Synthesis of Nonsymmetric Dibenzoyldihydromonobenzotetraazacycloannulenes as Transition Metal Hosts: X-ray Structure of 13,14-Benzo-3,10-di(p-chlorobenzoyl)-5, 8-dihydro-2,4,9,11-tetramethyl-1,5,8,12-tetraazacyclotetradeca-1,3,9,11-tetraene
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13,14-Benzo-5,8-dihydro-2,4,9,11-tetramethyl-1,5,8,12-tetraazacyclotetradeca-1,3,9,11-tetraene and 13,14-benzo-3,10-di(p-[X]benzoyl)-5,8-dihydro-2,4,9,11-tetramethyl-1,5,8,12-tetraazacyclotetradeca-1,3,9,11-tetraene, wherein X = CH3, H, Cl, NO2 and OCH3, were synthesized and characterized. IR spectra of the benzoylated compounds showed an intense band assigned to the stretching modes of C==O in the region 1632 ~ 1638 cm−1. Hammett plot of the energies of π → π* for the compounds was linear with a positive slope (+0.923). 1H NMR signals exhibited a deshielding effect due to benzoyl groups, while methyl protons only exhibited the shielding effect by the magnetic anisotropy of the group. The substituent effect on 13C NMR was similar to that on proton NMR. The cyclic voltammograms of the compounds mostly showed two one-electron irreversible oxidation peaks and one or two reduction waves between −0.280 and −2.500 V depending on the substituents. Hammett plots of 1st and 2nd oxidation potentials (E op(1) and E op(2)) were linear with slopes of +0.036 and +0.045, respectively. The structure of the compound 4 (monoclinic, C2/c, a = 26.0059 (19), b = 6.9058 (5), c = 33.082 (2), β = 109.5930°, Z = 8) was determined using X-ray diffraction method.
Key wordscrystal structure demetallation free-based tetraazaannulene spectral and electrochemical properties
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