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

Abstract

Affinities of six anions (mesylate, acetate, trifluoroacetate, p-toluenecarboxylate, p-toluenesulfonate, and perfluorooctanoate) for three related Pt2+ -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 M6 L3 12+ (1b) and M4 L2 8+ (2) composition (M=(en)Pt2+ , 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 M6 L3 12+ nanoprism (1a, M=(tmeda)Pt2+ ) that lacks N-H groups. Considerable variation in association constants (K1 =1.6×103 M-1 to 1.3×108 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.