Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes : Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion
Pamuła, M., Nissinen, M., & Helttunen, K. (2020). Correlating Solution‐ and Solid‐State Structures of Conformationally Flexible Resorcinarenes : Significance of a Sulfonyl Group in Intramolecular Self‐Inclusion. Chemistry : A European Journal, 26(33), 7374-7383. https://doi.org/10.1002/chem.201905211
Published in
Chemistry : A European JournalDate
2020Copyright
© The Authors 2020
In this study, the synthesis of tetramethoxy resorcinarene podands bearing p‐toluene arms connected by ‐SO3‐ (1) and ‐CH2O‐ (2) linkers is presented. In the solid state, the resorcinarene podand 1 forms an intramolecular self‐inclusion complex of the p‐toluene group, whereas the resorcinarene podand 2 did not show self‐inclusion. The conformation of the flexible resorcinarene podands in solution was investigated by 1D and 2D NMR spectroscopic techniques using variable temperature experiments, as well as, with computational methods including conformational search and subsequent density functional theory (DFT) optimization for 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 chemical shift time scale. An energy barrier (ΔG‡298) of 55.5 kJ/mol and 52.0 kJ/mol was 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 podand1 adopts similar conformation to that present in its crystal structure, whereas podand 2 populates more versatile range of conformations in solution.
...
Publisher
Wiley-VCH VerlagISSN Search the Publication Forum
0947-6539Keywords
Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/34708414
Metadata
Show full item recordCollections
Related funder(s)
Research Council of FinlandFunding program(s)
Research costs of Academy Research Fellow, AoF; Academy Research Fellow, AoFAdditional information about funding
Academy of Finland (grants 309910, 314287, 257246) is gratefully acknowledged for funding.License
Related items
Showing items with similar title or keywords.
-
Host-guest complexes of conformationally flexible C-hexyl-2-bromoresorcinarene and aromatic N-oxides : solid-state, solution and computational studies
Puttreddy, Rakesh; Beyeh, Ngong Kodiah; Taimoory, S. Maryamdokht; Meister, Daniel; Trant, John F.; Rissanen, Kari (Beilstein-Institut zur Foerderung der Chemischen Wissenschaften, 2018)Host–guest complexes of C-hexyl-2-bromoresorcinarene (BrC6) with twelve potential aromatic N-oxide guests were studied using single crystal X-ray diffraction analysis and 1H NMR spectroscopy. In the solid state, of the ... -
Exploring the self-assembly of resorcinarenes : from molecular level interactions to mesoscopic structures
Helttunen, Kaisa (University of Jyväskylä, 2012) -
Binding of ion pairs and neutral guests by aryl-extended meso‑p-hydroxyphenyl calix[4]pyrrole : The interplay between three binding sites
Pamuła, Małgorzata; Bulatov, Evgeny; Helttunen, Kaisa (Elsevier BV, 2023)An aryl-extended calix[4]pyrrole with four meso‑p-hydroxyphenyl substituents was investigated as a host for chloride, acetate, and benzoate anions. Crystal structures of pyridinium and imidazolium chloride complexes were ... -
Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives
Rissanen, Kari; Taipale, Essi; Truong, Khai-Nghi; Siepmann, Marcel (Wiley, 2021)The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp 2 N -containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the ... -
The Effect of the Side Chain on Gelation Properties of Bile Acid Alkyl Amides
Kuosmanen, Riikka T.; Truong, Khai‐Nghi; Rissanen, Kari T.; Sievänen, Elina I. (Wiley-VCH Verlag, 2021)Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all ...