Conformational features of calix[4]arenes with alkali metal cations: A quantum chemical investigation with density functional theory

Rozhenko, Alexander; Schoeller, Wolfgang W.; Letzel, Matthias C.; Decker, Björn; Agena, Ceno; Mattay, Jochen

doi:10.1016/j.theochem.2005.06.041

Cited by 24 publications

(16 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[15] Although van der Waals interactions are poorly described by DFT methods, the latter provide reliable structures and reaction enthalpies for the formation of adducts based on the cation-p interactions. This was proven by previous investigations that focused on the inclusion of calixarenes [16] and even their dimers. [17] In all cases, the mass-spectrometric investigation results were in good agreement with the calculation data.…”

Section: Introductionmentioning

confidence: 69%

Calixarenes as Hosts for Ammonium Cations: A Quantum Chemical Study and Mass‐Spectrometric Investigations

Rozhenko

Schoeller

Letzel

et al. 2006

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Host-guest complexes of tetramethylcavitand with different ammonium cations were investigated by using a quantum chemical method at the density functional level (BP86, B3 LYP). The NH4+ cation is strongly bound to the host. Increasing methyl substitution at the cation decreases its inclination towards the complex formation. The calculated data are in line with results from electrospray ionization mass spectrometry (ESI-MS) experiments. They reveal stable aggregates only for the NH4+ cation and for the primary alkylammonium cations.

show abstract

Section: Introductionmentioning

confidence: 69%

Calixarenes as Hosts for Ammonium Cations: A Quantum Chemical Study and Mass‐Spectrometric Investigations

Rozhenko

Schoeller

Letzel

et al. 2006

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although, other complexes of resorcinarene have previously been modeled, [14] to the best of our knowledge complexes with sugars have not been reported, and so we were constrained to looking more closely at the conformation of the oligosaccharides by using theoretical calculations. In the first stage, the structures of Glu, Glc 2 , Glc 3 , Glc 4 , and Glc 5 were optimized ( Figure 6).…”

Section: Resultsmentioning

confidence: 99%

“…[17,18] Resorcinarene 2 was prepared according to earlier reported procedures. [14,19] Resorcinarene 1 was dissolved in methanol and resorcinarene 2 in dimethyl sulfoxide (DMSO). The final samples were prepared in methanol with a resorcinarene concentration of 4.0 mm.…”

Section: Methodsmentioning

confidence: 99%

Size‐ and Structure‐Selective Noncovalent Recognition of Saccharides by Tetraethyl and Tetraphenyl Resorcinarenes in the Gas Phase

Kalenius

Kekäläinen

Neitola

et al. 2008

Chemistry A European J

View full text Add to dashboard Cite

The noncovalent complexation of tetraethyl and tetraphenyl resorcinarenes with mono-, di-, and oligosaccharides was studied with negative-polarization electrospray ionization quadrupole ion trap and electrospray ionization Fourier-transform ion cyclotron resonance mass-spectrometric analysis. The saccharides formed 1:1 complexes with deprotonated resorcinarenes, which exhibited clear size and structure selectivity in their complexation. In the case of the monosaccharides, hexoses formed much more abundant and kinetically stable complexes than pentoses or deoxyhexoses. A comparison of the mono-, di-, and oligosaccharides revealed that both the relative abundance and stability of the complexes increase up to biose and triose, but start to decrease after that point, as the length of the oligosaccharide is increased. This behavior was rationalized by comparing the lowest-energy conformations of the complexes formed between the resorcinarene and oligosaccharides. This comparison was achieved by using theoretical calculations and X-ray crystal studies.

show abstract

“…We observed a reversed trend in comparison to the anthracene‐substituted ligands. This means that 7 more effectively binds cationic guests than 4 , because its geometry in the free form is better prepared for coordination;38 the alkyl chain tightens two ‘boards’ of the ‘boat’ in the free ligand 7 .…”

Section: Resultsmentioning

confidence: 99%

A kinetic study of guest displacement reactions on a host–guest complex with a photoswitchable calixarene

et al. 2008

Self Cite

View full text Add to dashboard Cite

The displacement processes of several guests, incorporated in a calixarene host system, were investigated in the gas phase by electrospray ionization-Fourier transform-ion cyclotron resonance (ESI-FT-ICR) mass spectrometry. The complexes resulting from a resorcin[4]arene host with ammonia and sec-butylamine guests were isolated in an ICR-cell, separately using both states of the photoswitch as well as two reference systems for the open and closed forms of the photoswitchable host. The isolated complexes were forced to exchange the guest by using methylamine, ethylamine and sec-butylamine, resulting in different reaction rates for all the measured systems. Especially, the reaction rates of both states of the photoswitch are dependent on the provided guest. Potential side effects like proton exchanges were examined by an H/D-exchange experiment. The results were investigated and supported by quantum chemical calculations (DFT).

show abstract

Conformational features of calix[4]arenes with alkali metal cations: A quantum chemical investigation with density functional theory

Cited by 24 publications

References 47 publications

Calixarenes as Hosts for Ammonium Cations: A Quantum Chemical Study and Mass‐Spectrometric Investigations

Calixarenes as Hosts for Ammonium Cations: A Quantum Chemical Study and Mass‐Spectrometric Investigations

Size‐ and Structure‐Selective Noncovalent Recognition of Saccharides by Tetraethyl and Tetraphenyl Resorcinarenes in the Gas Phase

A kinetic study of guest displacement reactions on a host–guest complex with a photoswitchable calixarene

Contact Info

Product

Resources

About