2,5-DisubstitutedN, N′-Dicyanoquinone Diimines (DCNQIs) − Syntheses and Redox Properties

Abstract

Quinones 1a−q and DCNQIs 2a−g have been synthesized in order to investigate substituent effects. It was necessary to employ novel synthetic routes for the introduction of iodine into 1f (7), the trifluoromethyl group into 1g−i, deuterium into 1m−p, and especially for the chloride/fluoride exchange of 1j to 1k, and 1l. With few exceptions both 1 and 2 undergo reversible electron transfer in two steps including thermodynamically very stable radical cations (lg KSEM > 10, cyclic voltammetry). Linear correlations have been found between E2 (OX/SEM) data of 1 and 2 with (σm + σp)/2 and between E2 of 1 and 2. Correlations have also been found between E2 and the LUMO energies of 1 and 2. The crystal structure of quinone 1i shows some special interactions due to the two CF3 groups, whereas the structures of DCNQIs 2d and 2g link up with those evaluated earlier.

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

“…, in particular for F-PDO ) during redox cycling, suggesting that the anionic monoradical (Scheme , route A) is likely gradually involved in the formation of the homodimeric species. The third reduction signal measured at ∼−1.7 V for F-PD and F-PDO after the first reduction sweep are likely attributed either to the reduction of the quinone methide radical or to quinone methide polymerization, as observed for difluoromethyl-menadione and related compounds. , …”

“…The third reduction signal measured at ∼−1.7 V for F-PD and F-PDO after the first reduction sweep are likely attributed either The Journal of Organic Chemistry to the reduction of the quinone methide radical 34 or to quinone methide polymerization, as observed for difluoromethyl-menadione 33 and related compounds. 33,35 For route A (Scheme 5), the radical species formed after the reductive elimination of F − might spontaneously self-dimerize (i.e., a radical−radical homocoupling reaction). A hetero-dimeric coupling or the formation of polymeric species are unlikely to occur, since this dimeric species (vide infra), which corresponds to the binaphthoquinone homodimer, was unambiguously characterized.…”

A study of ion charge transfer on electrochemical behaviors of poly(vinylidene fluoride)-derived carbon electrodes

“…The micropore widths in the range from 0.62 to 0.64 nm for PVDF-derived carbon may be formed because the trifluorine group of CF 3 functional group was released from the carbon chain at higher carbonization temperatures. Considering the rotational diameter of CF 3 functional group ranges from 0.52 to 0.56 nm [29], release of fluoride groups from the chain is the main factor which causes the formation of ultramicropores in PVDF-derived carbons. It was noted that porous parameters for PVDF-derived carbon depend strongly on both residual fluorine contents and carbonization temperature.…”