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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
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0001-9577-6845
Department of Chemical Sciences, Division of Chemical Engineering, Tezpur University, Tezpur, Assam.
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0002-0292-1159
University of Oulu, NMR Research Group, Division of Chemical Engineering, Faculty of Science, University of Oulu.
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2016 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, Vol. 20, p. 3278-3291Article in journal (Refereed) Published
Abstract [en]

We present a structural analysis method for molecular and electronic structure of yttrium diethyldithiocarbamato-phenanthroline complex {[Y(S2CNR2)3PHEN] with R = C2H5 and PHEN = 1,10-phenanthroline} combining solid-state NMR spectroscopy, XRD, and first principles DFT calculations. Replacing the Nd3+ ion with Y3+ in the reported crystal structure of [Nd(S2CNR2)3PHEN] 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 13C and 15N 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 S2CN-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

Place, publisher, year, edition, pages
2016. Vol. 20, p. 3278-3291
National Category
Physical Chemistry Other Physics Topics
Research subject
Chemistry of Interfaces; Tillämpad fysik
Identifiers
URN: urn:nbn:se:ltu:diva-15691DOI: 10.1002/ejic.201600059ISI: 000379985600009Scopus ID: 2-s2.0-84978397931Local ID: f3cebb95-1de1-4acf-b56e-aebed545a76cOAI: oai:DiVA.org:ltu-15691DiVA, id: diva2:988666
Note
Validerad; 2016; Nivå 2; 20160615 (andbra)Available from: 2016-09-29 Created: 2016-09-29 Last updated: 2018-07-10Bibliographically approved
In thesis
1. Experimental and Computational Magnetic Resonance Studies of Selected Rare Earth and Bismuth Complexes
Open this publication in new window or tab >>Experimental and Computational Magnetic Resonance Studies of Selected Rare Earth and Bismuth Complexes
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The rare-earth elements (REEs) and bismuth, being classified as the ‘most critical raw materials’ (European Raw Materials Initiatives, 2017), have a high economic importance to the EU combined with a high relative supply risk. REEs are highly important for the evolving technologies such as clean-energy applications, high-technology components, rechargeable batteries, permanent magnets, electric and hybrid vehicles, and phosphors monitors.This scientific research work aims at building a fundamental knowledge base concerning the electronic/molecular structure and properties of rare-earth element (REE) and bismuth complexes with dithiocarbamate (DTC) and 1,10-phenanthroline (PHEN) by employing state-of-the-art experimental techniques such as nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) techniques together with ab initioquantum mechanical computational methods. This combination of methods has played a vital role in analysing the direct and significant effect of the heavy metal ions on the structural and magnetic resonance properties of the complexes, thereby, providing a framework of structure elucidation. This is of special importance for REEs, which are known to exhibit similar chemical and physical properties. The objectives of the work involve i) a systematic investigation of series of REE(III) as well as bismuth(III) complexes to get a profound understanding of the structure-properties relationship and ii) to find an appropriate theoretical modelling and NMR calculation methods, especially, for heavy metal systems in molecular and/or solid-state. This information can later be used in surface interaction studies of REE/bismuth minerals with DTC as well as in design and development of novel ligands for extraction/separation of metal ions.The REE(III) and bismuth(III) complexes with DTC and PHEN ligands have all provided aunique NMR fingerprint of the metal centre both in liquid and solid phase. The solid-state 13C and 15NNMR spectra of the diamagnetic REE(III) and bismuth(III) complexes were in accord with their structural data obtained by single crystal XRD. The density functional theory (DFT) methods were used to get complementary and refined structural and NMR parameters information for all diamagnetic complexes in the solid-state. The relativistic contributions due to scalar and spin-orbit correlations for the calculated 1H/13C/15N chemical shifts of REE complexes were analysed using two-component zeroth-order regular approximation (ZORA)/DFT while the ‘crystal-lattice’ effects on the NMR parameters were calculated by combining DFT calculations on molecular and periodic solid-state models. The paramagnetic REE complexes display huge differences in their 1H and 13C NMR spectral patterns. The experimental paramagnetic NMR (pNMR) chemical shifts, as well as the sizable difference of the 1H and 13C NMR shifts for these isoelectronic complexes, are well reproduced by the advanced calculations using ab initio/DFT approach. The accuracy of this approach is very promising for further applications to demanding pNMR problems involving paramagnetic f-block elements.The results presented in this thesis demonstrate that a multidisciplinary approach of combined experimental NMR and XRD techniques along with computational modelling and property calculations is highly efficient in studying molecular complexes and solids containing heavy metal systems, such as rare-earths and bismuth.

Place, publisher, year, edition, pages
Luleå University of Technology, 2017
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Chemical Sciences Physical Sciences
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-65378 (URN)978-91-7583-947-9 (ISBN)978-91-7583-948-6 (ISBN)
Public defence
2017-09-29, C305, Luleå tekniska universitet, Luleå, 10:00
Supervisors
Available from: 2017-08-29 Created: 2017-08-28 Last updated: 2018-06-05Bibliographically approved

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Gowda, VasanthaÖberg, SvenLarsson, Anna-CarinAntzutkin, Oleg

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