniline) coated on materials such as LiFePO 4 and carbon nanotubes have been suggested as promising positive electrodes with significantly enhanced electronic conductivities and electrochemical activities. , Abruña and co-workers suggested that yolk–shell structures, consisting of sulfur coated with polyaniline and incorporating an internal void space within the shell, could accommodate the volume expansion of sulfur occurring during repeated lithiation/delithiation processes in lithium–sulfur batteries .…”

“…They reported that the macrocyclic skeletons in P5QLi n structures were predicted to be distorted to different extents as a result of the interactions between Li atoms and P5Q. Genorio studied the redox properties of diquinone and dihydroquinone derivatives of calix[4]­arene for positive electrodes in lithium-ion batteries . Tuntulani and co-workers also studied the electrochemical properties of calix[4]­quinones, derived from double calix[4]­arenes, not only for lithium-ion batteries but also for sodium- and potassium-ion batteries .…”

Lanthanoid coordination with a tetrazole-substituted calix[4]diquinone and calix[4]dihydroquinone

“…In addition to the usual suite of characterisation techniques, crystals of appropriate quality for a single Table 1 with the hydrogen bonding polymer shown in Figure 3. The chemical reduction of quinone calixarenes has been reported using aqueous sodium dithionite, 18 and sodium borohydride. 19 Here we chose to use N,N-diethylhydroxylamine (DEH), which has been reported to reduced quinones, 16 to reduce Q to the dihydroquinone QR, to simplify the isolation of the product.…”

Lanthanoid Coordination with a Tetrazole-Substituted Calix[4]diquinone and Calix[4]dihydroquinone

“…Hydrogen bonding geometrical details are listed in Table 1 with the hydrogen bonding polymer shown in Figure 3. The chemical reduction of quinone calixarenes has been reported using aqueous sodium dithionite, 18 and sodium borohydride. 19 Here we chose to use N,N-diethylhydroxylamine (DEH), which has been reported to reduced quinones, 16 to reduce Q to the dihydroquinone QR, to simplify the isolation of the product.…”