1H NMR spectral analysis of structural features in a series of paramagnetic homoleptic binuclear triple-decker phthalocyaninato lanthanide complexes

Analysis of the lanthanide-induced shifts and relaxation rates in 1H NMR spectra of a series of tetra-15-crown-5-phthalocyanine complexes with Nd3+, Tb3+, Dy3+, Ho3+, Er3+ and Tm3+ showed the isostructurality of the whole series of complexes despite f-compression and this result was confirmed by DFT calculations. [Display omitted] The search for efficient methods of comparative structural investigations of coordination compounds in solid state and solutions is a very relevant task. In this study, structural assignments in a series of Ln2[(15C5)4Pc]3 complexes (where [(15C5)4Pc]2- is 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninato-dianion, Ln = Nd3+, Tb3+, Dy3+, Ho3+, Er3+ and Tm3+) was performed using NMR relaxation and paramagnetic lanthanide-induced shifts (LIS) data. Analysis of the paramagnetic chemical shifts and relaxation rates evidenced of isostructurality of the complete series of the investigated triple-decker complexes in the solutions. The performed systematic DFT calculations for a series of model complexes with methoxy-substituted ligands Ln2[(MeO)8Pc]3 demonstrate that the calculated geometrical factors are in agreement with characteristics extracted from experimental NMR data.