Nickel(II) Cyclidenes with Appended Ethylpyridine Receptor Centers as Molecular Tweezers for Dicarboxylic Acids

A series of 14-, 15-, and 16-membered nickel(II) cyclidene macrocycles appended with 2-aminoethyl(2-pyridine)
receptors I−III, respectively, were prepared and characterized by X-ray crystallography and NMR techniques. The
14- and 15-membered macrocycles I and II exist in a planar or extended Z-configuration, whereas the 16-membered
macrocycle III was saddle shaped and had two asymmetric configurations in the unit cell (IIIa in a “capped”
configuration and IIIb in an “open” configuration). Variable-temperature 1H NMR studies of III in CD3CN were
conducted (25−65 °C), and at room temperature, the interconversion between capping and uncapping is slow on
the NMR time scale, resulting in a broad spectrum, whereas at 65 °C, interconversion was fast. 1H NMR binding
studies indicated I−III bind unsaturated dicarboxylic acids in a 1:1 stoichiometry with binding constants approaching
400 M-1 in CD3CN, and the binding strength was dependent on the shape of the macrocyclic cyclidene platforms,
whereas monocarboxylic acids were not bound. Generally, the planar 14-membered cyclidene I bound diacids the
weakest and the 16-membered cyclidene III bound diacids the strongest. The presence of nuclear Overhauser
effect spectrometry cross peaks in a 20 mM solution of 1:1 II−maleic acid indicates that the binding mode is ditopic
with the guest being encapsulated by the aminoethylpyridine arms above the macrocyclic framework.