Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3]
Abstract
:1. Introduction
2. Results and Discussion
2.1. Basic Characterization and Deeper Insight into the Crystal Structure of TMACdN3
2.2. Thermal Characterization (DSC) and Barocaloric Parameters
2.3. Raman Studies
2.3.1. Room Temperature Raman Spectrum
2.3.2. Raman Spectra as a Function of Temperature
3. Materials and Methods
3.1. Synthesis
3.2. Powder X-Ray Diffraction
3.3. Hirshfeld Surface Analysis
3.4. Differential Scanning Calorimetry—DSC
3.5. Temperature-Dependent Raman Spectroscopy
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compound [(CH3)4N][Cd(N3)3] is available from the authors. |
Parameters | Heating | Cooling | ||
---|---|---|---|---|
Tα→β/Tβ→γ | Tγ→δ | Tα←β/Tβ←γ | Tγ←δ | |
Tt (K) | 270.4/277.6 | 322.0 | 263.9/269.6 | 319.5 |
|∆Hib| (J·g−1) | 8.40 | 8.46 | 9.22 | 9.14 |
|∆Sib| (J·Kg−1K−1) | 29.83 | 25.97 | 32.26 | 28.51 |
N | 2.9 | 2.5 | 3.2 | 2.8 |
δTt/δP (K kbar−1) | 12.39 | −6.52 | - | - |
C2/c (80 K) | P21/m (298 K) | Pm-3m (373 K) | Assignment |
---|---|---|---|
3044 m | νsCH3 | ||
3037 s | 3032 m | 3031m | νasCH3 νsCH3 |
2982 s | 2978 m | 2978 m | νsCH3 |
2972 m | 2969 sh | 2970 sh | νasCH3 νsCH3 |
2961 m/2949 s | 2953 m | 2954 | νsCH3 |
2917 vw | 2921 m | 2923 m | νasCH3 νsCH3 |
2821 vw | 2820 w | 2824 w | 2xδasCH3 |
2812 vw | 2813 w | 2814 vw | 2xνs(ν1)N3− |
1479 vw | 1481 vw | 1471 vw | δasCH3 δsCH3 |
1462 vw | 1453 w | 1451 w | δasCH3 δsCH3 |
1454 s/1438 s/1418 vw | 1440 vw | 1440 vw/ | combination |
1399 vw | combination | ||
1366 vs | 1367 s | νs(ν1)N3− | |
1360 vs/135 5m | 1359 vs | 1359 vs/ | νs(ν1)N3 |
1338 w | 1337 vw | 1337 w | |
1290 m | 1289 w | 1285 vw | ρCH3 |
1273 w | 1267 vw | ρCH3 | |
1217 w | 1218 vw | ρCH3 | |
1179 w | 1171 vw | 1174 | ρCH3 |
1170 w | ρCH3 | ||
1045 w | 1047 vw | 1043 w/1047 vw | ρCH3 |
958 m/952 m | 952 w | 950 w | νasNC4 |
762 m | 758 m | 759 m | νsNC4 |
755 m | 752 sh | 753 w-sh | |
730 vw | 741 vw | 741 vw | |
609 w | 609 w | ||
463 w/453 w | 458 vw | 458 vw | δNC4 |
378 w/369 w | 370 vw | 373 vw | δNC4 τCH3 |
302 vw-sh | 291 vw-sh | ||
275 s | 274 m | 261 w | τCH3 T′(Cd) |
223 vs | 220 m | 217 w | LN3− |
208 s | 186 w | 189 w | LN3− |
168 s | 161 w | 159 w | T’N3− T′(Cd) |
154 m | 149 m | 147 m | |
134 w | 137 w | 134 w | |
121 m | 121 w | 117 m | T’(TMA) |
116 s/115 m | T’(TMA) | ||
98 w/90 m | 101 w/92 vw | 101 w/91 w |
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da Silva, R.X.; de Araujo Paschoal, C.W.; Costa dos Santos, C.; García-Fernández, A.; Salgado-Beceiro, J.; Señarís-Rodríguez, M.A.; Sanchez-Andujar, M.; Nonato Almeida de Abreu Silva, A. Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3]. Molecules 2020, 25, 4754. https://doi.org/10.3390/molecules25204754
da Silva RX, de Araujo Paschoal CW, Costa dos Santos C, García-Fernández A, Salgado-Beceiro J, Señarís-Rodríguez MA, Sanchez-Andujar M, Nonato Almeida de Abreu Silva A. Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3]. Molecules. 2020; 25(20):4754. https://doi.org/10.3390/molecules25204754
Chicago/Turabian Styleda Silva, Rosivaldo Xavier, Carlos William de Araujo Paschoal, Clenilton Costa dos Santos, Alberto García-Fernández, Jorge Salgado-Beceiro, María Antonia Señarís-Rodríguez, Manuel Sanchez-Andujar, and Ariel Nonato Almeida de Abreu Silva. 2020. "Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3]" Molecules 25, no. 20: 4754. https://doi.org/10.3390/molecules25204754