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 M , 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 . DOI: 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
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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