Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)
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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.
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
Chemistry - A European Journal
© 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
DescriptionThe 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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