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Structure Elucidation of an Yttrium Diethyldithiocarbamato‐Phenanthroline Complex by X‐ray Crystallography, Solid‐State NMR, and ab‐initio Quantum Chemical Calculations
Author(s) -
Gowda Vasantha,
Sarma Bipul,
Öberg Sven,
Telkki VilleVeikko,
Larsson AnnaCarin,
Lantto Perttu,
Antzutkin Oleg N.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600059
Subject(s) - chemistry , ab initio , crystal structure , crystallography , yttrium , molecular orbital , fragment molecular orbital , electronic structure , ab initio quantum chemistry methods , computational chemistry , molecule , organic chemistry , oxide
We present a structural analysis method for molecular and electronic structure of yttrium diethyldithiocarbamato‐phenanthroline complex {[Y(S 2 CNR 2 ) 3 PHEN] with R = C 2 H 5 and PHEN = 1,10‐phenanthroline} combining solid‐state NMR spectroscopy, XRD, and first principles DFT calculations. Replacing the Nd 3+ ion with Y 3+ in the reported crystal structure of [Nd(S 2 CNR 2 ) 3 PHEN] complex generated an approximate 3D structure of the title complex. The structure was then subjected to first principles quantum chemical geometry optimisation using periodic DFT method. The quality of the method is discussed by comparing predicted and experimental powder XRD patterns. Full assignment of 13 C and 15 N solid‐state CP‐MAS NMR spectra as well as analyses of the principal values of the chemical shift tensors were carried out using periodic scalar relativistic DFT modelling. Spin‐orbit relativistic effects, estimated by SO‐ZORA formalism for one molecular unit, were evaluated. Finally, the X‐ray structure of the title complex was determined, which proved that the former procedure is appropriate. The most important orbital interactions were investigated by Natural Bond Orbital analysis. The isotropic shielding values for S 2 CN‐carbons were analysed by Natural Localised Molecular Orbital analysis. The present approach can be further extended to study other rare earth metal complexes, particularly those having similar but not yet solved crystal structures.