Discrete {Ni₄₀} Coordination Cage: A Calixarene-Based Johnson-Type (J₁₇) Hexadecahedron

Abstract

We report a Johnson hexadecahedronal coordination cage, constructed via 10 Ni4-p-tert-butylthiacalix[4]arene (Ni4-TC4A) units as vertices and 16 5-(pyridin-4-yl)isophthalate (PIP) ligands as tiles. It features a gyroelongated square bipyramidal geometry, equivalent to two square pyramids pillared by a square antiprism, a J17 Johnson solid. Remarkably, the cage compound exhibits a much higher uptake capacity of C3H8 than CH4, representing a promising material for separation of these two gases. In contrast, Co4-TC4A units are linked by PIP ligands and rare {Co4O4Cl2} clusters, providing a one-dimensional bamboo stick-like polymer.

A Cobalt Supramolecular Triple-Stranded Helicate-based Discrete Molecular Cage

“…Complex 2 also shows little adsorption towards CH 4 and N 2 (Supplementary Figs S21–S23). To the best of our knowledge, the CO 2 uptake capacity of 1 at 298 K and 1 atm is among the highest values for discrete molecular platforms constructed from metal ions/clusters with organic ligands (Supplementary Table S5)91011606162636465666768.…”

Inorganic–Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework

“…While, owing to the challenge of discovering metal clusters suitable for making cluster‐OPs, little progress has been achieved in the assembly of cluster‐OPs compared to that of MOPs. The common metal clusters observed in reported cluster‐OPs are 3d transition‐metal clusters, such as the {Cu 2 } dimer, {Fe 3 O(SO 4 ) 3 } trimer, or {Ni 4 Cl} tetramer. Interestingly, during the past decade, a handful of polyoxometalates (POMs) have been successfully used as building blocks to yield a series of novel cluster‐OPs, mainly based on polyoxovanadates {V 3 O 12 }, {V 4 O 16 }, {V 5 O 17 }, {WV 5 O 22 }, {V 6 O 6 (OCH 3 ) 9 (SO 4 )}, and {P 4 V 5 O 20 }, polyoxotungstate {Ni 6 PW 9 O 34 }, and polyoxomolybdate {PMo 9 O 31 }.…”

Inorganic–Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework

“…Zeng-Kui Zhu, Ya-Yun Lin, Hao Yu,Xin-Xiong Li, and Shou-Tian Zheng* Abstract: The combination of polyoxoniobates (PONbs) with 3d metal ions,azoles,and organoamines is ageneral synthetic procedure for making unprecedented PONb metal complex cage materials,i ncluding discrete molecular cages and extended cage frameworks.B yt his method, the first two PONb metal complex cages K 4 @{[Cu 29 (OH) 7 (H 2 O) 2 (en) 8 -(trz) 3 ] 4 }a nd [Cu(en) 2 ]@{[Cu 2 (en) 2 -(trz) 2 ] 6 (Nb 68 O 188 )} have been made.T he former exhibits ah uge tetrahedral cage with more than 120 metal centers, which is the largest inorganic-organic hybrid PONb knownto date.T he later shows al arge cubic cage,w hichc an act as building blocks for cage-based extended assembly to form a3 Dc age framework {[Cu(en) 2 ]@{[Cu 2 (trz) 2 -(en) 2 ] 6 [H 10 Nb 68 O 188 ]}}. These materials exhibit visible-lightdriven photocatalytic H 2 evolution activity and high vapor adsorption capacity.T he results hold promise for developing both novel cage materials and largely unexplored inorganicorganic hybrid PONb chemistry.…”