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Exploring 12'-apo-beta-carotenoic-12'-acid as an ultrafast polarity probe for ionic liquids.
J Phys Chem B. 2008 Mar 13; 112(10):3048-57.JP

Abstract

The ultrafast excited-state dynamics of the carbonyl-containing carotenoid 12'-apo-beta-carotenoic-12'-acid (12'CA) have been used for probing the microscopic environment in various ionic liquids (ILs). The following IL cations were investigated: 1,3-di-n-alkyl-imidazolium featuring different n-alkyl chain lengths and also additional methylation at the C2 position, triethylsulfonium, as well as two tetraalkylammonium ions. These were combined with different anions: [BF4]-, [PF6]-, ethyl sulfate ([EtOSO3]-), and bis(trifluoromethylsulfonyl)amide ([Tf2N]-). The probe molecule was excited via the S0 --> S2 transition at 425 or 430 nm, and the characteristic stimulated emission decay of the low-lying excited electronic S1/ICT (intramolecular charge transfer) state of 12'CA was monitored in the near IR (850 or 860 nm). Its lifetime tau1 is sensitive to the micropolarity-induced stabilization of S1/ICT relative to S0. The lifetime tau1 of the S1/ICT state varies only moderately in all ionic liquids studied here (approximately 40-110 ps), which lies in the range between ethanol (109 ps) and methanol (49 ps). While organic solvents show an excellent correlation of tau1 with the solvent polarity function Deltaf = (epsilon - 1)/(epsilon + 2) - (n2 - 1)/(n2 + 2), where epsilon and n are the static dielectric constant and the refractive index of the solvent, respectively, this is not the case for ILs. This is due to dominant local electrostatic probe-cation interactions which cannot be easily quantified by macroscopic quantities. Methylation at the C2 position of 1,3-di-n-alkyl-imidazolium reduces the accessibility of the cation and therefore the electrostatic stabilization of the probe, resulting in an increase of tau1. A similar increase is observed upon extension of one of the n-alkyl chains from ethyl to n-decyl. Tetraalkylammonium ILs show an increased tau1 probably due to their more delocalized positive charge which cannot interact so favorably with the probe, in contrast to trialkylsulfonium ILs where the charge is more localized on the sulfur atom. The dependence of tau1 on the IL anion is much weaker, the only notable exception being [EtOSO3]-, where 12'CA experiences a less polar local environment than expected on the basis of extrapolated static dielectric constants. This is possibly due to the competition of the anion and probe for the cation interaction sites. Considerable electrostatic probe-cation interactions can be also introduced by addition of large amounts of LiClO4 salt to ethanol and diethyl ether. In this case, tau1 also strongly decreases, indicating an efficient coordination of Li+ cation(s) with the carbonyl oxygen at the negative end of the probe molecule. The S1/ICT --> S0 internal conversion of the 12'CA probe in ILs accelerates with increasing temperature, which can be characterized by an apparent activation energy of a few kJ mol-1, which is expected for energy-dependent nonradiative processes.

Authors+Show Affiliations

Georg-August-Universität Göttingen, Institut für Physikalische Chemie, Tammannstrasse 6, Göttingen, Germany.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

