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How ions arrange in solution: detailed insight from NMR spectroscopy of paramagnetic ion pairs

Abstract Ion pairing between the paramagnetic anion [Tb(obPc)2]? (obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), which has a very large magnetic anisotropy, with various diamagnetic counterions [P(Ph)4]+ (1?a), [As(Ph)4]+ (1?b), bis(triphenylphosphine)iminium ([PPN]+, 1?c) and tetra-n-butyla...

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Bibliographic Details
Main Authors: Damjanović, Marko (Author) , Morita, Takaumi (Author) , Horii, Yoji (Author) , Katoh, Keiichi (Author) , Yamashita, Masahiro (Author) , Enders, Markus (Author)
Format: Article (Journal)
Language:English
Published: 1 September 2016
In: ChemPhysChem
Year: 2016, Volume: 17, Issue: 21, Pages: 3423-3429
ISSN:1439-7641
DOI:10.1002/cphc.201600804
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/cphc.201600804
Verlag, lizenzpflichtig, Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cphc.201600804
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Author Notes:Marko Damjanović, Takaumi Morita, Yoji Horii, Keiichi Katoh, Masahiro Yamashita, Markus Enders
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Summary:Abstract Ion pairing between the paramagnetic anion [Tb(obPc)2]? (obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), which has a very large magnetic anisotropy, with various diamagnetic counterions [P(Ph)4]+ (1?a), [As(Ph)4]+ (1?b), bis(triphenylphosphine)iminium ([PPN]+, 1?c) and tetra-n-butylammonium ([TBA]+, 1?d) was studied by means of 1H, 13C, 14N, and 31P?NMR spectroscopy in solution at various temperatures. The influence of the paramagnetic anion on the NMR spectroscopy properties of the diamagnetic cations allowed a detailed insight into the distances and relative orientations of the paired ions. Isotropic tumbling models for the description of the quaternary cations are inaccurate, particularly for [TBA]+ with its flexible butyl chains. The effects of temperature and concentration were also assessed. The advantage of this technique is that relatively large distances and the orientation between molecules or ions in solution can be studied.
Item Description:Gesehen am 06.05.2020
Physical Description:Online Resource
ISSN:1439-7641
DOI:10.1002/cphc.201600804

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