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Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)

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Date
16/02/2015
Author
Knight, Fergus Ross
Diamond, Louise
Athukorala Arachchige, Kasun Sankalpa
Sanz Camacho, Paula
Randall, Rebecca Amy Michele
Ashbrook, Sharon Elizabeth
Buehl, Michael
Slawin, Alexandra Martha Zoya
Woollins, J Derek
Keywords
Bis(tellurides)
Conformational dependence
DFT calculations
NMR spectroscopy
Spin–spin coupling
X-ray crystallography
QD Chemistry
DAS
BDC
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Abstract
Three related series of peri‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap=naphthalene‐1,8‐diyl N ; Acenap=acenaphthene‐5,6‐diyl A ; Aceyl=acenaphthylene‐5,6‐diyl Ay ; Y=Ph 1 ; Fp 2 ; Tol 3 ; An‐p­ 4 ; An‐o­ 5 ; Tp 6 ; Mes 7 ; Tip 8 ) have been synthesised and their solid‐state structures determined by X‐ray crystallography. Molecular conformations were classified as a function of the two C9‐C‐Te‐C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J(125Te,125Te) spin–spin coupling constants between 3289–3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050–2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through‐space coupling is supported by DFT calculations.
Citation
Knight , F R , Diamond , L , Athukorala Arachchige , K S , Sanz Camacho , P , Randall , R A M , Ashbrook , S E , Buehl , M , Slawin , A M Z & Woollins , J D 2015 , ' Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri -substituted bis(tellurides) ' , Chemistry - A European Journal , vol. 21 , no. 9 , pp. 3613-3627 . https://doi.org/10.1002/chem.201405599
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201405599
ISSN
0947-6539
Type
Journal article
Rights
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Knight, F. R., Diamond, L. M., Arachchige, K. S. A., Sanz Camacho, P., Randall, R. A. M., Ashbrook, S. E., Bühl, M., Slawin, A. M. Z. and Woollins, J. D. (2014), Conformational Dependence of Through-Space Tellurium–Tellurium Spin–Spin Coupling in Peri-Substituted Bis(Tellurides). Chem. Eur. J.., which has been published in final form at http://dx.doi.org/10.1002/chem.201405599
Description
The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC). M.B. wishes to thank EaStCHEM and the University of St Andrews for support.
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  • University of St Andrews Research
URL
https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201405599#support-information-section
URI
http://hdl.handle.net/10023/7927

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