Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes

A new strategy for the design of container molecules is presented. Sulfonylcalix[4]­arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal–organic “supercontainers” (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable. The unique features of MOSCs are expected to provide exciting new opportunities for the exploration of their functional applications

Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes

A new strategy for the design of container molecules is presented. Sulfonylcalix[4]­arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal–organic “supercontainers” (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable. The unique features of MOSCs are expected to provide exciting new opportunities for the exploration of their functional applications

Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes

A new strategy for the design of container molecules is presented. Sulfonylcalix[4]­arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal–organic “supercontainers” (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable. The unique features of MOSCs are expected to provide exciting new opportunities for the exploration of their functional applications

Synthetic Supercontainers Exhibit Distinct Solution versus Solid State Guest-Binding Behavior

The phase-dependent host–guest binding behavior of a new family of synthetic supercontainers has been probed in homogeneous solution and at liquid–liquid, solid–liquid, and solid–gas interfaces. The synthetic hosts, namely, type II metal–organic supercontainers (MOSCs), are constructed from the assembly of divalent metal ions, 1,4-benzenedicarboxylate (BDC) linker, and sulfonylcalix[4]­arene-based container precursors. One member of the MOSCs, MOSC-II-tBu-Ni, which is derived from Ni­(II), BDC, and <i>p</i>-<i>tert</i>-butylsulfonylcalix­[4]­arene (TBSC), crystallizes in the space group <i>R</i>3̅ and adopts pseudo face-centered cubic (fcc) packing, whereas other MOSCs, including TBSC analogue MOSC-II-tBu-Co, <i>p</i>-<i>tert</i>-pentylsulfonylcalix­[4]­arene (TPSC) analogues MOSC-II-tPen-Ni/Co, and <i>p</i>-<i>tert</i>-octylsulfonylcalix­[4]­arene (TOSC) analogues MOSC-II-tOc-Ni/Mg/Co, all crystallize in the space group <i>I</i>4/<i>m</i> and assume a pseudo body-centered cubic (bcc) packing mode. This solid-state structural diversity is nevertheless not reflected in their solution host–guest chemistry, as evidenced by the similar binding properties of MOSC-II-tBu-Ni and MOSC-II-tBu-Co in solution. Both MOSCs show comparable binding constants and adsorb ca. 7 equiv of methylene blue (MB) and ca. 30 equiv of aspirin in chloroform. In contrast, the guest-binding behavior of the MOSCs in solid state reveals much more variations. At the solid–liquid interface, MOSC-II-tBu-Co adsorb ca. 5 equiv of MB from an aqueous solution at a substantially faster rate than MOSC-II-tBu-Ni does. However, at the solid–gas interface, MOSC-II-tBu-Ni has higher gas uptake than MOSC-II-tBu-Co, contradicting their overall porosity inferred from the crystal structures. This discrepancy is attributed to the partial collapse of the solid-state packing of the MOSCs upon solvent evacuation. It is postulated that the degree of porosity collapse correlates with the molecular size of the MOSCs, i.e., the larger the MOSCs, the more severe they suffer from the loss of porosity. The same principle can rationalize the negligible N₂ and O₂ adsorption seen in the larger MOSC-II-tPen-Co and MOSC-II-tOC-Ni/Mg/Co molecules. MOSC-II-tPen-Ni features an intermediate molecular size and endures a partial structural collapse in such a way that the resulting pore dimension permits the inclusion of kinetically smaller O₂ (3.46 Å) but excludes larger N₂ (3.64 Å), explaining the observed remarkable O₂/N₂ adsorption selectivity

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data

Europium Pyrimidine-4,6-dicarboxylate Framework with a Single-Crystal-to-Single-Crystal Transition and a Reversible Dehydration/Rehydration Process

In this paper, a novel three-dimensional (3D) porous lanthanide–organic framework, Eu₂(μ₄-pmdc)₂(OH)₂·3H₂O (<b>1</b>), which is stable up to 400 °C, has been hydrothermally synthesized and characterized. It shows intriguing single-crystal-to-single-crystal transformation and reversible dehydration/rehydration phenomenon upon removal and rebinding of the lattice water molecules, which is supported by single-crystal X-ray diffraction, powder X-ray diffraction, and photoluminescence data