Structural, Electric and Dynamic Properties of (Pyrrolidinium)3[Bi2I9] and (Pyrrolidinium)3[Sb2I9]: New Lead-Free, Organic–Inorganic Hybrids with Narrow Band Gaps
Abstract
:1. Introduction
2. Results and Discussion
2.1. Thermal Properties of 1 and 2
2.2. Crystal Structure of Phase I
2.3. Low-Temperature Phases in 1
2.4. Electronic Properties
2.5. Dielectric Response
2.6. Cations Dynamics in 1 from Proton Magnetic Resonance (1H NMR)
- (i).
- Small-angle rotations of the pentagonal ring;
- (ii).
- Changes of the pyrrolidinium ring conformation (twisted/envelope conformation);
- (iii).
- Rotation about the pseudo-C5 axis perpendicular to the pyrrolidine ring;
- (iv).
- Isotropic rotation and possibly cationic self-diffusion/rotational diffusion at the highest temperatures.
3. Experimental Section
3.1. Synthesis
3.2. Single-Crystal X-ray Diffraction
3.3. Synchrotron Powder Diffraction
3.4. Optical Measurements
3.5. Thermal Analysis
3.6. Electrical Measurements
3.7. NMR
3.8. Calculation Details
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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(PYR)3[Bi2I9] [24] | (PYR)3[Sb2I9] [24] | (IM)3[Bi2I9] [19] | (IM)3[Sb2I9] [19] | 1 (This Work) | 2 (This Work) | |
---|---|---|---|---|---|---|
Average bond length (Å) | 3.105 | 3.061 | 3.101 | 3.065 | 3.095 | 3.045 |
Polyhedral volume (Å3) | 39.51 | 37.891 | 39.36 | 38.05 | 39.17 | 37.30 |
Distortion index (bond length) * | 0.042 | 0.049 | 0.049 | 0.057 | 0.047 | 0.060 |
Bond angle variance (deg.2) | 23.98 | 21.82 | 22.85 | 19.38 | 25.08 | 20.79 |
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Rowińska, M.; Piecha-Bisiorek, A.; Medycki, W.; Durlak, P.; Jakubas, R.; Gagor, A. Structural, Electric and Dynamic Properties of (Pyrrolidinium)3[Bi2I9] and (Pyrrolidinium)3[Sb2I9]: New Lead-Free, Organic–Inorganic Hybrids with Narrow Band Gaps. Molecules 2023, 28, 3894. https://doi.org/10.3390/molecules28093894
Rowińska M, Piecha-Bisiorek A, Medycki W, Durlak P, Jakubas R, Gagor A. Structural, Electric and Dynamic Properties of (Pyrrolidinium)3[Bi2I9] and (Pyrrolidinium)3[Sb2I9]: New Lead-Free, Organic–Inorganic Hybrids with Narrow Band Gaps. Molecules. 2023; 28(9):3894. https://doi.org/10.3390/molecules28093894
Chicago/Turabian StyleRowińska, Magdalena, Anna Piecha-Bisiorek, Wojciech Medycki, Piotr Durlak, Ryszard Jakubas, and Anna Gagor. 2023. "Structural, Electric and Dynamic Properties of (Pyrrolidinium)3[Bi2I9] and (Pyrrolidinium)3[Sb2I9]: New Lead-Free, Organic–Inorganic Hybrids with Narrow Band Gaps" Molecules 28, no. 9: 3894. https://doi.org/10.3390/molecules28093894