The S1 state dynamics of methoxy methylcinnamate (MMC) has been investigated under supersonic jet-cooled conditions. The vibrationally resolved S1-S0 absorption spectrum was recorded by laser induced fluorescence and mass-resolved resonant two-photon ionization spectroscopy and separated into conformers by UV-UV hole-burning (UV-UV HB) spectroscopy. The S1 lifetime measurements revealed different dynamics of para-methoxy methylcinnamate from ortho-methoxy methylcinnamate and meta-methoxy methylcinnamate (hereafter, abbreviated as p-, o-, and m-MMCs, respectively). The lifetimes of o-MMC and m-MMC are on the nanosecond time scale and exhibit little tendency of excess energy dependence. On the other hand, p-MMC decays much faster and its lifetime is conformer and excess energy dependent. In addition, the p-MMC-H2O complex was studied to explore the effect of hydration on the S1 state dynamics of p-MMC, and it was found that the hydration significantly accelerates the nonradiative decay. Quantum chemical calculation was employed to search the major decay route from S1(ππ(∗)) for three MMCs and p-MMC-H2O in terms of (i) trans → cis isomerization and (ii) internal conversion to the (1)nπ(∗) state. In o-MMC and m-MMC, the large energy barrier is created for the nonradiative decay along (i) the double-bond twisting coordinate (∼1000 cm(-1)) in S1 as well as (ii) the linear interpolating internal coordinate (∼1000 cm(-1)) from S1 to (1)nπ(∗) states. The calculation on p-MMC decay dynamics suggests that both (i) and (ii) are available due to small energy barrier, i.e., 160 cm(-1) by the double-bond twisting and 390 cm(-1) by the potential energy crossing. The hydration of p-MMC raises the energy barrier of the IC route to the S1/(1)nπ(∗) conical intersection, convincing that the direct isomerization is more likely to occur.
The nonradiative decay pathways of jet-cooled para-methoxy methylcinnamate (p-MMC) and para-methoxy ethylcinnamate (p-MEC) have been investigated by picosecond pump-probe and nanosecond UV-Deep UV pump-probe spectroscopy. The possible relaxation pathways were calculated by the (time-dependent) density functional theory. We found that p-MMC and p-MEC at low excess energy undergo multistep intersystem crossing (ISC) from the bright S (ππ*) state to the lowest triplet T (ππ*) state via two competing pathways through the T state in the time scale of 100 ps: (a) stepwise ISC followed after the internal conversion (IC) from S to the dark nπ* state; (b) direct ISC from the S to T states. These picosecond multistep ISCs result in the torsion of C═C double bond by ∼95° in the T state, whose measured adiabatic energy and lifetime are 16577 cm and ∼20 ns, respectively, for p-MMC. These results suggest that the ISC processes play an indispensable role in the photoprotecting sunscreens in natural plants.
An experimental and theoretical study has been carried out to elucidate the nonradiative decay (NRD) and trans(E) → cis(Z) isomerization from the S1 (1ππ*) state of structural isomers of hydroxy methylcinnamate (HMC); ortho-, meta- and para-HMC (o-, m- and p-HMC). A low temperature matrix-isolation Fourier Transform Infrared (FTIR) spectroscopic study revealed that all the HMCs are cis-isomerized upon UV irradiation. A variety of laser spectroscopic methods have been utilized for jet-cooled gas phase molecules to investigate the vibronic structure and lifetimes of the S1 state, and to detect the transient state appearing in the NRD process. In p-HMC, the zero-point level of the S1 state decays as quickly as 9 ps. A transient electronic state reported by Tan et al. (Faraday Discuss. 2013, 163, 321-340) was reinvestigated by nanosecond UV-tunable deep UV pump-probe spectroscopy and was assigned to the T1 state. For m- and o-HMC, the lifetime at the zero-point energy level of S1 is 10 ns and 6 ns, respectively, but it becomes substantially shorter at an excess energy higher than 1000 cm-1 and 600 cm-1, respectively, indicating the onset of NRD. Different from p-HMC, no transient state (T1) was observed in m- nor o-HMC. These experimental results are interpreted with the aid of TDDFT calculations by considering the excited-state reaction pathways and the radiative/nonradiative rate constants. It is concluded that in p-HMC, the trans → cis isomerization proceeds via a [trans-S1 → 1nπ* → T1 → cis-S0] scheme. On the other hand, in o- and m-HMC, the isomerization proceeds via a [trans-S1 → twisting along the C[double bond, length as m-dash]C double bond by 90° on S1 → cis-S0] scheme. The calculated barrier height along the twisting coordinate agrees well with the observed onset of the NRD channel for both o- and m-HMC.
The photoisomerization of para-methoxy methylcinnamate (p-MMC) has been studied by low-temperature matrix-isolation FTIR spectroscopy. In particular, the difference spectrum of the mid-IR frequency region (1100-1800 cm(-1)) allows us to distinguish the structural change before and after ultraviolet (UV) light irradiation at ≥300 nm and to convince that the cis-isomer is produced from the trans-isomer by comparing with the calculated IR spectra. Additionally, a reversible isomerization of p-MMC is demonstrated upon a sequential irradiation with different wavelengths of UV light. These findings provide a new insight into the electronic excited-state dynamics of p-MMC.
Against the backdrop of increased needs for longer operating life of turbine oils, there is a tendency to use amine
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