A Trigonal Prismatic Ligand in the Metal-Mediated Self-Assembly of One- and Two-Dimensional Metallosupramolecular Polymers

Abstract

A novel trispyrazine-pillared prismatic bicycooxacalixaromatic ligand L is synthesized, and its application in metal-mediated self-assembly is described. Under self-assembly conditions, single chain, double-stranded cross-linked coordination polymer and two-dimensional (2D) coordination polymeric networks were formed via M-L (Ag(+), Cu(2+), and Zn(2+)) coordinative interactions. Structural analyses revealed that the antiparallelly arranged one-dimensional coordination polymers (Cu(2+) and Zn(2+)) are arranged to generate well-defined voids to host aromatic guests (benzene) via C-H···π and π···π interactions, while the double-stranded cross-linked coordination polymer (Ag(+)) contains a rhomboidal [Ag2(L(3))2] (L(3): tridentate ligand) cage motif to include a benzene guest; the "thicker" (thickness: ac 5 Å) 2D coordination polymeric networks (Ag(+), Cu(2+), and Zn(2+)), however, are all formed by connection of one or two kinds of topologically different metallomacrocyclic cage units. These unique metallomacrocyclic cage units in the 2D coordination polymeric networks are capable of hosting different guest species. For instance, the rhomboidal [M2(L(3))2] (M = Ag(+), Cu(2+)) cage units were found to host a benzene or a nitrate anion; a hexahedral [M3(L(3))3] (M = Ag(+)) cage was found to host a ligand L or a DMF molecule; the hexahedral [M4(L(3))4] (M = Cu(2+)) cage was found to host four solvent molecules of benzene; and the rectangular [M3(L(3))3] (M = Cu(2+), Zn(2+)) cage units, however, were found to host two THF molecules. The results highlight the potential of ligand L for applications in the construction of "thicker" 2D coordination polymeric networks with well-defined metallomacrocyclic cage units capable of hosting various guest species.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

“…The fusion of hexagonal and rhomboidal metallomacrocyclic cages of a Cu­(II) complex was investigated by Wen et al . It is derived from a unique tritopic tris -pyrazine-pillared prismatic bicycooxacalixaromatic ligand, L, via the coordination-driven self-assembly process in a 1:1 metal–ligand ratio.…”

“…(c) The overall 2D polymeric network structure. Reproduced with permission from ref . Copyright 2013 American Chemical Society.…”

“…273,303,343−345 In addition, several interesting 2D MOFs with fes topology have been reported in the literature. 240,311,346−366 The fusion of hexagonal and rhomboidal metallomacrocyclic cages of a Cu(II) complex was investigated by Wen et al 367 It is derived from a unique tritopic tris-pyrazine-pillared prismatic bicycooxacalixaromatic ligand, L, via the coordination-driven self-assembly process in a 1:1 metal−ligand ratio. The structure is planar in nature, with rhombic [Cu 2 (L 3 ) 2 ] and hexameric [Cu 4 (L 3 ) 4 ] cage units (Figure 44).…”

Single-Pot Self-Assembly of Heteroleptic Mn(I)-Based Aminoquinonato-Bridged Ester/Amide-Functionalized Dinuclear Metallastirrups: Potential Anticancer and Visible-Light-Triggered CORMs

“…2 It is well-known that the ligating topologies of the organic ligands used in metal-mediated self-assembly play a key role in determining the binding abilities, size, geometry, and functionality of resulting metallasupramolecular objects. 3 It is a continuous endeavor to diversify the choice of chelating linkers and to functionalize the resulting complexes to achieve supramolecular architectures with interesting properties. 4 Recently, researchers have focused on developing different varieties of fac -Re(CO) 3 - and fac -Mn(CO) 3 -based compounds for their probable utility as CO releasing molecules and studied their related antiproliferative properties.…”

Trimeric Cage Complexes of Platinum Group and Coin Metals

“…To generate different 3D architectures, the multiple binding sites of the ligand systems need to be equipped with specific angularities so that they fit with the preferred coordination geometry of the metal center 3–7. In this way, cage compounds can be constructed, which provide enough space to encapsulate small molecules 8,9. This allows for an interesting host–guest chemistry10–13 with applications in sensing,7 molecular recognition,14 luminescent devices,15,16 as well as in catalysis 17–21…”