The syntheses, structures and spectroelectrochemical properties of 6-oxo-verdazyl derivatives bearing surface anchoring groups

A series of 6-oxo verdazyl radicals functionalised at the 1- and 5-positions by methyl, thiomethyl and iodo groups were synthesised using conventional strategies. Facile Sonogashira cross-coupling reactions of terminal alkynes...

The syntheses, structures and spectroelectrochemical properties of 6-oxo-verdazyl derivatives bearing surface anchoring groups

A series of 6-oxo verdazyl radicals functionalised at the 1- and 5-positions by methyl, thiomethyl and iodo groups were synthesised using conventional strategies. Facile Sonogashira cross-coupling reactions of terminal alkynes with the diiodo analogue were used for synthetic elaboration of the verdazyl core structure with π-conjugated ethynyl groups. The radicals were characterised by EPR spectroscopy, single-crystal X-ray diffraction, cyclic voltammetry and optical spectroscopy. The chemically and electrochemically reversible oxidation and reduction of these radicals within a convenient redox window permitted further studies on the closed-shell cationic and anionic forms using spectroelectrochemical methods, supported by (TD-)DFT calculations.

SYNTHESIS OF 3,3´-(1,4-PHENYLENE)BIS(1-(4-R-PHENYL)-5-PHENYL-5,6-DIHYDRO-1,2,4,5-TETRAZINIUM) PERCHLORATES

A series of 3,3'-(1,4-phenylene)bis(1-4-R-phenyl)-5-phenyl-5,6-dihydro-1,2,4,5-tetrazinium) perchlorates containing hydrogen, methyl, bromio, methoxy, acetyl and nitro groups (R = H, Me, Br, OMe, COMe, NO2) as substituents were obtained as a result of a three-stage synthesis from terephthalic aldehyde. The synthesis of tetrazinium salts was carried out by reaction of the corresponding formazans with formalin in the presence of perchloric acid in dioxane. Formazans were obtained by reaction of terephthalic aldehyde phenylhydrazone with arenediazonium tosylates in a mixture of DMF and pyridine. The usage of arenediazonium tosylates made it possible to extremely simplify the segregation and purification of formazans. The phenylhydrazone was synthesized according to the standard procedure from terephthalic aldehyde and phenylhydrazine/hydrochloric acid in aqueous dioxane. The formazans and tetrazinium perchlorates were isolated in individual state and characterized by elemental analysis, IR, UV, 1H and 13C NMR spectroscopy data. The process of electrochemical reduction of tetrazinium perchlorates was studied using the method of cyclic voltammetry (CV). Thus, the CV curves of all salts in the cathode region contain two one-electron reduction peaks, which are related to the sequential formation of a radical cation and a biradical. It was found that electron-donating substituents (R = Me, OMe) in the aromatic ring at position 1 facilitate the reduction of tetrazinium cation, while electron-withdrawing substituents (R = COMe, NO2) hinder this process. On this basis, it was suggested that the corresponding bis-verdazyl radicals should be easily formed in the presence of electron-donating substituents in the aromatic ring at position 1. Thus, 3,3´-(1,4-phenylene)bis(1-(4-R-phenyl)-5-phenyl-5,6-dihydro-1,2,4,5-tetrazinium-1) perchlorates are perspective precursors of symmetric biradical systems based on verdazyl radicals.

Enhanced Synthesis of oxo-Verdazyl Radicals Bearing Sterically-and Electronically-Diverse C3-Substitents

The synthetic viability of the hydrazine- and phosgene-free synthesis of 1,5-dimethyl oxo-verdazyl radicals has been improved via a detailed study investigating the influence of the aryl substituent on the tetrazinanone...

Kinetic investigation of thermal and photoinduced homolysis of alkylated verdazyls

The generation of verdazyl radicals under heating or irradiation have been highlighted.

Verdazyls as Possible Building Blocks for Multifunctional Molecular Materials: A Case Study on 1,5-Diphenyl-3-(p-iodophenyl)-verdazyl Focusing on Magnetism, Electron Transfer and the Applicability of the Sonogashira-Hagihara Reaction

This work explores the use of Kuhn verdazyl radicals as building blocks in multifunctional molecular materials in an exemplary study, focusing on the magnetic and the electron transfer (ET) characteristics, but also addressing the question whether chemical modification by cross-coupling is possible. The ET in solution is studied spectroscopically, whereas solid state measurements afford information about the magnetic susceptibility or the conductivity of the given samples. The observed results are rationalized based on the chemical structures of the molecules, which have been obtained by X-ray crystallography. The crystallographically observed molecular structures as well as the interpretation based on the spectroscopic and physical measurements are backed up by DFT calculations. The measurements indicate that only weak, antiferromagnetic (AF) coupling is observed in Kuhn verdazyls owed to the low tendency to form face-to-face stacks, but also that steric reasons alone are not sufficient to explain this behavior. Furthermore, it is also demonstrated that ET reactions proceed rapidly in verdazyl/verdazylium redox couples and that Kuhn verdazyls are suited as donor molecules in ET reactions.

Verdazyls as Possible Building Blocks for Multifunctional Molecular Materials: A case Study on 1,5-Diphenyl-3-(p-iodophenyl)-verdazyl Focusing on Magnetism, Electron Transfer and the Applicability of the Sonogashira-Hagihara Reaction

This work explores the use of Kuhn verdazyl radicals as building blocks in multifunctional molecular materials in an exemplary study, focusing on the magnetic and the electron transfer (ET) characteristics, but also addressing the question whether chemical modification by cross-coupling is possible. The ET in solution is studied spectroscopically whereas solid state measurements afford information about the magnetic susceptibility or the conductivity of the given samples. The observed results are rationalized based on the chemical structures of the molecules, which have been obtained by X-ray crystallography. The crystallographically observed molecular structures as well as the interpretation based on the spectroscopic and physical measurements are backed up by DFT calculations. The measurements indicate that only weak, antiferromagnetic coupling is observed in Kuhn verdazyls owed to the low tendency to form face-to-face stacks, but also that steric reasons alone are not sufficient to explain this behavior. Furthermore, it is also demonstrated that ET reactions proceed rapidly in verdazyls/verdazylium redox couples and that Kuhn verdazyls are suited as donor molecules in ET reactions.

The aromaticity of verdazyl radicals and their closed-shell charged species

The aromaticity of fourteen 3-oxo-verdazyl (1–8) and Kuhn verdazyl (9–14) radicals with different substituents has been investigated computationally using the gauge-including magnetically induced current-density (GIMIC) method.