Zirconium Metal–Organic Cages: Synthesis and Applications

Controlling phase in low-nuclearity calixarene-capped porous coordination cages with ligand functionalization

“…However, reaction of 2,7,9-triphenylcarbazole-3,6-dicarboxylic acid (H 2 tpcd) with MgCl 2 ·6H 2 O, MnCl 2 ·4H 2 O, Co(NO 3 ) 2 ·6H 2 O, or Ni(NO 3 )·6H 2 O and p-tert -butylsulfonylcalix[4]arene in amide/alcohol mixtures affords the targeted [(M 4 X(SC4A)) 2 (tpcd) 4 ] 2− (M = Mg 2+ , Mn 2+ , Co 2+ , and Ni 2+ ; X = OH − or OMe − ; hereafter referred to as M-TriPhenyl-cdc) cages in high yield. While the μ 4 species present in the metal cation clusters that comprise these cages can vary 2,23,30 the cages isolated here feature either methoxide or hydroxide ions in these positions. As a result, the cages present as 2 − anions.…”

“…As reports of permanent porosity in coordination cages have increased over the past decade, 1 so too have investigations into tuning the properties of these materials. [2][3][4] The packing of cages in the solid state and their amenability to solutionbased characterization and modification strategies can be controlled through choice of the metal cations that comprise these cages or functionalization of their organic ligands. 5,6 The former approach is particularly important for porous coordination cages containing metal cations with coordinatively-unsaturated sites.…”

“…Calixarene-capped coordination cages have previously been reported for a wide variety of metal ions, including, Mg, Fe, Co, Ni, and Zn. 2,[26][27][28][29] With this in mind, we targeted the synthesis of a large family of isostructural species based on these metal cations. Despite our best efforts, and our prior success in isolating iron(II)-based cages with these capping ligands, 2 we were unable to isolate an Fe 2+ cage and typically produced partially metalated cap with no carboxylic acid ligand.…”

“…2,26–29 With this in mind, we targeted the synthesis of a large family of isostructural species based on these metal cations. Despite our best efforts, and our prior success in isolating iron( ii )-based cages with these capping ligands, 2 we were unable to isolate an Fe 2+ cage and typically produced partially metalated cap with no carboxylic acid ligand. However, reaction of 2,7,9-triphenylcarbazole-3,6-dicarboxylic acid (H 2 tpcd) with MgCl 2 ·6H 2 O, MnCl 2 ·4H 2 O, Co(NO 3 ) 2 ·6H 2 O, or Ni(NO 3 )·6H 2 O and p-tert -butylsulfonylcalix[4]arene in amide/alcohol mixtures affords the targeted [(M 4 X(SC4A)) 2 (tpcd) 4 ] 2− (M = Mg 2+ , Mn 2+ , Co 2+ , and Ni 2+ ; X = OH − or OMe − ; hereafter referred to as M-TriPhenyl-cdc) cages in high yield.…”

Metal–Organic Frameworks and Their Composites for Environmental Applications

“…[40,41] MOFs are crystal compounds composed of organic linkers and infinite lattice or secondary building units (SBUs, metal ions or clusters), which are connected by coordination bonds with moderate strength. [42][43][44][45][46][47][48][49] In order to improve the performance of MOFs, all kinds of types of functional materials including polymers, carbons, and graphene, have been integrated with MOFs to generate MOF-based composites. Due to synergistic effects, the resulting MOF composites combine the intrinsic characteristic of each component and exhibit novel physicochemical properties.…”