DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline

摘要: The molecular, crystal, and electronic structures as well spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13C 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern CP-MAS NMR spectra indicated that the title compound is not isostructural to previously reported analogous rare earth complexes space group P21/n. Both revealed presence six structurally dithiocarbamate groups in asymmetric unit cell, implying non-centrosymmetric packing arrangement molecules. This was supported single-crystal crystallography showing crystallised triclinic P1[combining macron]. In addition, crystal structure also one has conformational disorder. chemical shift calculations employing periodic gauge including projector augmented wave (GIPAW) approach assignment experimental spectra. However, best correspondences obtained where atomic positions cell optimised at DFT level. roles scalar spin-orbit relativistic effects on shielding investigated using zeroth-order regular approximation (ZORA) method outcome already level qualitatively reproduces shifts. evaluated based results natural bond orbital (NBO) topology electron analyses. Overall, we apply multidisciplinary acquiring comprehensive information about metal-ligand bonding lanthanum complex.