Synthesis of Nonsymmetric Dibenzoyldihydromonobenzotetraazacyclo[14]annulenes as Transition Metal Hosts:X-ray Structure of 13,14-Benzo-3,10-di(p-chlorobenzoyl)-5,8-dihydro-2,4,9,ll-tetramethyl-l,5,8,12-tetraazacyclotetradeca-l,3,9,ll-tetraene

摘要

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 = CH_3,H,Cl,NO_2 and OCH_3,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 approx 1638 cm~(-1).Hammett plot of the energies of pi -> pi~* 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 ~(13)C 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),beta = 109.5930~°,Z = 8) was determined using X-ray diffraction method.