Aryl- and Superaryl-Extended Calix[4]pyrroles: From Syntheses to Potential Applications

Rather, Ishfaq Ahmad; Danjou, Pierre-Edouard; Ali, Rashid

doi:10.1007/s41061-022-00419-0

Cited by 10 publications

(6 citation statements)

References 181 publications

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“…Over the last 15 years, our research group focused on the design and synthesis of AE-C[4]P receptors for the selective and efficient binding of anions, ion-pairs, and neutral polar molecules. In this Account, we discuss the binding properties of “two-wall” and “four-wall” AE-C[4]Ps and their derivatives, such as AE-C[4]P cavitands and super aryl-extended C[4]Ps (SAE-C[4]Ps) . We also describe their applications in molecular sensing, facilitated transmembrane transport, and modulation of chemical reactivity.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

confidence: 99%

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

2023

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“…Analytical methods utilizing optical signatures and supramolecular sensors/receptors have been of great interest to the scientific community in recent years. 14,15 Among the diverse supramolecular receptors available, the tetrapyrollic macrocyclic receptor known as calix [4]pyrrole (C4P) has shown a promising role in the recognition of diverse analytes 16 . C4P possess a built-in recognition site able to recognize anions or polar guests, while its functionalization at the level of meso-carbon or pyrrole allow to achieve cation or ion-pair recognition throught non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%

Revisiting -dicyanovinyl substituted calix[4]pyrrole : toward the chemodosimetric detection of hydrazine in solution

Kasprowiak

Rather

Ali

et al. 2023

Preprint

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Calix[4]pyrrole derivatives are usually used to recognize charged species or polar guests through non-covalent interactions, but the chemodosimetric approach remains scarce in the literature. In this study, the selective chemodosimetric detection and quantification of hydrazine, a hazardous pollutant commonly used in industy, was performed using UV-spectroscopy with a repurposed -dicyanovinyl substituted calix[4]pyrrole sensor. The selectivity of the chemodosimeter towards hydrazine was evaluated in acetonitrile with various nucleophiles (nitrogen-containing compounds and a thiol). In addition, the influence of several parameters (time, water content, and temperature) on hydrazine detection by the sensor was evaluated. This study allows for the sensing of hydrazine with a limit of detection (LOD) of 1.3 mg/L and a linear response in the 10-1000 M range. The ability to detect hydrazine with the naked eye has also been demonstrated. This paper reports one of the first chemodosimetric approach employed with calix[4]pyrrole to detect and quantify a neutral molecule, namely hydrazine.

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“…[23][24][25][26][27][28][29][30][31] However, holding various functionalization sites at meso-and/or C-/N-rims, [32][33][34] displayed a promising roles in molecular recognition (anion/ ion-pair/neutral molecule binding, transmembrane ion transport, polymers, molecular switches, etc.) [35][36][37][38][39][40][41][42][43][44][45][46] and self-assembly (capsular/caged structures, adsorption, etc.). [47][48][49] Notably, the tetrapyrrolic macrocyclic supramolecular receptors, namely calix [4]pyrroles are yet to be explored for boronic acid chemistry from fundamental to advanced level.…”

Section: Introductionmentioning

confidence: 99%

“…However, holding various functionalization sites at meso‐ and/or C‐/N ‐rims, [32–34] displayed a promising roles in molecular recognition (anion/ion‐pair/neutral molecule binding, transmembrane ion transport, polymers, molecular switches, etc . ) [35–46] and self‐assembly (capsular/caged structures, adsorption, etc .) [47–49] .…”

Section: Introductionmentioning

confidence: 99%

Probing and Evaluating the Anion Binding Effects in One‐Walled meso‐Phenylboronic Acid Appended Calix[4]pyrrole (C4P) Based Supramolecular Receptors

Rather,

Alam,

Ali

2023

ChemistrySelect

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Herein, binding affinities of one‐walled meso‐phenylboronic acid functionalized calix[4]pyrroles (C4Ps, 3 a & 3 b) with diverse anions including spherical, linear, trigonal, and tetrahedral through UV‐Vis spectroscopy have successfully been revealed in acetonitrile solvent. The C4P derivative 3 b was newly synthesized from an easily accessible 3‐acetylphenylboronic acid via both conventional as well as green protocols. Structure of the final compound 3 b and the dipyrromethane (DPM) 2 b, were unambiguously established by means of 1H‐NMR, 13C‐NMR, and HRMS spectral data. From the outcomes of the UV‐Vis titrations of 3 a/3 b with different anions (e. g., F−, Cl−, Br−, I−, NO3−, HSO4−, H2PO4−, CH3COO−, & SCN−), used as their tetrabutylammonium (TBA) salts in CH3CN, 1 : 1 stoichiometric binding mode were observed from the BindFit v0.5 and Job plots. Overall, the binding affinity of receptor (3 b) with different anions were found higher in comparison to the receptor (3 a), presumably due to more cooperative NH and/or OH hydrogen bonding interactions. On the basis of varied size of halide ions, typical trend of anion binding affinity i. e., F−>Cl−>Br−>I−, was detected with increase in size of halide ions from F− to I−. Hopefully, these anion binding investigations with C4P‐based meso‐functionalized architectures will open new possibilities to the researchers to generate even more interesting artificial anion receptors based on vital boronic acid functionality, as biological and chemical importance of the anions is continuously motivating the synthetic chemists worldwide.

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Aryl- and Superaryl-Extended Calix[4]pyrroles: From Syntheses to Potential Applications

Cited by 10 publications

References 181 publications

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

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

Revisiting -dicyanovinyl substituted calix[4]pyrrole : toward the chemodosimetric detection of hydrazine in solution

Probing and Evaluating the Anion Binding Effects in One‐Walled meso‐Phenylboronic Acid Appended Calix[4]pyrrole (C4P) Based Supramolecular Receptors

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