Cage Match: Comparing the Anion Binding Ability of Isostructural Versus Isofunctional Pairs of Metal-Organic Nanocages.

Autor: Dutton KG; Department of Chemistry and Chemical Biology, Rutgers University - New Brunswick, 123 Bevier Road Piscataway, NJ, 08854, USA., Jones TJ; Department of Chemistry and Chemical Biology, Rutgers University - New Brunswick, 123 Bevier Road Piscataway, NJ, 08854, USA., Emge TJ; Department of Chemistry and Chemical Biology, Rutgers University - New Brunswick, 123 Bevier Road Piscataway, NJ, 08854, USA., Lipke MC; Department of Chemistry and Chemical Biology, Rutgers University - New Brunswick, 123 Bevier Road Piscataway, NJ, 08854, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 08; Vol. 30 (2), pp. e202303013. Date of Electronic Publication: 2023 Nov 14.
DOI: 10.1002/chem.202303013
Abstrakt: Affinities of six anions (mesylate, acetate, trifluoroacetate, p-toluenecarboxylate, p-toluenesulfonate, and perfluorooctanoate) for three related Pt 2+ -linked porphyrin nanocages were measured to probe the influence of different noncovalent recognition motifs (e. g., hydrogen bonding, electrostatics, π bonding) on anion binding. Two new hosts of M 6 L 3 12+ (1b) and M 4 L 2 8+ (2) composition (M=(en)Pt 2+ , L=(3-py) 4 porphyrin) were prepared in a one-pot synthesis and allowed comparison of hosts that differ in structure while maintaining similar N-H hydrogen-bond donor ability. Comparisons of isostructural hosts that differ in hydrogen-bonding ability were made between 1b and a related M 6 L 3 12+ nanoprism (1a, M=(tmeda)Pt 2+ ) that lacks N-H groups. Considerable variation in association constants (K 1 =1.6×10 3  M -1 to 1.3×10 8  M -1 ) and binding mode (exo vs. endo) were found for different host-guest combinations. Strongest binding was seen between p-toluenecarboxylate and 1b, but surprisingly, association of this guest with 1a was only slightly weaker despite the absence of NH⋅⋅⋅O interactions. The high affinity between p-toluenecarboxylate and 1a could be turned off by protonation, and this behavior was used to toggle between the binding of this guest and the environmental pollutant perfluorooctanoate, which otherwise has a lower affinity for the host.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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