1H and 13C NMR spectra, structure and physicochemical features of phenyl acridine-9-carboxylates and 10-methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulphonates – alkyl substituted in the phenyl fragment

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2011, Vol.78 (1), p.401-409
• Main Authors: Krzymiński, K., Malecha, P., Zadykowicz, B., Wróblewska, A., Błażejowski, J.
• Format: Article
• Language: English
• Subjects: 10-Methyl-9-(phenoxycarbonyl)acridinium cations; 1H and 13C NMR spectroscopy; Phenyl acridine-9-carboxylates; Physicochemical features; Spectral versus structural or physicochemical characteristics; Structure
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2010.10.029

The 1H and 13C NMR spectra of twelve phenyl acridine-9-carboxylates – alkyl-substituted in the phenyl fragment – and their 10-methyl-9-(phenoxycarbonyl)acridinium salts dissolved in CD 3CN, CD 3OD, CDCl 3 and DMSO- d 6 were recorded in order to examine the influence of the structure of these compounds and the properties of the solvents on chemical shifts and 1H– 1H coupling constants. Experimental data were compared with 1H and 13C chemical shifts predicted at the GIAO/DFT level of theory for DFT(B3LYP)/6-31G** optimised geometries of molecules, as well as with values of 1H chemical shifts and 1H– 1H coupling constants, estimated using ACD/HNMR database software to ensure that the assignment was correct. To investigate the relations between chemical shifts and selected structural or physicochemical characteristics of the target compounds, the values of several of these parameters were determined at the DFT or HF levels of theory. The HOMO and LUMO energies obtained at the HF level yielded the ionisation potentials and electron affinities of molecules. The DFT method provided atomic partial charges, dipole moments, LCAO coefficients of p z LUMO of selected C atoms, and angles reflecting characteristic structural features of the compounds. It was found that the experimentally determined 1H and 13C chemical shifts of certain atoms relate to the predicted dipole moments, the angles between the acridine and phenyl moieties, and the LCAO coefficients of the p z LUMO of the C atoms believed to participate in the initial step of the oxidation of the target compounds. The spectral and physicochemical characteristics of the target compounds were investigated in the context of their chemiluminogenic ability.