Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution

A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cav…

Simultaneous Endo- and Exo-Complex Formation of Pyridine[4]arene Dimer with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6−) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI‐QTOF‐MS, IM‐MS, DFT calculations), in the solid state (X‐ray crystallography), and in chloroform solution (1H, 19F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6− anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase. peerReviewed

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers

Pyridine[4]arenes have previously been considered as anion binding hosts due to the electron-poor nature of the pyridine ring. Herein, we demonstrate the encapsulation of Me4N+ cations inside a dimeric hydrogen-bonded pyridine[4]arene capsule, which contradicts with earlier assumptions. The complexation of a cationic guest inside the pyridine[4]arene dimer has been detected and studied by multiple gas-phase techniques, ESI-QTOF-MS, IRMPD, and DT-IMMS experiments, as well as DFT calculations. The comparison of classical resorcinarenes with pyridinearenes by MS and NMR experiments reveals clear differences in their host–guest chemistry and implies that cation encapsulation in pyridine[4]arene…

Selective gas adsorption by calixarene-based porous octahedral M32 coordination cages

Giant octahedral M32 coordination cages were prepared via self-assembly of sulfonylcalix[4]arene-supported tetranuclear M(II) clusters (M = Co, Ni) with hybrid linker based on tris(dipyrrinato)cobalt(III) complexes appended with peripherical carboxylic groups. Due to intrinsic and extrinsic porosity, the obtained solid-state supramolecular architectures demonstrated good performance as adsorbents for the separation of industrially important gases mixtures. peerReviewed

Simultane endo - und exo -Komplexbildung von Pyridin[4]aren-Dimeren mit neutralen und anionischen Gästen

Ion-Pair Complexation with Dibenzo[21]Crown-7 and Dibenzo[24]Crown-8 bis-Urea Receptors

Synthesis and ion-pair complexation properties of novel ditopic bis-urea receptors based on dibenzo[21]crown-7 (R(1) ) and dibenzo[24]crown-8 (R(2) ) scaffolds have been studied in the solid state, solution, and gas phase. In a 4:1 CDCl3 /[D6 ]DMSO solution, both receptors clearly show positive heterotropic cooperativity toward halide anions when complexed with Rb(+) or Cs(+) , with the halide affinity increasing in order I(-) <Br(-) <Cl(-) . In solution, the rubidium complexes of both receptors have higher halide affinities compared to the caesium complexes. However, Rb(+) and Cs(+) complexes of R(2) show stronger affinities toward all the studied anions compared to the corresponding catio…

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution

A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cav…

Thermodynamically driven self-assembly of pyridinearene to hexameric capsules

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 …

Structural studies of five novel bile acid-4-aminopyridine conjugates

Abstract Synthesis and solid-state structural characterization of five bile acid amides of 4-aminopyridine (4-AP) are reported. Systematic crystallization experiments revealed a number of structural modifications and/or solvate/hydrate systems for these conjugates. Particularly, cholic acid conjugate exhibited five distinct structure modifications, including one anhydrous form, mono- and dihydrates, as well as ethanol and 2-butanol solvates. The obtained crystal forms were examined extensively with various analytical methods, including solid-state NMR, Raman, and IR spectroscopies, powder and single crystal X-ray diffraction methods, thermogravimetry, and differential scanning calorimetry. …

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution† †Electronic supplementary information (ESI) available: MS, NMR, dynamic NMR and computational details and a DFT-based video of complexation. CCDC 1514736–1514741, 1521388. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05058a Click here for additional data file. Click here for additional data file. Click here for additional data file.

Chiral (all-R)-cyclohexanohemicucurbit[8]uril binds anions in a 1 : 1 ratio in pure methanol like a molecular Pac-Man™ with remarkable selectivity based on the size, shape and charge distribution of the anion.

Simultaneous endo and exo  Complex Formation of Pyridine[4]arene Dimers with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6- ) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI-QTOF-MS, IM-MS, DFT calculations), in the solid state (X-ray crystallography), and in chloroform solution (1 H, 19 F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6- anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase.

CCDC 1478712: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1543476: Experimental Crystal Structure Determination

Related Article: Anniina Kiesilä, Lauri Kivijärvi, Ngong Kodiah Beyeh, Jani O. Moilanen, Michael Groessl, Tatiana Rothe, Sven Götz, Filip Topić, Kari Rissanen, Arne Lützen and Elina Kalenius|2017|Angew.Chem.,Int.Ed.|56|10942|doi:10.1002/anie.201704054

CCDC 1478717: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1478716: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1478713: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1478715: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1514740: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

CCDC 1478709: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1478711: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1514737: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

CCDC 1478714: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1514738: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

CCDC 1514739: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution

Chiral (all-R)-cyclohexanohemicucurbit[8]uril binds anions in a 1 : 1 ratio in pure methanol like a molecular Pac-Man™ with remarkable selectivity based on the size, shape and charge distribution of the anion.

CCDC 1899745: Experimental Crystal Structure Determination

Related Article: Anniina Kiesilä, Ngong Kodiah Beyeh, Jani O. Moilanen, Rakesh Puttreddy, Sven Götz, Kari Rissanen, Perdita Barran, Arne Lützen, Elina Kalenius|2019|Org.Biomol.Chem.|17|6980|doi:10.1039/C9OB01383K

CCDC 1478710: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1478718: Experimental Crystal Structure Determination

Related Article: Toni Mäkelä, Anniina Kiesilä, Elina Kalenius and Kari Rissanen|2016|Chem.-Eur.J.|22|14264|doi:10.1002/chem.201602362

CCDC 1521388: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

CCDC 1514736: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A

CCDC 1514741: Experimental Crystal Structure Determination

Related Article: Sandra Kaabel, Jasper Adamson, Filip Topić, Anniina Kiesilä, Elina Kalenius, Mario Öeren, Mart Reimund, Elena Prigorchenko, Aivar Lõokene, Hans J. Reich, Kari Rissanen, Riina Aav|2017|Chemical Science|8|2184|doi:10.1039/C6SC05058A