Conformational Dependence of Through‐Space Tellurium–Tellurium Spin–Spin Coupling in Peri‐Substituted Bis(Tellurides). Issue 9 (22nd December 2014)

• Record Type: Journal Article
• Authors: Knight, Fergus R.; Diamond, Louise M.; Arachchige, Kasun S. Athukorala; Sanz Camacho, Paula; Randall, Rebecca A. M.; Ashbrook, Sharon E.; Bühl, Michael; Slawin, Alexandra M. Z.; Woollins, J. Derek
• Is Part Of: Chemistry. Volume 21:Issue 9(2015)
• Page Start: 3613
• Page End: 3627
• Publication Date: 2014-12-22
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201405599
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Three related series of <italic>peri</italic>‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)<sub>2</sub> (Nap=naphthalene‐1, 8‐diyl <bold>N</bold>; Acenap=acenaphthene‐5, 6‐diyl <bold>A</bold>; Aceyl=acenaphthylene‐5, 6‐diyl <bold>Ay</bold>; Y=Ph <bold>1</bold>; Fp <bold>2</bold>; Tol <bold>3</bold>; An‐<italic>p</italic>­ <bold>4</bold>; An‐<italic>o</italic>­ <bold>5</bold>; Tp <bold>6</bold>; Mes <bold>7</bold>; Tip <bold>8</bold>) 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 (<italic>θ</italic>); in the solid all members adopt AB or CC<italic>t</italic> configurations, with larger Te(aryl) moieties exclusively imposing the CC<italic>t</italic> variant. Exceptionally large <italic>J</italic>(<sup>125</sup>Te, <sup>125</sup>Te) 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 CC<italic>t</italic>‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller <italic>J</italic> 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.</p> </abstract>