Title

Directional Self-Sorting with Cucurbit[8]uril Controlled by Allosteric π–π and Metal–Metal Interactions

Document Type

Article

Publication Date

6-18-2018

Abstract

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim To maximize Coulombic interactions, cucurbit[8]uril (CB[8]) typically forms ternary complexes that distribute the positive charges of the pair of guests (if any) over both carbonylated portals of the macrocycle. We present here the first exception to this recognition pattern. Platinum(II) acetylides flanked by 4′-substituted terpyridyl ligands (tpy) form 2:1 complexes with CB[8] in an exclusively stacked head-to-head orientation in a water/acetonitrile mixture. The host encapsulates the pair of tpy substituents, and both positive Pt centers sit on top of each other at the same CB[8] rim, leaving the other rim free of any interaction with the guests. This dramatic charge imbalance between the CB[8] rims would be electrostatically penalizing, were it not for allosteric π–π interactions between the stacked tpy ligands, and possible metal-metal interactions between both Pt centers. When both tpy and acetylides are substituted with aryl units, the metal-ligand complexes form 2:2 assemblies with CB[8] in aqueous medium, and the directionality of the assembly (head-to-head or head-to-tail) can be controlled, both kinetically and thermodynamically.

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