“Eggs in egg cartons”: co-crystallization to embed molecular cages into crystalline lattices

Abstract

Discrete (M3L2)n cages assembled from a tripodal ligand (L) and metal ions (M: Cu(I) or Ag(I)) are embedded in networked coordination hosts formed by partial dissociation of the same discrete...

A Highly Entangled (M3L2)8 Truncated Cube from the Anion-Controlled Oligomerization of a π-Coordinated M3L2 Subunit

“…Acetylene π-coordination is a well-known organometallic interaction that is frequently involved in organometallic transformations. , However, unlike other coordination bonds, , this weak and reversible interaction has seldomly been used for metal-directed self-assembly, presumably on account of its low bond energy and poor directionality. We have recently found that the acetylene spacers in tripodal ligand 1 serve as weak secondary coordination sites upon metal binding at the primary pyridyl sites . This generates predominantly an M 3 L 2 building block (Figure a) that further oligomerizes into the discrete (M 3 L 2 ) n cages 2 , 3 , and 4 ( n = 2, 4, and 6, respectively, M = Cu I or Ag I ; Figure b).…”

Knotting matters: orderly molecular entanglements

“…The Fujita group has reported a series of entangled cage architectures, including a double-walled cage capable of guest-adaptive molecular recognition, 63 and a series of interconvertible entangled cages driven by weak secondary π-acetylene interactions. 64 These architectures display unusual co-crystallisation behaviour 65 and show potential for enantioselective catalytic and host–guest applications. 66 …”

Adaptive coordination assemblies based on a flexible tetraazacyclododecane ligand for promoting carbon dioxide fixation

“…7,8 Inspired by this, many unusual metal complexes which can be used to fix CO 2 through binding with carbonate have been reported. 9–13 Coordination-directed self-assembly has been proven to be an effective approach toward the predictable construction of multicomponent artificial hosts, 14–77 where enhanced guest reactivity, 73,74,78–87 stabilization of metastable species, 88–90 and unusual reaction pathways 78,91–94 have been realized. While atmospheric CO 2 sequestration by selective binding of carbonate with coordination hosts has already been reported, 95–102 adaptive coordination hosts that contain multiple active metal sites and can reversibly encapsulate and release the carbonate are still rare.…”