Macrocyclic Template-Directed Synthesis of MOCs
Introduction. Macrocyclic ligands have been extensively applied to recognize single metal ions and construct macrocycle-metal complexes, which often show a high selectivity and an enhanced kinetic and thermodynamic stability due to the size-match principle and the known macrocyclic effect. By virtue of such extraordinary coordination properties of macrocyclic ligands, we herein employ polydentate macrocyclic ligands with large cavity to access multinuclear organometallic clusters.
Zhang, S. ; Zhao, L. Acc. Chem. Res. 2018, 51, 2535.
Results. A variety of organometallic clusters centered by sp or sp2 carbon anions have been successfully fabricated by using size-tunable and flexible azacalixpyridines (Py[n]s) as macrocyclic ligands to elucidate (i) the precise control of nuclearity numbers of the encapsulated silver clusters (ranging from 3, 4, 5, 7, 9, 10 to 15) by tuning the size of Py[n]s; (ii) the construction of structurally diverse supramolecular assemblies including metal cluster-centered capsules, rotaxanes, catenanes and polygons; (iii) the isolation of unconventional metal cluster entities based on further organometallic transformations (e.g. cascade and multi-step cyclizations) of the macrocycle-encapsulated MOCs; (iv) the capture of reactive intermediates such as a merged copper(I/II)-alkynyl-hrdroxyl cluster in Glaser coupling; (v) the achievement of unprecedented aryl vicinal dicarbanion bonded Ag13/Ag15 nanoclusters based on the cluster-to-cluster transformationby removing the outer macrocycle template.
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