Self-assembly of a water-soluble endohedrally functionalized coordination cage including polar guests

Sun, Qingqing; Escobar, Luis; Jong, Jaap de; Ballester, Pablo

doi:10.1039/d1sc03751j

Cited by 11 publications

(12 citation statements)

References 60 publications

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“…Over the last two decades, the coordination chemistry of tetrapyrrolato C4P ligands with diverse metal ions has progressed by virtue of the ability of C4Ps to form σ/π-complexes, offering a new catalytic pathway for various synthetic conversions. [121][122][123][124][125] In this direction, Greb and teammates revealed the reversible OH-bond activation of primary/secondary/tertiary alcohols (118)(119)(120)(121)(122)(123) under reduced pressure by means of a calix [4]pyrrolato aluminate-based catalyst (116, Fig. 20).…”

Section: Structurally Constrained P-block C4p-compounds In Catalysismentioning

confidence: 97%

“…of pyridine-N-oxide (106) in a 2 : 1 solution mixture of CDCl 3 / CD 3 CN. 119,120 Consequently, upon the addition of 1 equiv. of [Pd (MeCN) 4 ](BF 4 ) 2 to the 1 : 1 host-guest complex solution, the selfassembled metal coordination cage [103•Pd] 2+ , featuring two polar binding sites, was formed via Pd II coordination with the pyridyl units of 103 (Fig.…”

Section: Metal Ion Caged Systems Based On C4pmentioning

confidence: 99%

“…Importantly, the authors also divulged the formation of the Pd(II) cage system [104•Pd] 6+ via the self-assembly of the tetra cationic superaryl extended C4P (104) with [Pd(MeCN) 4 ](BF 4 ) 2 . 120 Furthermore, [104•Pd] 6+ is water soluble and possesses two polar binding sites endohedrally. For efficient self-assembly, the inclusion of mono/ditopic pyridyl N-oxides (106-108) and aliphatic formamide guests (109)(110)(111) was found to be necessary (Fig.…”

Section: Metal Ion Caged Systems Based On C4pmentioning

confidence: 99%

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Recent developments in calix[4]pyrrole (C4P)-based supramolecular functional systems

Rather

Ali

2022

Org. Chem. Front.

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Section: Structurally Constrained P-block C4p-compounds In Catalysismentioning

confidence: 97%

Section: Metal Ion Caged Systems Based On C4pmentioning

confidence: 99%

Section: Metal Ion Caged Systems Based On C4pmentioning

confidence: 99%

See 1 more Smart Citation

Recent developments in calix[4]pyrrole (C4P)-based supramolecular functional systems

Rather

Ali

2022

Org. Chem. Front.

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“…In 63 In water, [28b•Pd] 6+ also encapsulated 5a and 23a. 64 Moreover, [28b•Pd] 6+ showed high-conformational selectivity by exclusively binding cis,cis-30 (K a > 10 5 M −1 ).…”

Section: Encapsulation Of Neutral Polar Guestsmentioning

confidence: 99%

“…We also attached four pyridinium residues at the lower rim in 28b. 64 In the presence of suitable polar guests, 28b and Pd(II) (added as NO 3 − salt) self-assembled into a water-soluble CC, [28b•Pd] 6+ . In water, the CC experienced significant aggregation at r.t., which was reduced by heating the solution at 333 K.…”

Section: Dynamic Covalent Capsulesmentioning

confidence: 99%

Aryl-Extended and Super Aryl-Extended Calix[4]pyrroles: Design, Synthesis, and Applications

