In 1987, Pedersen, Cram, and Lehn were awarded the Nobel Prize in Chemistry to honor their achievements in, among other things, the selective recognition of alkali metal ions by synthetic hosts. Almost three decades later, the 2016 Nobel Prize went to Stoddart, Sauvage, and Feringa for the development of artificial molecular machines, in which interlocked molecules play a significant role. Surprisingly, although many rotaxane- and catenane-based molecular machines have been constructed using various templating approaches, alkali metal ions, which are good templates for crown ether synthesis, have only rarely been applied as templates for the assembly of these interlocked molecules. This paucity of examples is probably due to the less well defined coordination numbers and geometries in the complexation of alkali metal ions to common oxygen-containing ligands, resulting in much weaker metal-ligand interactions and less predictable structures for their complexes compared with those formed between transition metal ions and common pyridine-containing ligands. Nevertheless, the ease of removing alkali metal ions from interlocked compounds and their much lower toxicity compared with that of transition metal ions are attractive features that have inspired their use as templates in the synthesis of interlocked molecules. About a decade ago, we began investigating the feasibility of using alkali metal ions to template the formation of catenanes and rotaxanes, with the hope of developing facile, broadly applicable, green, and efficient methods for their construction. We noticed that the interactions between oxygen-containing ligands and alkali metal ions can be strengthened by minimizing the effects of competing interactions from solvent molecules and counteranions. Thus, to increase the solubility of the metal ion salts in less polar solvents (e.g., CHCl, CHCl) and minimize ion pairing, we chose tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB), a weakly coordinating anion, as the counteranion for the alkali metal ions applied as templates. Our strategy has been based on the association of simple and general recognition units: (i) the orthogonal arrangement of two oligo(ethylene glycol) chains around an alkali metal ion and (ii) the encircling of a single urea/amide unit by an oligo(ethylene glycol)-containing macrocycle in the presence of a templating alkali metal ion. The former recognition system has allowed the facile construction of many interesting interlocked structures, including cyclic [2]catenane trimers and tetramers; the latter has provided several rotaxanes, including some incorporating monomers of practically important (macro)molecules (e.g., peptides, polymers) and some that behave as switches with unique functions (e.g., catalysis, gelation). The components in these recognition systems possess high flexibility in terms of their structures and the choice of suitable alkali metal ion templates. This Account tells the story of the concept behind this alkali metal ion-templating approach as well as its elab...

Calixarenes are widely used as molecular platforms in supramolecular chemistry.T heir efficient modification is key for appendingf unctional moieties such as binding, sensing, chiral, or hydrophilic subunits. Due to the presence of multiple identicalf unctional groups, selectivef unctionalization of such macrocyclic compounds is highly challenging. Indeed, the control of the chemo-, regio-, stereo-as wella s iteroselectivity is required. Thisr eview describes rational methods leadingt oahigh degree of regio-and/or iteroselectivitya nd classifies them into specific strategies. Many of these strategies are conceptually very general and hopefully will be as ource of inspiration for developing selectivem ethods for other macrocyclic platforms.