Resorcinarene Podand with Amine‐Functionalized Side Arms – Synthesis, Structure, and Binding Properties of a Neutral Anion Receptor

Salorinne, Kirsi; Weimann, Dominik P.; Schalley, Christoph A.; Nissinen, Maija

doi:10.1002/ejoc.200900814

Cited by 26 publications

(16 citation statements)

References 48 publications

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“…The boat conformation is defined by two resorcinol rings being almost vertically oriented and the two remaining ones horizontally aligned. Previously, self‐inclusion dimers of resorcinarene tetrapodands have been observed by us and others . Nevertheless, resorcinarene podands tend to display collapsed cavities in the solid state …”

Section: Introductionmentioning

confidence: 74%

Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes: Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion

Pamuła

Nissinen

Helttunen

2020

Chemistry A European J

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The synthesis of tetramethoxyresorcinarene podands bearing p‐toluene arms connected by ‐SO3‐ (1) and ‐CH2O‐ (2) linkers is presented herein. In the solid state, the resorcinarene podand 1 forms an intramolecular self‐inclusion complex with the pendant p‐toluene group of a podand arm, whereas the resorcinarene podand 2 does not show self‐inclusion. The conformations of the flexible resorcinarene podands in solution were investigated by variable‐temperature experiments using 1D and 2D NMR spectroscopic techniques as well as by computational methods, including a conformational search and subsequent DFT optimisation of representative structures. The 1H NMR spectra of 1 and 2 at room temperature show a single set of proton signals that are in agreement with C4v symmetry. At low temperatures, the molecules exist as a mixture of boat conformations featuring slow exchange on the NMR timescale. Energy barriers (ΔG≠298) of 55.5 and 52.0 kJ mol−1 were calculated for the boat‐to‐boat exchange of 1 and 2, respectively. The results of the ROESY experiments performed at 193 K and computational modelling suggest that in solution the resorcinarene podand 1 adopts a similar conformation to that present in its crystal structure, whereas podand 2 populates a more versatile range of conformations in solution.

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Section: Introductionmentioning

confidence: 74%

Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes: Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion

Pamuła

Nissinen

Helttunen

2020

Chemistry A European J

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“…Resorcarenes represent a class of macrocyclic phenolic compounds obtained from the condensation reaction of resorcinol with several aldehydes in acidic solutions, 3 and they can be modified with various substituents on the upper and lower rim to provide specific functionality and selectivity. The many possible structural variations lead to potential applications as voltammetric sensors, 4 dendrimer synthesis, 5,6 dyeing of fibers, 7,8 nuclear magnetic resonance (NMR) solvating agents, 9,10 chemical receptors for molecules and ions [11][12][13] and absorption of heavy metal ions, 14,15 besides, resorcarene derivatives can be absorbed or covalently bound to multiple surface types. Thus resorcarenes are used in high performance liquid chromatography (HPLC) for modification of the stationary phase, and the process involves the lower rim of the resorcarene derivate with polar carbonate groups covalently bonded to a silica substrate.…”

Section: Introductionmentioning

confidence: 99%

Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes

Castillo-Aguirre¹,

Velásquez-Silva²,

Palacio³

et al. 2018

J. Braz. Chem. Soc.

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Surface modification of poly(GMA-co-EDMA-co-MMA), whose synthesis was performed by copolymerization of 2,3-epoxypropyl methacrylate (GMA), methyl methacrylate (MMA), and ethylene glycol dimethacrylate (EDMA), was compared between aliphatic and aromatic substituted resorcarenes. The copolymer surface was modified by reacting with resorcarenes, and the vibrational properties of the modified copolymers were investigated via attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman spectroscopies in dry state at room temperature. Those analysis showed that only tetra(p-hydroxyphenyl)resorcarene was linked to the copolymer, the reaction was regioselective with the crown conformer. Additionally, quantification of incorporated macrocyclic was performed, specifically, the maximum fixation of resorcarene in the copolymer was 95% when employing two molar resorcarene excesses per glycidyl residue.The modification was carried out in both acidic and basic medium and it was established that the polymer is modified with the aromatic resorcarene only in basic medium, while the reaction in basic medium with aliphatic resorcarenes produces their corresponding tetrasodium salt.

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“…Resorcinarenes represent a class of macrocyclic phenolic compounds obtained from the condensation reaction of resorcinol with several aromatic and aliphatic aldehydes in acidic solutions [ 1 , 2 ], and they can be modified with various substituents on the upper and lower rim in order to provide specific functionality and selectivity. The many possible structural variations lead to potential applications, such as voltammetric sensors [ 3 ], dendrimer synthesis [ 4 , 5 ], dyeing of fibers [ 6 , 7 ], NMR solvating agents [ 8 , 9 ], chemical receptors for molecules and ions [ 10 , 11 , 12 ], and absorption of heavy metal ions [ 13 , 14 ]. Furthermore, resorcinarene derivatives can be absorbed or covalently bound to multiple surface types.…”

Section: Introductionmentioning

confidence: 99%

Selective O-Alkylation of the Crown Conformer of Tetra(4-hydroxyphenyl)calix[4]resorcinarene to the Corresponding Tetraalkyl Ether

2017

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Reactions of glycidyl methacrylate with the crown and chair conformers of tetra(4-hydroxyphenyl)calix[4]resorcinarene were studied. The reactions were done over epoxide groups present in the ester, which can easily undergo an opening reaction with hydroxyl groups in the macrocyclic system. Initially, epoxidation reactions were carried out with pure conformers, and it was observed that the reaction between tetra(4-hydroxyphenyl)calix[4]resorcinarene fixed in the chair conformation does not occur, while for the molecule fixed in the crown conformation only one tetraalkylated derivative was obtained. The obtained product was characterized using IR, 1H-NMR, 13C-NMR, COSY, HMQC and HMBC techniques. An exhaustive NMR study showed that the reaction is selective at the hydroxyl groups in the lower rim, without affecting the hydroxyl groups in the upper rim. In addition, the RP–HPLC analysis of the epoxidation reaction mixture, using both crown and chair conformers, showed that only the crown conformer reacted under tested conditions. Finally, a comparative study of the reactivity of tetranonylcalix[4]resorcinarene with glycidyl methacrylate showed that the reaction does not take place. Instead, the formation of the tetranonylcalix[4]resorcinarene tetrasodium salt was observed, which confirms that the hydroxyl groups in the upper rim are unreactive under these conditions.

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Resorcinarene Podand with Amine‐Functionalized Side Arms – Synthesis, Structure, and Binding Properties of a Neutral Anion Receptor

Cited by 26 publications

References 48 publications

Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes: Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion

Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes: Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion

Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes

Selective O-Alkylation of the Crown Conformer of Tetra(4-hydroxyphenyl)calix[4]resorcinarene to the Corresponding Tetraalkyl Ether

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