Nanocapsules of unprecedented internal volume seamed by calcium ions

Sikligar, Kanishka; Kelley, Steven P.; Wagle, Durgesh V.; Ishtaweera, Piyuni; Baker, Gary A.; Atwood, Jerry L.

doi:10.1039/d3sc01629c

Cited by 4 publications

(3 citation statements)

References 48 publications

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“…Surprisingly, we discovered that incorporating Ca 2+ led to a unique connectivity in which Ca 2+ forms polyatomic ions which bridged pyrogallol[4]arene moieties into a capsule of unprecedented size and complexity. 35 In the current study, we again find that the inclusion of a different alkaline earth metal, in this case Ba 2+ , yields yet another unprecedented capsule geometry and stoichiometry. Most strikingly, the large size (ionic radius) of Ba 2+ allowed direct connectivity of MONC faces, leading to the formation of a 2D honeycomb-like coordination network from barium-seamed MONCs.…”

supporting

confidence: 63%

Hierarchical 2D honeycomb-like network from barium-seamed nanocapsules

Sikligar,

Kelley,

Baker

et al. 2023

Chem. Commun.

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confidence: 63%

Hierarchical 2D honeycomb-like network from barium-seamed nanocapsules

Sikligar,

Kelley,

Baker

et al. 2023

Chem. Commun.

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“…Most recent examples of these assemblies are based on pyrogallol [4]arenes. [20,56] Homodimeric capsules, glued together by hydrogen bonds, were observed in solutions and crystals of calix [4]arenes derivatized with carboxylic groups at the upper rim in chlorinated hydrocarbons. [57,58] A strong hydrogen OÀ H•••N bond between the pyridyl group and carboxylic acid attached to separate calix [4]arene molecules enabled the construction of heterodimeric non-covalent calixarene capsules.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Handshakes: Characterization of Urea‐Carboxylate Interactions Within Calixarene Frameworks

Cvetnić,

Cindro,

Topić

et al. 2024

ChemPlusChem

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The research of molecular capsules offers high application potential and numerous benefits in various fields. With the aim of forming supramolecular capsules which can be reversibly assembled and dissociated by simple external stimuli, we studied interactions between calixarenes containing urea and carboxylate moieties. To this end two ureido‐derivatives of p‐tert‐butylcalix[4]arene comprising phenylureido‐moieties and diacetate‐calix[4]arenes were prepared. The binding of acetate by ureido‐derivatives of calixarene in acetonitrile was characterized, revealing high affinity of ureido‐calixarenes for carboxylates. This suggested high potential for uniting the complementary calix[4]arenes via H‐bonds between carboxylic groups and urea moieties. The assembly of calixarenes was examined in detail by means of UV, 1H NMR, ITC, DOSY, MS, and conductometry providing insight in the structure‐stability relationship. The tetraureido calixarene derivative formed the most stable heterodimers with diacetate‐calix[4]arenes featuring practically quantitative association upon mixing the two calixarene counterparts. The possibility of controlling the formation of the heterodimer by protonating the carboxylates, thereby hindering the interactions critical for capsule assembly, was investigated. Indeed, the reversibility of breaking and re‐forming the heterodimer by addition of an acid and base to the solution containing urea‐ and carboxylate‐derivative calix[4]arene was demonstrated using NMR spectroscopy.

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“…Macrocycles have recently become a popular building element for creating metal–organic cages. The main examples included calixarenes 24 , 36 – 42 , pillar[n]arene 43 , and porphyrin 41 , 44 – 46 , etc. These coordination cages are prospects for advanced functional materials due to their large interior volume, regulated cavity environment, and high porosity.…”

Section: Introductionmentioning

confidence: 99%

Thermally-induced atropisomerism promotes metal-organic cage construction

Liang,

Lu,

Yang

et al. 2023

Nat Commun

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Molecular folding regulation with environmental stimuli is critical in living and artificial molecular machine systems. Herein, we described a macrocycle, cyclo[4] (1,3-(4,6-dimethyl)benzene)[4](1,3-(4,6-dimethyl)benzene)(4-pyridine). Under 298 K, it has three stable stiff atropisomers with names as 1 (Cs symmetry), 2 (Cs symmetry), and 3 (C4v symmetry). At 393 K, 1 can reversibly transform into 2, but at 473 K, it can irrevocably transform into 3. At 338 K, 3 and (PhCN)2PdCl2 complex to produce the metal-organic cage 4. Only at 338 K does the combination of 1 or 2 and (PhCN)2PdCl2 create a gel-like structure. Heating both gels to 473 K transforms them into 4. In addition to offering a thermally accelerated method for modifying self-assembled systems using macrocyclic building blocks, this study also has the potential to develop the nanoscale transformation material with a thermal response.

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Nanocapsules of unprecedented internal volume seamed by calcium ions

Abstract: The inception of an unprecedented class of voluminous Platonic solids displaying hierarchical geometry based on pyrogallol[4]arene moieties seamed by divalent calcium ion is described. Single-crystal X-ray structural determination has established...

Cited by 4 publications

References 48 publications

Hierarchical 2D honeycomb-like network from barium-seamed nanocapsules

Hierarchical 2D honeycomb-like network from barium-seamed nanocapsules

Supramolecular Handshakes: Characterization of Urea‐Carboxylate Interactions Within Calixarene Frameworks

Thermally-induced atropisomerism promotes metal-organic cage construction

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