2023

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Conspectus Proteins exhibit high-binding affinity and selectivity, as well as remarkable catalytic performance. Their binding pockets are hydrophobic but also contain polar and charged groups to contribute to the binding of polar organic molecules in aqueous solution. In the past decades, the synthesis of biomimetic receptors featuring sizable aromatic cavities equipped with converging polar groups has received considerable attention. “Temple” cages, naphthotubes, and aryl-extended calix[4]pyrroles are privileged examples of synthetic scaffolds displaying functionalized hydrophobic cavities capable of binding polar substrates. In particular, calix[4]pyrroles are macrocycles containing four pyrrole rings connected through their pyrrolic 2- and 5-positions by tetra-substituted sp3 carbon atoms (meso-substituents). In 1996, Sessler introduced the meso-octamethyl calix[4]pyrrole as an outstanding receptor for anion binding. Independently, Sessler and Floriani also showed that the introduction of aryl substituents in the meso-positions produced aryl-extended calix[4]pyrroles as a mixture of configurational isomers. In addition, aryl-extended calix[4]pyrroles bearing two and four meso-aryl substituents (walls) were reported. The cone conformation of “two-wall” αα-aryl-extended calix[4]pyrroles features an aromatic cleft with a polar binding site defined by four converging pyrrole NHs. On the other hand, “four-wall” αααα-calix[4]pyrrole isomers possess a deep polar aromatic cavity closed at one end by the converging pyrrole NHs. Because of their functionalized interior, aryl-extended calix[4]pyrroles are capable of binding anions, ion-pairs, and electron-rich neutral molecules in organic solvents. However, in water, they are restricted to the inclusion of neutral polar guests. Since the early 2000s, our research group has been involved in the design and synthesis of “two-wall” and “four-wall” aryl-extended calix[4]pyrroles and their derivatives, such as aryl-extended calix[4]pyrrole cavitands and super aryl-extended calix[4]pyrroles. In this Account, we mainly summarize our own results on the binding of charged and neutral polar guests with these macrocyclic receptors in organic solvents and in water. We also describe the applications of calix[4]pyrrole derivatives in the sensing of creatinine, the facilitated transmembrane transport of anions and amino acids, and the monofunctionalization of bis-isonitriles. Moreover, we explain the use of calix[4]pyrrole receptors as model systems for the quantification of anion−π interactions and the hydrophobic effect. Finally, we discuss the self-assembly of dimeric capsules and unimolecular metallo-cages based on calix[4]pyrrole scaffolds. We comment on their binding properties, as well as on those of bis-calix[4]pyrroles having a fully covalent structure. In molecular recognition, aryl-extended calix[4]pyrroles and their derivatives are considered valuable receptors owing to their ability to interact with a wide variety of electron-rich, neutral, and charged guests. Calix[4]pyrro...

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Solvent Induced Conversion of a Self‐Assembled Gyrobifastigium to a Barrel and Encapsulation of Zinc‐Phthalocyanine within the Barrel for Enhanced Photodynamic Therapy

et al. 2023

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A rare gyrobifastigium architecture (GB) was constructed by self‐assembly of a tetradentate donor (L) with PdII acceptor in DMSO. The GB was converted to its isomeric tetragonal barrel (MB) upon treatment with water. The hydrophobic cavity of MB has been explored for the encapsulation of zinc‐phthalocyanine (ZnPc), which is an excellent photosensitizer for photodynamic therapy (PDT). However, the poor water‐solubility and aggregation tendency are the main reasons for the suboptimal PDT performance of free ZnPc in the aqueous medium. Effective solubilization of ZnPc in an aqueous medium was achieved by encapsulating it in the cavity of MB. The inclusion complex (ZnPc⊂MB) showed enhanced singlet oxygen generation in water. Higher cellular uptake and anticancer activity of the ZnPc⊂MB compared to free ZnPc on HeLa cells indicate that encapsulation of ZnPc in an aqueous host is a potential strategy for enhancement of its PDT activity in water.

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Self-assembly of a water-soluble endohedrally functionalized coordination cage including polar guests

Abstract: Coordination cages containing endohedrally functionalized aromatic cavities are scarce in literature. Herein, we report the self-assembly of a tetra-cationic super aryl-extended calix[4]pyrrole tetra-pyridyl ligand into a water-soluble Pd(II)-cage featuring two...

Cited by 11 publications

References 60 publications

Recent developments in calix[4]pyrrole (C4P)-based supramolecular functional systems

Recent developments in calix[4]pyrrole (C4P)-based supramolecular functional systems

Aryl-Extended and Super Aryl-Extended Calix[4]pyrroles: Design, Synthesis, and Applications

Solvent Induced Conversion of a Self‐Assembled Gyrobifastigium to a Barrel and Encapsulation of Zinc‐Phthalocyanine within the Barrel for Enhanced Photodynamic Therapy

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