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Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering. NMR Research Unit, University of Oulu.
Department of Chemical Sciences, Tezpur University.
Laboratory of Inorganic Chemistry, University of Oulu.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.
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2017 (English)In: Polyhedron, ISSN 0277-5387, E-ISSN 1873-3719, Vol. 129, 123-132 p.Article in journal (Refereed) Published
Abstract [en]

Two crystalline polymorphs of a binuclear tris(di-n-butyldithiocarbamato)bismuth(III) complex, I and II, with an empirical formula of [Bi{S2CN(n-C4H9)2}3] were synthesised and characterised by X-ray diffraction (XRD), solid-state NMR and density functional theory (DFT) calculations. At the supramolecular level, these mononuclear molecular units interact in pairs via secondary Bi⋯S bonds, yielding binuclear formations of [Bi2{S2CN(n-C4H9)2}6]. The polymorph I () contains two isomeric non-centrosymmetric binuclear molecules of [Bi2{S2CN(n-C4H9)2}6], which are related to each other as conformers, therefore having four structurally inequivalent bismuth atoms and twelve inequivalent dithiocarbamate ligands. In contrast, the structurally simpler polymorph II (P21/n) exists as a single molecular form of the corresponding centrosymmetric binuclear formation, comprising two structurally equivalent bismuth atoms and three structurally different dithiocarbamate groups. The polymorphs I and II were found to be interconvertible by altering the solvent system during the recrystallisation process. Sun et al. (2012) has reported a crystalline form of the title compound which resembles, but is not identical with, polymorph II. Experimental solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR spectra of both polymorphs I and II were in accord with the direct structural data on these complexes. Assignments of the resonance lines in the solid-state 13C and 15N NMR spectra were assisted by chemical shift calculations of the crystals using periodic DFT.

Place, publisher, year, edition, pages
2017. Vol. 129, 123-132 p.
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
URN: urn:nbn:se:ltu:diva-62688DOI: 10.1016/j.poly.2017.03.018ISI: 000401382500017Scopus ID: 2-s2.0-85017200488OAI: oai:DiVA.org:ltu-62688DiVA: diva2:1084688
Note

Validerad; 2017; Nivå 2; 2017-04-12 (rokbeg)

Available from: 2017-03-27 Created: 2017-03-27 Last updated: 2017-11-24Bibliographically 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: 2017-11-24Bibliographically approved

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