Influence of Chiral Ionic Liquids on the Excited-State Properties of Naproxen Analogs

Adhikary, Ramkrishna; Bose, Sayantan; Mukherjee, Prasun; Thite, Aniket; Kraus, George A.; Wijeratne, Aruna B.; Sharma, Pritesh S.; Armstrong, Daniel W.; Petrich, Jacob W.

doi:10.1021/jp711508b

Cited by 18 publications

(19 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A 10% difference in lifetime (∼8.9 and ∼8.1 ns) is observed in the two chiral solvents at room temperature (Figure 4), which is consistent with our previous results in the menthyl-based ionic liquids. 26 As a control, similar experiments were also done with (S)-naproxen, which is the parent compound of the dyad, and the stereodifferentiation in the lifetimes is also observed at room temperature ( Figure 5). To ensure that this discrimination is not due to impurities in the ionic liquids, (S)-and (R)-naproxen were also studied in the same ionic liquids, and a ∼10% difference in fluorescence lifetimes was observed for the two naproxen isomers ( Table 1).…”

Section: Resultsmentioning

confidence: 85%

Influence of Chiral Ionic Liquids on Stereoselective Fluorescence Quenching by Photoinduced Electron Transfer in a Naproxen Dyad

et al. 2009

Self Cite

View full text Add to dashboard Cite

In a previous study of a naproxen dyad in a pair of N-methylimidazoliummethyl menthylether−NTf2 chiral ionic liquids (J. Phys. Chem. B 2008, 112, 7555), we observed that though intramolecular electron transfer was impeded, a consistent small stereodifferentiation in the fluorescence lifetime of the dyad was obtained. We proposed that this discrimination was purely electronic in nature and did not arise from geometrical effects, which can influence nonradiative rate processes, such as intramolecular electron transfer. In our present work, we have studied the interaction of the same chiral naproxen dyad molecule in both the previously studied menthyl-based NTf2 ionic liquids and also in bis(tertrabutylphosphonium) (TBP) d-,l-tartrate ionic liquids. Unlike in the menthyl-based IL pair, the amount of quenching is different in the bis(TBP) tartrate enantiomeric liquids and the tartrate enantiomers have a different temperature dependence on the nonradiative rate of the dyad. This chiral discrimination most likely arises from the steric effects of the different conformations of the chiral molecules. We have shown that the viscosity and polarity of the solvents can influence the rate of electron transfer. On the other hand, no such electron transfer quenching is observed in the menthyl-based NTf2 IL solvents. To our knowledge, this is the first example of chiral ionic liquids inducing a stereoselective fluorescence quenching by photoinduced, intramolecular electron transfer. In a previous study of a naproxen dyad in a pair of N-methylimidazoliummethyl menthylether-NTf 2 chiral ionic liquids (J. Phys. Chem. B 2008, 112, 7555), we observed that though intramolecular electron transfer was impeded, a consistent small stereodifferentiation in the fluorescence lifetime of the dyad was obtained. We proposed that this discrimination was purely electronic in nature and did not arise from geometrical effects, which can influence nonradiative rate processes, such as intramolecular electron transfer. In our present work, we have studied the interaction of the same chiral naproxen dyad molecule in both the previously studied menthyl-based NTf 2 ionic liquids and also in bis(tertrabutylphosphonium) (TBP) D-,L-tartrate ionic liquids. Unlike in the menthyl-based IL pair, the amount of quenching is different in the bis(TBP) tartrate enantiomeric liquids and the tartrate enantiomers have a different temperature dependence on the nonradiative rate of the dyad. This chiral discrimination most likely arises from the steric effects of the different conformations of the chiral molecules. We have shown that the viscosity and polarity of the solvents can influence the rate of electron transfer. On the other hand, no such electron transfer quenching is observed in the menthyl-based NTf 2 IL solvents. To our knowledge, this is the first example of chiral ionic liquids inducing a stereoselective fluorescence quenching by photoinduced, intramolecular electron transfer.

show abstract

Section: Resultsmentioning

confidence: 85%

Influence of Chiral Ionic Liquids on Stereoselective Fluorescence Quenching by Photoinduced Electron Transfer in a Naproxen Dyad

et al. 2009

Self Cite

View full text Add to dashboard Cite

show abstract

“…119 They observed a reproducible stereodifferentiation ($ 10%) in the fluorescence lifetime of (S,S)-NPX-PYR and (S)-naproxen in 6 CIL 98 (see Fig. 24).…”

Section: Cils In Spectroscopymentioning

confidence: 89%

Chiral ionic liquids: A compendium of syntheses and applications (2005–2012)

Payagala¹,

Armstrong²

2011

Chirality

Self Cite

125

View full text Add to dashboard Cite

In recent years, the field of chiral ionic liquids (CILs) has undergone exponential growth. As the technology has advanced, new ways of synthesizing stable and structurally diverse ionic liquids have been established. This has led to heretofore unknown applications of CILs as well as in improving efficiency of previously identified applications. In this review article we have compiled a comprehensive database containing structures and physical properties of notable CILs that have been synthesized during the last 6 years. Their applications in the fields of asymmetric organic synthesis, spectroscopy, and chromatography are also illustrated. This is an expansion of our previous review, which covered the literature before 2005.

show abstract

“…Chiral recognition, enantioselectivity, and influence of room temperature CILs (RTIL) synthesized from 1-methyl imidazole and chloromethyl menthyl ether on excited-state photophysics of (S)-N-methyl-2-pyrrolidinemethyl 2(S)-(6-methoxy-2-naphthyl)propionate [(S,S)-NPX-PYR] was recently investigated using a fluorescence lifetime [114]. The chemical structures of the CILs and chiral analytes used for the lifetime study are shown in Fig.…”

Section: Life Time Studymentioning

confidence: 99%

“…In the CILs, the lifetime is significantly increased and there is a difference in lifetime in the two solvents. Adapted from [114] Table 2 Fluorescence lifetime parameters of (S,S)-NPX-PYR and related systems. Data from [114] Ionic liquid selector and selectand system τ (ns) A similar study conducted using S-naproxen as chiral analyte also demonstrates a 10% difference in fluorescence lifetimes of S-naproxen in the presence of (+)-RTIL and (−)-RTIL [115].…”

Section: Life Time Studymentioning

confidence: 99%

Chiral Ionic Liquids in Chromatographic Separation and Spectroscopic Discrimination

Bwambok

Fakayode

et al. 2010

Chiral Recognition in Separation Methods

View full text Add to dashboard Cite

Influence of Chiral Ionic Liquids on the Excited-State Properties of Naproxen Analogs

Cited by 18 publications

References 38 publications

Influence of Chiral Ionic Liquids on Stereoselective Fluorescence Quenching by Photoinduced Electron Transfer in a Naproxen Dyad

Influence of Chiral Ionic Liquids on Stereoselective Fluorescence Quenching by Photoinduced Electron Transfer in a Naproxen Dyad

Chiral ionic liquids: A compendium of syntheses and applications (2005–2012)

Chiral Ionic Liquids in Chromatographic Separation and Spectroscopic Discrimination

Contact Info

Product

Resources

About