7-Dialkylaminocoumarin Oximates: Small Molecule Fluorescent “Turn-On” Chemosensors for Low-Level Water Content in Aprotic Organic Solvents
Abstract
:1. Introduction
2. Results and Discussion
2.1. Spectral Characteristics
2.2. Water Sensing
3. Materials and Methods
3.1. General Information
3.2. Synthesis
3.2.1. Synthesis of Coumarin Oximes 1 and 2
3.2.2. Product Characterization
3.3. Spectroscopic Measurements
3.4. Titration Experiments
3.4.1. Materials
3.4.2. General Method
3.4.3. Detection and Quantification Limits
3.5. Quantum-Chemical Calculations
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are available from the authors. |
Compd. | λA (nm) | Log εA | λF (nm) | ΦF | τ (ns) | χ2 |
---|---|---|---|---|---|---|
MeCN | ||||||
1 | 413 | 4.27 | 487 | 0.80 | τ1 = 1.6 (10%) | 1.111 |
τ2 = 3.5 (90%) | ||||||
2 | 438 | 4.28 | 504 | 0.87 | τ1 = 0.5 (2%) | 1.050 |
τ2 = 3.6 (98%) | ||||||
DMF | ||||||
1 | 414 | 4.52 | 491 | 0.87 | τ1 = 0.3 (3%) | 1.171 |
τ2 = 3.3 (97%) | ||||||
2 | 442 | 4.55 | 507 | 0.95 | τ1 = 0.5 (2%) | 1.196 |
τ2 = 3.6 (98%) | ||||||
DMSO | ||||||
1 | 419 | 4.54 | 497 | 0.88 | τ1 = 1.5 (8%) | 1.007 |
τ2 = 3.3 (92%) | ||||||
2 | 442 | 4.51 | 512 | 1.00 | τ = 3.6 (100%) | 1.130 |
7-Dimethylaminocoumarin Oximate 1 | ||||
---|---|---|---|---|
Excited State | Orbital Contributions | Energy | Oscillator Strength | |
[eV] | [nm] | |||
T1 | HOMO → LUMO (2%) | 1.31 | 946 | 0.0000 |
HOMO → LUMO+1 (10%) | ||||
HOMO → LUMO+2 (77%) | ||||
T2 | HOMO−1 → LUMO+1 (7%) | 1.36 | 914 | 0.0000 |
HOMO−1 → LUMO+2 (54%) | ||||
S1 | HOMO−1 → LUMO+1 (8%) | 1.80 | 686 | 0.0003 |
HOMO−1 → LUMO+2 (61%) | ||||
S2 | HOMO → LUMO (12%) | 3.06 | 406 | 0.5360 |
HOMO → LUMO+1 (10%) | ||||
HOMO → LUMO+2 (73%) |
LOD (3σ/S) | LOQ (10σ/S) | |||
---|---|---|---|---|
wt % | v/v % | wt % | v/v % | |
MeCN | ||||
1/F− | 0.0014 | 0.0012 | 0.0048 | 0.0039 |
2/F− | 0.0175 * | 0.0137 * | 0.0583 * | 0.0457 * |
DMF | ||||
1/F− | 0.0059 | 0.0046 | 0.0196 | 0.0153 |
2/F− | 0.0046 | 0.0044 | 0.0154 | 0.0146 |
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Cigáň, M.; Horváth, M.; Filo, J.; Jakusová, K.; Donovalová, J.; Garaj, V.; Gáplovský, A. 7-Dialkylaminocoumarin Oximates: Small Molecule Fluorescent “Turn-On” Chemosensors for Low-Level Water Content in Aprotic Organic Solvents. Molecules 2017, 22, 1340. https://doi.org/10.3390/molecules22081340
Cigáň M, Horváth M, Filo J, Jakusová K, Donovalová J, Garaj V, Gáplovský A. 7-Dialkylaminocoumarin Oximates: Small Molecule Fluorescent “Turn-On” Chemosensors for Low-Level Water Content in Aprotic Organic Solvents. Molecules. 2017; 22(8):1340. https://doi.org/10.3390/molecules22081340
Chicago/Turabian StyleCigáň, Marek, Miroslav Horváth, Juraj Filo, Klaudia Jakusová, Jana Donovalová, Vladimír Garaj, and Anton Gáplovský. 2017. "7-Dialkylaminocoumarin Oximates: Small Molecule Fluorescent “Turn-On” Chemosensors for Low-Level Water Content in Aprotic Organic Solvents" Molecules 22, no. 8: 1340. https://doi.org/10.3390/molecules22081340