Thermodynamically driven self-assembly of pyridinearene to hexameric capsules
Kiesilä, A., Beyeh, N. K., Moilanen, J. O., Puttreddy, R., Götz, S., Rissanen, K., Barran, P., Lützen, A., & Kalenius, E. (2019). Thermodynamically driven self-assembly of pyridinearene to hexameric capsules. Organic and Biomolecular Chemistry, 17(29), 6980-6984. https://doi.org/10.1039/C9OB01383K
Published inOrganic and Biomolecular Chemistry
© The Royal Society of Chemistry, 2019
Pyridinearene macrocycles have previously shown unique host–guest properties in their capsular dimers including endo complexation of neutral molecules and exo complexation of anions. Here, we demonstrate for the first time the formation of hydrogen bonded hexamer of tetraisobutyl-octahydroxypyridinearene in all three states of matter – gas phase, solution and solid-state. Cationic tris(bipyridine)ruthenium(II) template was found to stabilize the hexamer in gas phase, whereas solvent molecules do this in condensed phases. In solution, the capsular hexamer was found to be the thermodynamically favoured self-assembly product and transition from dimer to hexamer occurred in course of time. The crystal structure of hexamer revealed 24 N–H⋯O direct intermolecular hydrogen bonds between the six pyridinearene macrocycles without any bridging solvent molecules. Hydrogen bond patterns correlate well with DFT computed structures. Thus, all structural chemistry methods (IM-MS, DOSY NMR, DFT, X-ray crystallography) support the same structure of the hexameric capsule that has a diameter of ca. 3 nm and volume of 1160 Å3. ...
PublisherRoyal Society of Chemistry
Publication in research information system
MetadataShow full item record
Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Research Fellow, AoF; Research post as Academy Research Fellow, AoF; Postdoctoral Researcher, AoF
Additional information about fundingThe authors acknowledge the Academy of Finland for the funding (JOM: 285855, 315829, 320015, RP: 298817, EK: 284562, 278743 and 312514) as well as Prof. H. M. Tuononen, University of Jyväskylä, CSC-IT Center for Science in Finland, and the Finnish Grid and Cloud Infrastructure (persistent identifierurn:nbn:fi:research-infras-2016072533) for providing computational resources. NKB gratefully acknowledge the financial support from Oakland University, MI, USA. ...
Showing items with similar title or keywords.
Shen, Hui; Xu, Zhen; Wang, Lingzheng; Han, Ying-Zi; Liu, Xianhu; Malola, Sami; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng (Wiley, 2021)Chiral hierarchical structures are universal in nature, whereas quite challenging to mimic in man-made synthesis. We report herein the synthesis and structure of tertiary chiral nanostructures with 100% optical purity. A ...
Synthetic and Structural Studies on the Effect of Non-Covalent Interactions on N(sp2)-Heterocyclic Molecules Taipale, Essi (2022)The thesis herein describes the synthesis and characterization of compounds designed to be utilized as acceptor molecules in non-covalent interactions. The non-covalent interactions are applied in fluorescence modulation ...
Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters : From 2D Colloidal Crystals to Spherical Capsids Nonappa; Lahtinen, Tanja; Haataja, Johannes S.; Tero, Tiia-Riikka; Häkkinen, Hannu; Ikkala, Olli (Wiley - VCH Verlag GmbH & Co. KGaA, 2016)We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au102-pMBA44) under aqueous conditions into hexagonally packed monolayer-thick ...
Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen-Bonds Shi, Qixun; Zhou, Xiaohong; Yuan, Wei; Su, Xiaoshi; Neniškis, Algirdas; Wei, Xin; Taujenis, Lukas; Snarskis, Gustautas; Ward, Jas S; Rissanen, Kari; de Mendoza, Javier; Orentas, Edvinas (American Chemical Society, 2020)We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal coordinating 2,2’-bipyridine units. When mixed with metal ions such as Fe2+ or ...
Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands Hovorka, Rainer; Hytteballe, Sophie; Piehler, Torsten; Meyer-Eppler, Georg; Topic, Filip; Rissanen, Kari; Engeser, Marianne; Lützen, Arne (Beilstein - Institut zur Foerderung der Chemischen Wissenschaften, 2014)Two new 9,9’-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)₂M₂L₂] rhombi with cis-protected ...