scholarly journals Spectroscopic Studies of a Phosphonium Ionic Liquid in Supercritical CO2

2020 ◽  
Vol 4 (2) ◽  
pp. 20
Author(s):  
Mark P. Heitz ◽  
Zackary C. Putney ◽  
Joel Campaign

Fluorescence spectroscopy was used to study a solution comprised of coumarin 153 (C153)+ trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P6,6,6,14]+ [Tf2N]−)+ supercritical CO2 (scCO2). We compare the spectroscopy of C153 in neat scCO2 to that of C153/scCO2 with the addition of ionic liquid (IL). Excitation and emission peak frequencies of C153 in scCO2 and in IL/scCO2 diverged at reduced densities (ρr = ρ/ρc) below the CO2 critical density. At low fluid density, spectral changes in the IL/scCO2 solutions showed evidence that C153 experiences a very different microenvironment—one that is unlike neat scCO2. The data show that the presence of IL clearly influences the C153 excitation and emission profiles. Excitation was broadened and red shifted by >2000 cm−1 and the presence of an additional low-energy emission component that was red shifted by ~3000 cm−1 was clearly visible and not observed in neat scCO2. The solution heterogeneity was controlled by changing the scCO2 density and at high fluid density, both the excitation and emission spectra were more similar to those in neat scCO2. Steady-state anisotropy also showed that at low fluid density, the C153 emission was significantly polarized. Aggregation of C153 has been reported in the literature and this led us to hypothesize the possibility that C153 dimer (aggregation) formation may be occurring in scCO2. Another possible explanation is that dye–IL aggregates may dissolve into the scCO2 phase due to C153 acting as a “co-solvent” for the IL. Time-resolved intensity decay measurements yielded only slightly non-exponential decays with accompanying time constants of ~3–4 ns that were significantly shorter than the 5–6 ns time constants in neat scCO2, which are suggestive of C153–IL interactions. However, these data did not conclusively support dimer formation. Pre-exponential factors of the time constants showed that almost all of the emission was due to monomeric C153.

Author(s):  
Maximilian Theiß ◽  
Merten Grupe ◽  
Tilman Lamparter ◽  
Maria Andrea Mroginski ◽  
Rolf Diller

AbstractDeactivation processes of photoexcited (λex = 580 nm) phycocyanobilin (PCB) in methanol were investigated by means of UV/Vis and mid-IR femtosecond (fs) transient absorption (TA) as well as static fluorescence spectroscopy, supported by density-functional-theory calculations of three relevant ground state conformers, PCBA, PCBB and PCBC, their relative electronic state energies and normal mode vibrational analysis. UV/Vis fs-TA reveals time constants of 2.0, 18 and 67 ps, describing decay of PCBB*, of PCBA* and thermal re-equilibration of PCBA, PCBB and PCBC, respectively, in line with the model by Dietzek et al. (Chem Phys Lett 515:163, 2011) and predecessors. Significant substantiation and extension of this model is achieved first via mid-IR fs-TA, i.e. identification of molecular structures and their dynamics, with time constants of 2.6, 21 and 40 ps, respectively. Second, transient IR continuum absorption (CA) is observed in the region above 1755 cm−1 (CA1) and between 1550 and 1450 cm−1 (CA2), indicative for the IR absorption of highly polarizable protons in hydrogen bonding networks (X–H…Y). This allows to characterize chromophore protonation/deprotonation processes, associated with the electronic and structural dynamics, on a molecular level. The PCB photocycle is suggested to be closed via a long living (> 1 ns), PCBC-like (i.e. deprotonated), fluorescent species.


2016 ◽  
Vol 20 (08n11) ◽  
pp. 1173-1181 ◽  
Author(s):  
Narra Vamsi Krishna ◽  
Puliparambil Thilakan Anusha ◽  
S. Venugopal Rao ◽  
L. Giribabu

Zinc phthalocyanine possessing triphenylamine at its peripheral position has been synthesized and its optical, emission, electrochemical and third-order nonlinear optical (NLO) properties were investigated. Soret band was broadened due to the presence of triphenylamine moiety. Electrochemical properties indicated that both oxidation and reduction processes were ring centered. Emission spectra were recorded in different solvents and the fluorescence yields obtained were in the range of 0.02–0.17 while the time-resolved fluorescence data revealed radiative lifetimes of typically few ns. Third-order NLO properties of this molecule have been examined using the Z-scan technique with picosecond (ps) and femtoseocnd (fs) pulses. Closed and open aperture Z-scan data were recorded with 2 ps/1 50 fs laser pulses at a wavelength of 800 nm and NLO coefficients were extracted from both the data. Our data clearly suggests the potential of this molecule for photonics applications.


2012 ◽  
Vol 8 (S287) ◽  
pp. 98-102
Author(s):  
Kazuhito Motogi ◽  
Kazuo Sorai ◽  
Kenta Fujisawa ◽  
Koichiro Sugiyama ◽  
Mareki Honma

AbstractThe water maser site associated with G353.273+0.641 is classified as a dominant blueshifted H2O maser, which shows an extremely wide velocity range (± 100 km s−1) with almost all flux concentrated in the highly blueshifted emission. The previous study has proposed that this peculiar H2O maser site is excited by a pole-on jet from high mass protostellar object. We report on the monitoring of 22-GHz H2O maser emission from G353.273+0.641 with the VLBI Exploration of Radio Astrometry (VERA) and the Tomakamai 11-m radio telescope. Our VLBI imaging has shown that all maser features are distributed within a very small area of 200 × 200 au2, in spite of the wide velocity range (> 100 km s−1). The light curve obtained by weekly single-dish monitoring shows notably intermittent variation. We have detected three maser flares during three years. Frequent VLBI monitoring has revealed that these flare activities have been accompanied by a significant change of the maser alignments. We have also detected synchronized linear acceleration (−5 km s−1yr−1) of two isolated velocity components, suggesting a lower-limit momentum rate of 10−3 M⊙ km s−1yr−1 for the maser acceleration. All our results support the previously proposed pole-on jet scenario, and finally, a radio jet itself has been detected in our follow-up ATCA observation. If highly intermittent maser flares directly reflect episodic jet-launchings, G353.273+0.641 and similar dominant blueshifted water maser sources can be suitable targets for a time-resolved study of high mass protostellar jet.


1968 ◽  
Vol 213 (3) ◽  
pp. 215-226 ◽  
Author(s):  
J. E. Persson ◽  
S. K. HÄndel ◽  
A. Englund ◽  
A. Dejke

1984 ◽  
Vol 25 (18) ◽  
pp. 1933-1936
Author(s):  
Shigeru Murata ◽  
Tadashi Sugawara ◽  
Nobuaki Nakashima ◽  
Keitaro Yoshihara ◽  
Hiizu Iwamura

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