resumo
The ever-increasing demand in the development of host molecules for the recognition of charged species is stimulated by their fundamental roles in numerous biological and environmental processes. Here, capitalizing on the inherent amphoteric nature of anisotropically polarized tellurium or iodine atoms, we demonstrate a proof of concept in charged guest recognition, where the same neutral host structure binds both cations or anions solely through its chalcogen or halogen donor atoms. Through extensive 1H nuclear magnetic resonance titration experiments and computational density functional theory studies, a library of chalcogen-bonding (ChB) and halogen-bonding (XB) mechanically interlocked [2]rotaxane molecules, including seminal examples of all-ChB and mixed ChB/XB [2]rotaxanes, are shown to function as either Lewis-acidic or Lewis-basic multidentate hosts for selective halide anion and metal cation binding. Notably, the exploitation of the inherent amphoteric character of an atom for the strategic purpose of either cation or anion recognition constitutes the inception of a previously unexplored area of supramolecular host-guest chemistry.
palavras-chave
BASIS-SETS; METAL; COORDINATION; COMPLEXES; CHEMISTRY; ENERGIES; PSEUDOPOTENTIALS; MACROCYCLES; DEFINITION; CATALYSIS
categoria
Chemistry
autores
Tse, YC; Docker, A; Marques, I; Félix, 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
We dedicate this publication to Professor Jean-Pierre Sauvage on the occasion of his 80th birthday. Y.C.T. thanks the Croucher Foundation for a scholarship. A.D. thanks EPSRC for studentship funding (grant reference number EP/N509711/1). The theoretical studies were developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC).