resumo
Chalcogen bonding (ChB) is rapidly rising to prominence in supramolecular chemistry as a powerful sigma (sigma)-hole-based noncovalent interaction, especially for applications in the field of molecular recognition. Recent studies have demonstrated ChB donor strength and potency to be remarkably sensitive to local electronic environments, including redox-switchable on/off anion binding and sensing capability. Influencing the unique electronic and geometric environment sensitivity of ChB interactions through simultaneous cobound metal cation recognition, herein, we present the first potassium chloride-selective heteroditopic ion-pair receptor. The direct conjugation of benzo-15-crown-5 ether (B15C5) appendages to Te centers in a bis-tellurotriazole framework facilitates alkali metal halide (MX) ion-pair binding through the formation of a cofacial intramolecular bis-B15C5 M+ (M+ = K+, Rb+, Cs+) sandwich complex and bidentate ChBmiddotmiddotmiddotX(- )formation. Extensive quantitative 1H NMR ion-pair affinity titration experiments, solid-liquid and liquid-liquid extraction, and U-tube transport studies all demonstrate unprecedented KCl selectivity over all other group 1 metal chlorides. It is demonstrated that the origin of the receptor's ion-pair binding cooperativity and KCl selectivity arises from an electronic polarization of the ChB donors induced by the cobound alkali metal cation. Importantly, the magnitude of this switch on Te-centered electrophilicity, and therefore anion-binding affinity, is shown to correlate with the inherent Lewis acidity of the alkali metal cation. Extensive computational DFT investigations corroborated the experimental alkali metal cation-anion ion-pair binding observations for halides and oxoanions.
palavras-chave
REDOX-CONTROLLED CHALCOGEN; ANION TRANSPORT; HALOGEN; HYDROGEN; BINDING; COMPLEXATION; HOST
categoria
Chemistry
autores
Docker, A; Marques, I; Kuhn, H; Zhang, ZY; Felix, V; Beer, PD
nossos autores
Igor Oliveira Marques
Investigador Júnior
Vítor Félix
Professor Associado com AgregaçãoProjectos
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
agradecimentos
A.D. and H.K. thank the EPSRC for studentships (Grant reference numbers EP/N509711/1 and EP/R513295/1) . Z.Z. thanks the University of Oxford and China Scholarship Council for a scholarship. The authors thank Dr. Amber L. Thompson and Dr. Kirsten E. Christensen for their helpful discussion and advice regarding crystallographic data collection and refinement. The computational studies were supported by project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, and LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC) .