Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes

Dai, Fulong; Wang, Zhenqiang

doi:10.1021/ja300095j

Cited by 154 publications

(109 citation statements)

References 36 publications

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“…Thepore volume is 0.55 cm 3 g À1 ,c lose to the theoretical value of about 0.57 cm 3 g À1 calculated using the PLATON program. TheBrunauer-Emmett-Teller (BET) and Langmuir surface areas derived from the N 2 sorption isotherms are of 1007 m 2 g À1 and 1568 m 2 g À1 ,w hich are distinctly higher than those of most ultramicroporous Co-BTC MOFs [13] and indicate ahigh C 2 H 2 storage potential. Notably,the pore width distribution of SNNU-45 is centered at 4.5 and 5.1 by the Horvath-Kawazoe (H-K) method ( Figure 2a,i nset).…”

Section: Resultsmentioning

confidence: 99%

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

et al. 2019

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As trategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical biporous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity,w hile larger inter-UBUp acking pores increase uptake capacity.T he effectiveness of this UBUs trategy is shown with ac obalt MOF (denoted SNNU-45) in which octahedral cages with 4.5 pore sizeserve as UBUs.The C 2 H 2 uptake capacity at 1atm reaches 193.0 cm 3 g À1 (8.6 mmol g À1 ) at 273 Kand 134.0 cm 3 g À1 (6.0 mmol g À1 )at298 K. Suchhigh uptake capacity is accompanied by ahigh C 2 H 2 /CO 2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1atm show aC 2 H 2 /CO 2 breakthrough time up to 79 min g À1 ,among top-performing MOFs.Grand canonical Monte Carlo simulations agree that ultrahigh C 2 H 2 /CO 2 selectivity is mainly from UBUultramicropores,while packing pores promote C 2 H 2 uptake capacity.

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Section: Resultsmentioning

confidence: 99%

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

et al. 2019

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“…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.…”

Section: Resultsmentioning

confidence: 99%

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

Duy

Kang

Kim

et al. 2017

Sci Rep

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We report a strategy to achieve a discrete cage molecule featuring a high level of structural hierarchy through a multiple-assembly process. A cobalt (Co) supramolecular triple-stranded helicate (Co-TSH)-based discrete molecular cage (1) is successfully synthesized and fully characterized. The solid-state structure of 1 shows that it is composed of six triple-stranded helicates interconnected by four linking cobalt species. This is an unusual example of a highly symmetric cage architecture resulting from the coordination-driven assembly of metallosupramolecular modules. The molecular cage 1 shows much higher CO2 uptake properties and selectivity compared with the separate supramolecular modules (Co-TSH, complex 2) and other molecular platforms.

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“…We recently reported au nique family of coordination containers,termed metal-organic supercontainers (MOSCs), which were obtained from the assembly of sulfonylcalix- [4]arene-based container precursors, [10] divalent metal ions, and carboxylate linkers of various shapes. [11] Forexample,the reaction of p-tert-butylsulfonylcalix [4]arene (TBSC), Co II or Ni II ,and an angular semi-flexible dicarboxylate linker such as 4,4'-methylenedibenzoic acid (H 2 L1) or 4,4'-iminobis(methylene)-dibenzoic acid (H 2 L2), gave rise to two members of the type IV MOSC family,d esignated here as MOSC-1 and MOSC-2, respectively (Scheme 1; Supporting Information, Scheme S1). [11e] These type IV MOSCs possess both endo and exo cavities and thus exhibit the trademark multi-pore architecture also observed in other prototypes of MOSCs.…”

mentioning

confidence: 99%

Switching on Supramolecular Catalysis via Cavity Mediation and Electrostatic Regulation

Qiao

Zhang

et al. 2016

Angew Chem Int Ed

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Synthetic supercontainers constructed from divalent metal ions, carboxylate linkers, and sulfonylcalix[4]arene-based container precursors exhibit great promise as enzyme mimics that function in organic solvents. The capacity of these artificial hosts to catalyze Knoevenagel condensation can be switched on when the aldehyde substrate possesses a molecular size and shape matching the nanocavity of the supercontainers. In contrast, little reactivity is observed for other aldehydes that do not match the binding pocket. This substrate-dependent catalytic selectivity is attributed to the Brønsted acidity of the metal-bound water molecules located inside the nanocavity, which is amplified when the size/shape of the aldehyde substrate fits the binding cavity. The electrostatic environment of the binding cavity and the Brønsted acidity of the supercontainer can be further modulated using tetraalkylammonium-based regulators, leading to higher reactivity for the otherwise unreactive aldehydes.

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Modular Assembly of Metal–Organic Supercontainers Incorporating Sulfonylcalixarenes

Cited by 154 publications

References 36 publications

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

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

Switching on Supramolecular Catalysis via Cavity Mediation and Electrostatic Regulation

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