Versatile Assembly of Metal-Coordinated Calix[4]resorcinarene Cavitands and Cages through Ancillary Linker Tuning

Abstract

We propose a design strategy for assembly of metal-coordinated calix[4]resorcinarene cavitands and cages by tuning of the ancillary linkers. Assembly of newly functionalized cavitand with angular isophthalic acid analogs affords three intriguing metal-coordinated cavitands with deep cavities, 1a-1c. Further, by mediating appropriate spacers between two isophthalic acids, two bowl-shaped cavitands are successfully joined together to produce three elegant coordination cages with tunable sizes and shapes, 2a-2c. The cavitand and cage crystals possess considerable amount of accessible porosities, as clearly established by gas adsorption measurements. Remarkably, 1a-1c also exhibit high structural flexibilities, reversibly transforming between the open-pore and the narrow-pore structures, upon removal and sorption of guest molecules, as evidenced by diffraction and gas adsorption measurements. By combining experimental studies with density functional theory (DFT) calculations, we thoroughly elucidated the mechanism of the structural transformations in response to external stimuli in this new class of flexible porous solids.

Three resorcin[4]arene-based lanthanide-coordination polymers with multifunctional photoluminescence sensing properties

“…calcd. for C 64 H 80 O 24 A mixture of H 8 L (27.0 mg, 0.1 mmol) and TbCl 3 $6H 2 O (18.0 mg, 0.048 mmol) was dissolved in a mixed solution of DMF (2 mL) and water (6 mL). Then the suspension was transferred into a Teon-lined autoclave (15 mL) and heated at 100 C for 3 days.…”

“…22,23 Thus far some metal-organic frameworks with fascinating structures and properties have been synthesized by applying the resorcin [4]arene-based ligands. 24,25 Remarkably, carboxylate-functionalized resorcin [4]arene ligands have been proven to exhibit strong "antennae effects" in building luminescent Ln-CPs. 26,27 Based on above consideration, we herein report three Ln-CPs, namely,…”

Solvent-assisted coordination driven assembly of a supramolecular architecture featuring two types of connectivity from discrete nanocages

“…From cubes to spheres, various nanometric objects have been used as building blocks to assemble nanoarchitectures for specific applications 2. As one type of nano-object, metal–organic cages (MOCs) that feature pre-designed windows and cavities have captured widespread attention3 in the areas of chemical sensing,4 catalysis,5 molecular encapsulation,6 and separation 7. The abundant metal sites of the nanocage complex8 make MOCs promising candidates for CO 2 adsorption.…”

Highly Stable Copper(I)–Thiacalix[4]arene‐Based Frameworks for Highly Efficient Catalysis of Click Reactions in Water

“…Generally, organic ligands play an important role in the rational construction of MOF catalysts featuring tunable structures . Calix[4]arenes, as one type of excellent candidate ligand, have attracted considerable attention from researchers due to the ease of modifying their upper and lower edges . Particularly, calix[4]arenes substituted by coordination hybrid atoms, such as N and S, can improve the stability of the resulting Cu I MOFs as recycled catalysts …”