5,7-Bis(2'-arylethenyl)-6H-1,4-diazepine-2,3-dicarbonitriles: synthesis, and experimental and theoretical evaluation of the effects of substituents at 5,6,7-positions on the molecular configuration and spectral properties.

A series of novel 5,7-bis(2'-arylethenyl)-6H-1,4-diazepine-2,3-dicarbonitriles was synthesized through sequential aldol condensation reactions of 1,3-diketones with diaminomaleonitrile, and the resulting 5,7-dimethyl-6H-1,4-diazepines were condensed with aromatic aldehydes. The substituents' effects on the spectral properties and conformational states of the molecules in solution were studied using 2D NMR techniques and DFT calculations. Specific intramolecular steric interactions in derivatives substituted at the C6 position were discovered and investigated in detail.

Novel A₃B-type tert-butyl-substituted tribenzodiazepinoporphyrazine: synthesis, spectral properties and DFT study.

Novel A3B-type 8(9),13(14),18(19)-tri-tert-butyl-2(5),4(7)-bis(4-tert-butylphenyl)tribenzo[g,l,q]-6H-1,4-diazepino[2,3-b]porphyrazine, which has high solubility in organic solvents, was obtained by template co-condensation of 2,3-dicyano-5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepine and 4-tert-butylphthalonitrile. It was characterized by UV/Vis, (1)H, (13)C NMR spectroscopy, and MALDI-TOF/TOF mass spectrometry. We have demonstrated for the first time using fluorescence spectroscopy measurements and quantum-chemical calculations that the complicated UV/Vis spectrum of A3B-type tribenzodiazepinoporphyrazine is due to the formation of stable H-type aggregates.