Indexed on: 14 Jun '16Published on: 07 Jun '16Published in: Journal of Porphyrins and Phthalocyanines
Journal of Porphyrins and Phthalocyanines, Volume 20, Issue 01n04, Page 525-533, January & April 2016. A thoroughly structural characterization of (TTC)GePh (TTC [math] 5,10,15-tritolylcorrole; Ph [math] phenyl) in solution has been carried out through a combination of 2D NMR (1H-1H COSY, 1H-1H ROESY, 1H-[math]C HSQC and 1H-[math]C HMBC) experiments and density functional theory (DFT) calculations of the molecular and electronic structure and the shielding constants. The 1H and [math]C chemical shifts computed at DFT-S12g and DFT-SAOP levels of theory nicely reproduce the experimental values, the agreement between theory and experiment being especially good for the DFT-S12g results. The calculations prove to be able to capture the fine details of the NMR spectra and to resolve some assignment ambiguities related to the inherent conformational flexibility of the macrocycle. The calculations also provide an explanation of the observed chemical shift trends in terms of diamagnetic and paramagnetic components of the shielding tensor. Reported herein is a thoroughly structural characterization of (TTC)GePh (TTC = 5,10,15-tritolylcorrole; Ph = phenyl) in solution by a combination of 2D NMR (1H-1H COSY, 1H-1H ROESY, 1H-13C HSQC and 1H-13C HMBC) experiments and density functional theory (DFT) calculations of the shielding constants.