Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 67, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202201838
Keywords
anion recognition; antimony; bismuth; pnictogen bonding; sigma-hole interactions
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Funding
- EPSRC [EP/ R513295, EP/ N509711/1]
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The synthesis and characterization of acyclic antimony(III) and bismuth(III) triaryl pnictogen bonding receptors were reported. The binding potency of halide anions was found to be closely related to the electronic properties of the aryl substituent and the polarisability of the pnictogen bonding donor. Selectivity profiles for chloride anions and oxoanions were revealed for the most potent receptors.
The synthesis and characterisation of a library of acyclic antimony(III) and bismuth(III) triaryl pnictogen bonding (PnB) receptor systems are reported. In the first-generation receptor series, quantitative H-1 NMR chloride titration experiments in THF solvent media reveal halide anion binding potency is intimately correlated with both the electronic-withdrawing nature of the aryl- substituent and the polarisability of the PnB donor. Further extensive anion binding investigations with the most potent Sb- and Bi-based PnB receptors: 1.Sb-2cF3 and 1.Bi-2cF3, reveal novel selectivity profiles, both displaying Cl- selectivity relative to the heavier halides and, impressively, to a range of highly basic oxoanions. The synthesis and preliminary chloride anion binding studies of a series of novel tripodal tris-proto-triazole triaryl Sb(III) and Bi(III) mixed PnB-HB receptor systems are also described. Whereas parent triphenyl Sb(III) and Bi(III) compounds are incapable of binding Cl- in THF solvent media, the PnB-triazole HB host systems exhibit notable halide affinity.
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