Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts
Abstract
:1. Introduction
2. Results and Discussion
2.1. The Effect of Methoxy Group Presence on the Ground-State Energy Landscape and the UV Absorption Spectrum
2.2. TT Formation, Single-vs. Two-Photon Mechanism
2.3. Photophysical Properties of TC-OCH3 in the Singlet Excited State
2.4. Theoretical Modelling of TC→TT Photoisomerization Mechanism
2.5. Role of the Methoxy Group
3. Materials and Methods
3.1. Materials
3.2. Transient UV-Vis Absorption Spectra Over Seconds
3.3. Transient UV-Vis Absorption Over Picoseconds
3.4. Computational Details
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Compound | Solvent | S0(TC) λabsmax | τS0, s | S1(TC) λabsmax | τS1, ps |
---|---|---|---|---|---|
TC-OCH3 | cyclohexane | 437 nm | 11.7 1 | 525 nm 3 | 0.47 2 |
acetonitrile | 447 nm | 17.0 1 | 545 nm | 0.27 2 | |
TC-H | cyclohexane | 427 nm | 9.3 1 | 520 nm 3 | 0.87 2 |
acetonitrile | 430 nm | 8.6 1 | 513 nm | 0.31 2 |
S0- or S1-State Form | R1 C3−O4 [Å] | θ1 C13−C14=C1−C2 [°] | θ2 C1−C2=C3−C15 [°] | σ [°] | τ [°] | R2 C13−O4 [Å] | RD C1−C14 [Å] | RS C1−C2 [Å] | RE C2−C3 [Å] | Ea [eV] |
---|---|---|---|---|---|---|---|---|---|---|
H-derivative | ||||||||||
S0 TC | 4.165 | 2.5 | −9.5 | 173.5 | 160.3 | 1.239 | 1.386 | 1.437 | 1.384 | 0.59 |
S1 TC | 3.921 | 22.5 | −18.7 | −174.8 | 174.2 | 1.399 | 1.478 | 1.371 | 1.440 | 2.14 |
S1 TW | 4.433 | 84.7 | −14.9 | −170.0 | 180.0 | 1.266 | 1.474 | 1.366 | 1.445 | 1.95 |
S1 BP | 4.243 | 59.2 | −68.5 | −176.5 | 176.6 | 1.266 | 1.482 | 1.344 | 1.492 | 2.00 |
OCH3-derivative | ||||||||||
S0 TC | 4.086 | 1.8 | −11.7 | 173.6 | 153.3 | 1.239 | 1.389 | 1.439 | 1.383 | 0.58 |
S1 TC | 3.818 | 25.5 | −27.0 | −174.9 | 172.8 | 1.390 | 1.483 | 1.364 | 1.450 | 2.15 |
S1 BP | 4.170 | 58.3 | −69.1 | −177.8 | 178.7 | 1.263 | 1.483 | 1.342 | 1.492 | 1.93 |
S1 TW | 4.308 | 82.6 | −13.7 | −177.2 | 177.3 | 1.260 | 1.476 | 1.366 | 1.439 | 1.94 |
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Brazevic, S.; Nizinski, S.; Sliwa, M.; Abe, J.; Rode, M.F.; Burdzinski, G. Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts. Int. J. Mol. Sci. 2020, 21, 7825. https://doi.org/10.3390/ijms21217825
Brazevic S, Nizinski S, Sliwa M, Abe J, Rode MF, Burdzinski G. Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts. International Journal of Molecular Sciences. 2020; 21(21):7825. https://doi.org/10.3390/ijms21217825
Chicago/Turabian StyleBrazevic, Sabina, Stanisław Nizinski, Michel Sliwa, Jiro Abe, Michał F. Rode, and Gotard Burdzinski. 2020. "Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts" International Journal of Molecular Sciences 21, no. 21: 7825. https://doi.org/10.3390/ijms21217825