Nature of alkali metal ion interactions with cyclic polyfunctional molecules. I. Vibrations of alkali ions encaged by crown ethers in solution

Tsatsas, Andreas T.; Stearns, Robert W.; Risen, William M.

doi:10.1021/ja00770a019

Cited by 55 publications

(10 citation statements)

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“…No crystal data for the Li + ·DB18C6 complex was put into the database. [68,69] In contrast, the Na + and K + complexes take quite different forms in the gas phase ( Figure 12). For all the K + complexes in crystals, the DB18C6 part has a boat-type open form.…”

Section: Structures Of the [Alkali Metal Ion·crown Ether] Inclusion Cmentioning

confidence: 99%

“…[64][65][66][67] The IR and NMR studies in solution suggested that the K + ·DB18C6 and Na + ·DB18C6 complexes have similar conformations to each other. [68,69] In contrast, the Na + and K + complexes take quite different forms in the gas phase ( Figure 12). The K + ·DB18C6 complex takes a boat conformation, similar to those in crystals and in solution.…”

Section: Structures Of the [Alkali Metal Ion·crown Ether] Inclusion Cmentioning

confidence: 99%

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Laser Spectroscopic Study of Cold Host–Guest Complexes of Crown Ethers in the Gas Phase

et al. 2012

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A laser spectroscopic study on the structure and dynamics of cold host-guest inclusion complexes of crown ethers (CEs) with various neutral and ionic species in the gas phase is presented. The complexes with neutral guest species are formed by using supersonic free jets, and those with ionic species are generated with electrospray ionization combined with a cold 22-pole ion trap. For CEs, various sizes of 3n-crown-n ethers (n=4, 5, 6, and 8) and their benzene-substituted species are used. For the guest species, water, methanol, ammonia, acetylene, and phenol are employed as neutral guest species, and for charged guest species, alkali metal cations are chosen. The electronic and vibrational spectra of the complexes are measured by using various laser spectroscopic methods; electronic spectra for the neutral complexes are measured by laser-induced fluorescence. Discrimination of different species such as conformers is performed by ultraviolet-ultraviolet hole-burning spectroscopy. The vibrational spectra of selected species are observed by infrared-ultraviolet double-resonance (IR-UV DR) spectroscopy. For the ionic complexes, ultraviolet photodissociation and IR-UV DR spectroscopy are applied. The complex structures are determined by comparing the observed spectra with those of possible structures obtained by density functional theory calculations. How the host CEs change their conformation or which conformer prefers to form unique inclusion complexes are discussed. These results reveal the key interactions for forming special complexes leading to molecular recognition.

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Section: Structures Of the [Alkali Metal Ion·crown Ether] Inclusion Cmentioning

confidence: 99%

Section: Structures Of the [Alkali Metal Ion·crown Ether] Inclusion Cmentioning

confidence: 99%

Laser Spectroscopic Study of Cold Host–Guest Complexes of Crown Ethers in the Gas Phase

et al. 2012

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“…The influence of cation-complexing agents like crown ethers 281 \ cryptands 283 « 298 > or biological macrocyclic systems 301} on the structure of ion pairs is very marked and can easily be seen in vibrational spectroscopy.…”

Section: Absorption Spectroscopymentioning

confidence: 99%

Non-aqueous electrolyte solutions in chemistry and modern technology

Barthel

Gores

Schmeer

et al. 1983

Topics in Current Chemistry

114

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“…The ' Y for the 5% copolymer is probably close to unity. Its A value above a crown to salt ratio larger than unity approaches 46 (the slight decrease at higher ratios is caused by increased viscosity of the solution). This compares with a A-value of 42 for BPhc-at 10-3 M (obtained from measurements on triisoamylbutylammonium tetraphenylboron by assuming that K = A + at 10-3 M).…”

Section: Conductance Measurementsmentioning

confidence: 99%

Solute Binding to Polymers Containing Macroheterocyclic Rings

Smid

1976

Pure and Applied Chemistry

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Abstraet-Interactions of macroheterocycles and polymers endowed with such cation binding ligands as pendant groups, with ions or ion pairs are discussed, emphasis being placed on the binding properties of the macrocyclic polyethers or crown ethers. The use of ßuorenyl and pierate salts permitted a spectrophotometric investigation of Iigand interactions with ion pairs and a determination of ion pair-crown ether structures, which is of importance in the study of ion transport through low polarity media. Conductometric and spectrophotometric studies were carried out to obtain the complex formation constants of bis(crown ethers) (e.g. crown compounds with two crown moieties at opposite ends of a short aliphatic chain) to cations and their pierate tight ion pairs, as a function of the length and structure of the bis(crown ether) chain. Studies of cation binding to homopolymers and styrene copolymers of vinylbenzo-15-crown-5 and of vinylbenzo-18-crown.{i using extraction equilibria, ion transport, conduc(ance and viscosity, demonstrated the formation of 1 : 1 and 2: 1 crown-cation complexes, selectivity of cation binding, the dependence of the complexation constant on the number of cations bound to the chain, and the possibility of intermolecular 2: 1 crown-cation complex formation and crosslinking in copolymers with a low crown content. The polymer poly(vinylbenzo-18-crown-6) exhibits unusually strong binding of organic neutral and anionic solutes in aqueous media. Binding of pierate salts, methyl orange, phenolphtaleine and other solutes were studied spectrophotometrically. The hydrophobic adsorption of organic solutes also causes this polymer to catalyze the decarboxylation of 6-nitrobenzisoxazole-3-carboxylate by dehydrating the anion. The reaction is accelerated in the presence of complexable cations, which are bound to the polycrown ether, thereby further enhancing the adsorption of organic anions by electrostatic interactions. The same polymer was found to precipitate polynucleotides in water in the presence of complexable cations such as K+. It also exerts a strong inh!bitory effect on the polyriboadenylate templated elongation of oligodeoxythymidine catalyzed by murine leukemia virions.

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Nature of alkali metal ion interactions with cyclic polyfunctional molecules. I. Vibrations of alkali ions encaged by crown ethers in solution

Cited by 55 publications

References 1 publication

Laser Spectroscopic Study of Cold Host–Guest Complexes of Crown Ethers in the Gas Phase

Laser Spectroscopic Study of Cold Host–Guest Complexes of Crown Ethers in the Gas Phase

Non-aqueous electrolyte solutions in chemistry and modern technology

Solute Binding to Polymers Containing Macroheterocyclic Rings

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