Visualization and quantitation of electronic communication pathways in a series of redox-active pillar[6]arene-based macrocycles
| Autor: | Sedigheh Etezadi, Burjor Captain, Angel E. Kaifer, Mehdi Rashvand Avei |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Chemistry Pillar Context (language use) General Chemistry 010402 general chemistry Electrochemistry 01 natural sciences Biochemistry Combinatorial chemistry Benzoquinone Redox 0104 chemical sciences lcsh:Chemistry lcsh:QD1-999 Materials Chemistry Structural isomer Environmental Chemistry Molecule Electronic communication |
| Zdroj: | Communications Chemistry, Vol 3, Iss 1, Pp 1-15 (2020) |
| ISSN: | 2399-3669 |
| Popis: | While oxidized pillar[5]arenes with 1-5 benzoquinone units are known, very few examples of oxidized pillar[6]arenes have been reported. We describe here the synthesis, characterization and electrochemical behavior of a series of macrocyclic hosts prepared by the stepwise oxidation of 1,4-diethoxypillar[6]arene, resulting in high-yield and high-purity isolation of two constitutional isomers for each macrocycle, in which two, three or four 1,4-diethoxybenzene units are replaced by benzoquinone residues. A careful structural comparison with their counterparts in the pillar[5]arene framework indicates that the geometries of the macrocycles are better described as non-Euclidean hyperbolic hexagons and elliptic pentagons, respectively. A comprehensive computational study to determine anisotropic induced current density (ACID) allows us to visualize and quantify through-space and through-bond communication pathways along the macrocyclic belt. Experimental and simulated voltammetric data, as well as UV-vis spectra, of the new macrocycles afford insights into the various electronic communication pathways in these compounds. Partially oxidised pillar[n]arenes exhibit interesting redox behaviour, but the pillar[6]arenes are poorly characterised in this context. Here stepwise oxidation of 1,4-diethoxypillar[6]arene allows detailed study of the structural and electrochemical properties of molecules with 2, 3, and 4 oxidised units. |
| Databáze: | OpenAIRE |
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