18275184

Citation

Lohse, Peter W., et al. "Exploring 12'-apo-beta-carotenoic-12'-acid as an Ultrafast Polarity Probe for Ionic Liquids." The Journal of Physical Chemistry. B, vol. 112, no. 10, 2008, pp. 3048-57.
Lohse PW, Bürsing R, Lenzer T, et al. Exploring 12'-apo-beta-carotenoic-12'-acid as an ultrafast polarity probe for ionic liquids. J Phys Chem B. 2008;112(10):3048-57.
Lohse, P. W., Bürsing, R., Lenzer, T., & Oum, K. (2008). Exploring 12'-apo-beta-carotenoic-12'-acid as an ultrafast polarity probe for ionic liquids. The Journal of Physical Chemistry. B, 112(10), 3048-57. https://doi.org/10.1021/jp710766z
Lohse PW, et al. Exploring 12'-apo-beta-carotenoic-12'-acid as an Ultrafast Polarity Probe for Ionic Liquids. J Phys Chem B. 2008 Mar 13;112(10):3048-57. PubMed PMID: 18275184.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Exploring 12'-apo-beta-carotenoic-12'-acid as an ultrafast polarity probe for ionic liquids. AU - Lohse,Peter W, AU - Bürsing,Reinhard, AU - Lenzer,Thomas, AU - Oum,Kawon, Y1 - 2008/02/15/ PY - 2008/2/16/pubmed PY - 2008/4/25/medline PY - 2008/2/16/entrez SP - 3048 EP - 57 JF - The journal of physical chemistry. B JO - J Phys Chem B VL - 112 IS - 10 N2 - The ultrafast excited-state dynamics of the carbonyl-containing carotenoid 12'-apo-beta-carotenoic-12'-acid (12'CA) have been used for probing the microscopic environment in various ionic liquids (ILs). The following IL cations were investigated: 1,3-di-n-alkyl-imidazolium featuring different n-alkyl chain lengths and also additional methylation at the C2 position, triethylsulfonium, as well as two tetraalkylammonium ions. These were combined with different anions: [BF4]-, [PF6]-, ethyl sulfate ([EtOSO3]-), and bis(trifluoromethylsulfonyl)amide ([Tf2N]-). The probe molecule was excited via the S0 --> S2 transition at 425 or 430 nm, and the characteristic stimulated emission decay of the low-lying excited electronic S1/ICT (intramolecular charge transfer) state of 12'CA was monitored in the near IR (850 or 860 nm). Its lifetime tau1 is sensitive to the micropolarity-induced stabilization of S1/ICT relative to S0. The lifetime tau1 of the S1/ICT state varies only moderately in all ionic liquids studied here (approximately 40-110 ps), which lies in the range between ethanol (109 ps) and methanol (49 ps). While organic solvents show an excellent correlation of tau1 with the solvent polarity function Deltaf = (epsilon - 1)/(epsilon + 2) - (n2 - 1)/(n2 + 2), where epsilon and n are the static dielectric constant and the refractive index of the solvent, respectively, this is not the case for ILs. This is due to dominant local electrostatic probe-cation interactions which cannot be easily quantified by macroscopic quantities. Methylation at the C2 position of 1,3-di-n-alkyl-imidazolium reduces the accessibility of the cation and therefore the electrostatic stabilization of the probe, resulting in an increase of tau1. A similar increase is observed upon extension of one of the n-alkyl chains from ethyl to n-decyl. Tetraalkylammonium ILs show an increased tau1 probably due to their more delocalized positive charge which cannot interact so favorably with the probe, in contrast to trialkylsulfonium ILs where the charge is more localized on the sulfur atom. The dependence of tau1 on the IL anion is much weaker, the only notable exception being [EtOSO3]-, where 12'CA experiences a less polar local environment than expected on the basis of extrapolated static dielectric constants. This is possibly due to the competition of the anion and probe for the cation interaction sites. Considerable electrostatic probe-cation interactions can be also introduced by addition of large amounts of LiClO4 salt to ethanol and diethyl ether. In this case, tau1 also strongly decreases, indicating an efficient coordination of Li+ cation(s) with the carbonyl oxygen at the negative end of the probe molecule. The S1/ICT --> S0 internal conversion of the 12'CA probe in ILs accelerates with increasing temperature, which can be characterized by an apparent activation energy of a few kJ mol-1, which is expected for energy-dependent nonradiative processes. SN - 1520-6106 UR - https://www.unboundmedicine.com/medline/citation/18275184/Exploring_12'_apo_beta_carotenoic_12'_acid_as_an_ultrafast_polarity_probe_for_ionic_liquids_ L2 - https://dx.doi.org/10.1021/jp710766z DB - PRIME DP - Unbound Medicine ER -
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