A Norbornadiene-Based Molecular System for the Storage of Solar–Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex
Abstract
:1. Introduction
2. Results and Discussion
2.1. Acid Dissociation of HNBD1 and HQC1 and Solution Stability
2.2. Photochemical Properties
2.3. Back-Conversion of HQC1/QC1− to HNBD1/NBD1−
3. Materials and Methods
3.1. General
3.2. Synthesis of HNBD1 and HQC1
3.2.1. Synthesis of Diethyl Bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate (1)
3.2.2. Synthesis of 3-(ethoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-2-carboxylic acid (2)
3.2.3. Synthesis of Ethyl 3-(pentylcarbamoyl)bicyclo[2.2.1]hepta-2,5-diene-2-carboxylate (3)
3.2.4. Synthesis of 3-(pentylcarbamoyl)bicyclo[2.2.1]hepta-2,5-diene-2-carboxylic Acid (HNBD1)
3.2.5. Synthesis of 5-(pentylcarbamoyl)tetracyclo[3.2.0.02,7.04,6]heptane-1-carboxylic Acid (HQC1)
3.3. Physicochemical Properties of HNBD1/NBD1− and HQC1/QC1−
3.3.1. Spectrophotometric Measurements
3.3.2. Isothermal Titration Calorimetry (ITC)
3.3.3. Differential Scanning Calorimetry (DSC)
3.3.4. Nuclear Magnetic Resonance (NMR)
3.3.5. Photoisomerization Quantum Yield
3.3.6. Mass Spectrometry
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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HNBD1/NBD1− | |||
pKa a | λonset a (nm) | Φiso a (%) | ΔHstorage b (kJ∙mol−1) |
3.73(1) | 364 (pH 2); 343 (pH 11) | 71 | 65(2) |
HQC1/QC1− | |||
pKa a | t½c Thermal, 298 K | t½c Thermal, 371 K | t½c Cat. Co-TPPC, 298 K |
3.60(1) | 100% stable over 3 months | 587 h | 11 min |
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Castro, F.; Gancheff, J.S.; Ramos, J.C.; Seoane, G.; Bazzicalupi, C.; Bianchi, A.; Ridi, F.; Savastano, M. A Norbornadiene-Based Molecular System for the Storage of Solar–Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex. Molecules 2023, 28, 7270. https://doi.org/10.3390/molecules28217270
Castro F, Gancheff JS, Ramos JC, Seoane G, Bazzicalupi C, Bianchi A, Ridi F, Savastano M. A Norbornadiene-Based Molecular System for the Storage of Solar–Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex. Molecules. 2023; 28(21):7270. https://doi.org/10.3390/molecules28217270
Chicago/Turabian StyleCastro, Franco, Jorge S. Gancheff, Juan C. Ramos, Gustavo Seoane, Carla Bazzicalupi, Antonio Bianchi, Francesca Ridi, and Matteo Savastano. 2023. "A Norbornadiene-Based Molecular System for the Storage of Solar–Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex" Molecules 28, no. 21: 7270. https://doi.org/10.3390/molecules28217270