ON/OFF Photostimulation of Isatin Bipyridyl Hydrazones: Photochemical and Spectral Study
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis
2.2. UV-Vis and Fluorescence Spectra of Studied Hydrazones
2.3. Photochemical and Thermal Reactivity of Hydrazones
2.4. Studied Hydrazones N-Anions Thermal Reactivity
TBAF Titration—UV-Vis Spectra
2.5. Titration with TBAF—NMR Spectra
2.6. Photochemical Reactivity of Studied Hydrazone N-anions
3. Materials and Methods
3.1. General Information
3.2. Synthesis
3.2.1. Synthesis of Hydrazones 1 and 2
3.2.2. Synthesis of Hydrazones 3 and 4
3.3. Spectroscopic Measurements
3.4. HPLC Chromatography
3.5. Quantum Chemical Calculations
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References and Notes
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Sample Availability: Samples of the compounds 1–4 are available from the authors. |
Compound | UV-Vis | Fluorescence | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
DMF | CHCl3 | DMF | CHCl3 | |||||||
λmax (nm) log(ε) (l mol cm−1) | λmax (nm) log(ε) (l mol cm−1) | λem/λexc (nm) | Stokes Shift (cm−1) | τ (ns) | ɸF | λem/λexc (nm) | Stokes Shift (cm−1) | τ (ns) | ɸF | |
1 | 383 4.40 | 391 4.22 | 557/383 | 8156 | τ1 = 0.13 (80.4%) τ2 = 7.69 (19.6%) χ2 = 0.97 | <0.01 | 521/390 | 6382 | τ1 = 0.17 (89.9%) τ2 = 5.54 (10.1%) χ2 = 0.92 | <0.01 |
2 | 382 4.38 | 386 4.38 | 464/383 | 4626 | τ1 = 0.12 (80%) τ2 = 8.17 (20%) χ2 = 1.16 | <0.01 | 561/390 | 8081 | τ1 = 0.26 (74%) τ2 = 7.82 (26%) χ2 = 1.3 | <0.01 |
3 | 414 4.40 | 422 4.37 | 490/412 | 3746 | τ1 = 4.21 (93.6%) τ2 = 9.51 (6.4%) χ2 = 1.33 | 0.04 | 483/420 | 2993 | τ1 = 3.46 (29.8%); τ2 = 6.77 (70.2%) χ2 = 1.33 | 0.02 |
4 * | 411 4.08 | 353 3.97 418 4.13 | 507/412 ** 640/412 | 8060 ** 8706 | τ1 = 0.11 (11.8%) τ2 = 4.99 (72.2%) τ3 = 19.5 (16.0%) χ2 = 1.23 | <0.01 | 480/420 | 3090 | τ1 = 0.41 (4.5%) τ2 = 3.41 (95.5%) χ2 = 1.29 | <0.01 |
Compound | DMF/25 °C | CHCl3/25 °C | DMF/80 °C | |
---|---|---|---|---|
[Z]/[E] | [Z]/[E] | 105 × kE-Z [s−1] | 104 × kt [s−1] | |
1 | 17.5 | 2.9 | - | 9.2 |
2 | 11.1 | 1.2 | - | 12.0 |
3 | 1.1 | 0.8 | 7.8 | - |
4 | 2.0 | 0.8 | 2002.0 | - |
Compound | pKa1 | pKa2 | k1E-Z × 105 (s−1) | k1Z-E × 105 (s−1) |
---|---|---|---|---|
1 | 8.7 | 9.3 | 4.98 | 17.5 |
2 | - | 9.6 | 23.49 | 320 |
3 | 8.8 | 9.4 | 7.09 | 78 |
4 | 7.8 | 8.6 | 157.03 | 186 |
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Šandrik, R.; Tisovský, P.; Csicsai, K.; Donovalová, J.; Gáplovský, M.; Sokolík, R.; Filo, J.; Gáplovský, A. ON/OFF Photostimulation of Isatin Bipyridyl Hydrazones: Photochemical and Spectral Study. Molecules 2019, 24, 2668. https://doi.org/10.3390/molecules24142668
Šandrik R, Tisovský P, Csicsai K, Donovalová J, Gáplovský M, Sokolík R, Filo J, Gáplovský A. ON/OFF Photostimulation of Isatin Bipyridyl Hydrazones: Photochemical and Spectral Study. Molecules. 2019; 24(14):2668. https://doi.org/10.3390/molecules24142668
Chicago/Turabian StyleŠandrik, Róbert, Pavol Tisovský, Klaudia Csicsai, Jana Donovalová, Martin Gáplovský, Róbert Sokolík, Juraj Filo, and Anton Gáplovský. 2019. "ON/OFF Photostimulation of Isatin Bipyridyl Hydrazones: Photochemical and Spectral Study" Molecules 24, no. 14: 2668. https://doi.org/10.3390/molecules24142668