University of Oulu

Roukala, J., Orr, S., Hanna, J., Vaara, J., Ivanov, A., Antzutkin, O., Lantto, P. (2016) Experimental and First-Principles NMR Analysis of Pt(II) Complexes With O,O′-Dialkyldithiophosphate Ligands. Journal of Physical Chemistry A, 120 (42), 8326-8338. doi:10.1021/acs.jpca.6b09586

Experimental and first-principles NMR analysis of Pt(II) complexes with O,O′-dialkyldithiophosphate ligands

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Author: Roukala, Juho1; Orr, Simon T.2; Hanna, John V.2;
Organizations: 1NMR Research Unit, University of Oulu, P.O. Box 3000, FI-90400 Oulu, Finland
2Department of Physics, The University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, United Kingdom
3Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences, Ryolochny Lane 1, Blagoveshchensk 675000, Amur Region, Russia
4Chemistry of Interfaces, Luleå University of Technology, SE-971 87, Luleå, Sweden
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 3.6 MB)
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Language: English
Published: American Chemical Society, 2016
Publish Date: 2017-09-30


Polycrystalline bis(dialkyldithiophosphato)Pt(II) complexes of the form [Pt{S₂P(OR)₂}₂] (R = ethyl, iso-propyl, iso-butyl, sec-butyl or cyclo-hexyl group) were studied using solid-state ³¹P and ¹⁹⁵Pt NMR spectroscopy, to determine the influence of R to the structure of the central chromophore. The measured anisotropic chemical shift (CS) parameters for ³¹P and ¹⁹⁵Pt afford more detailed chemical and structural information, as compared to isotropic CS and J couplings alone. Advanced theoretical modeling at the hybrid DFT level, including both crystal lattice and the important relativistic spin–orbit effects qualitatively reproduced the measured CS tensors, supported the experimental analysis, and provided extensive orientational information. A particular correction model for the non-negligible lattice effects was adopted, allowing one to avoid a severe deterioration of the ¹⁹⁵Pt anisotropic parameters due to the high requirements posed on the pseudopotential quality in such calculations. Though negligible differences were found between the ¹⁹⁵Pt CS tensors with different substituents R, the ³¹P CS parameters differed significantly between the complexes, implying the potential to distinguish between them. The presented approach enables good resolution and a detailed analysis of heavy-element compounds by solid-state NMR, thus widening the understanding of such systems.

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Series: The journal of physical chemistry. A
ISSN: 1089-5639
ISSN-E: 1520-5215
ISSN-L: 1089-5639
Volume: 120
Issue: 42
Pages: 8326 - 8338
DOI: 10.1021/acs.jpca.6b09586
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
119 Other natural sciences
Funding: J.R. thanks the Finnish Cultural Foundation for funding this research, with further support received from the National Doctoral Programme in Nanoscience (NGS-NANO), the Tauno Tönning Foundation, and University of Oulu. P.L. was supported by the Academy of Finland projects number 125316, 218191, 255641, and 285666, and the work of J.V. by the directed programme in Computational Science of the Academy of Finland, project number 258565. J.V.H. thanks the EPSRC and the University of Warwick for partial funding of the solid-state NMR infrastructure at Warwick and acknowledges additional support for this infrastructure obtained through Birmingham Science City: Innovative Uses for Advanced Materials in the Modern World (West Midlands Centre for Advanced Materials Projects 1 and 2), with support from Advantage West Midlands (AWM) and partial funding by the European Regional Development Fund (ERDF).
Academy of Finland Grant Number: 125316
Detailed Information: 125316 (Academy of Finland Funding decision)
218191 (Academy of Finland Funding decision)
255641 (Academy of Finland Funding decision)
285666 (Academy of Finland Funding decision)
258565 (Academy of Finland Funding decision)
Copyright information: © 2016 American Chemical Society. Published in this repository with the kind permission of the publisher.