New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis
2.2. Crystal Structure
2.2.1. Crystal Structure of the Salts κ-(BDH-TTP)4ReF6 (1) and κ-(BDH-TTP)4ReF6∙4.8H2O (2)
2.2.2. Crystal Structure of the Pseudo-κ″-(BDH-TTP)3(ReO4)2 (3) Salt
2.3. Electronic Structure of the BDH-TTP Salts
2.3.1. Electronic Structure of κ-(BDH-TTP)4ReF6 (1) and κ-(BDH-TTP)4ReF6∙4.8H2O (2)
2.3.2. Electronic Structure of the Pseudo-κ″-(BDH-TTP)3(ReO4)2 (3) Salt
2.4. Conductivity and Magnetic Properties
2.4.1. Conducting Properties of the κ-(BDH-TTP)4ReF6 (1) and κ-(BDH-TTP)4ReF6∙4.8H2O (2) Crystals
2.4.2. Conductivity of the Pseudo-κ″-(BDH-TTP)3(ReO4)2 (3) Crystals
2.4.3. ac- Magnetic Properties of the κ-(BDH-TTP)4[ReF6] Salt (1)
3. Materials and Methods
3.1. Synthesis of the Salts
3.1.1. Synthesis of the Crystals κ-(BDH-TTP)4ReF6 (1)
3.1.2. Synthesis of the Crystals κ-(BDH-TTP)4ReF6∙4.8H2O (2) and Pseudo-κ″-(BDH-TTP)3(ReO4)2 (3)
3.2. Electron-Probe X-ray Microanalysis
3.3. Single Crystal X-ray Analysis
3.4. Band Structure Analysis
3.5. Conducting Properties
3.6. Magnetic Properties
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Short Contact | Contact Length, Å | Symmetry Operation for the 1st Atom in Contact |
---|---|---|
S1…S2 | 3.584 | x, y, z |
S3…S1 | 3.531 | x, y, z |
S8…S3 | 3.549 | x, y, z |
S7…S5 | 3.516 | x, y, z |
S8…C5 | 3.434 | x, y, z |
S4…H10A | 2.977 | x, y, z |
S6…H10A | 2.942 | x, y, z |
S5…H9A | 2.858 | x, y, z |
C6…H9A | 2.822 | x, y, z |
Short Contact | Contact Length, Å | Symmetry Operation for the 1st Atom in Contact |
---|---|---|
S3…S1 | 3.569 | x, y, z |
S2…S5 | 3.581 | x, y, z |
S4…S6 | 3.537 | x, y, z |
S4…S1 | 3.531 | x, y, z |
S3…S6 | 3.593 | x, y, z |
S5…S8 | 3.490 | x, y, z |
C5…S6 | 3.416 | x, y, z |
C7H…S2 | 2.057 | x, y, z |
C7H…S7 | 2.878 | x, y, z |
S8…H8B | 2.957 | x, y, z |
C6…H8B | 2.782 | x, y, z |
Short Cotact | Length, Å | Sym. Operation for the 1st Atom | Short Contact | Length, Å | Sym. Operation for the 1st Atom |
---|---|---|---|---|---|
O3…S10 | 3.045 | x, y, z | S12… 3 | 3.498 | x, y, z |
O4…S5 | 3.045 | x, y, z | S12…S2 | 3.260 | x, y, z |
O1…C5 | 3.126 | x, y, z | S10…S4 | 3.579 | x, y, z |
O3…C14 | 3.160 | x, y, z | C15…S3 | 3.466 | x, y, z |
O3…C6 | 3.204 | x, y, z | S9…S6 | 3.482 | x, y, z |
O4…C10 | 3.160 | x, y, z | S9…C7 | 3.296 | x, y, z |
O3…C6 | 3.204 | x, y, z | S6…S2 | 3.423 | x, y, z |
O2…C6 | 3.059 | x, y, z | S11…S7 | 3.244 | x, y, z |
O2…H6A | 2.246 | x, y, z | S11…S6 | 3.531 | x, y, z |
O1…H6A | 2.707 | x, y, z | C15…S7 | 3.383 | x, y, z |
O4…H14B | 2.533 | x, y, z | S9…S8 | 3.457 | x, y, z |
O2…H13A | 2.496 | x, y, z | S3…S7 | 3.466 | x, y, z |
O1…H5B | 2.559 | x, y, z | S10…H6B | 2.943 | −1 + x, 1 + y, z |
O1…H9A | 2.612 | x, y, z | S4…H6B | 2.873 | x, y, z |
C=C Bond in the Dimer Radical Cation | Length of C=C Bond, Å | C=C Bond in the Single Radical Cation | Length of C=C Bond, Å |
---|---|---|---|
central C1=C2 | 1.374 | central C15=C15 | 1.362 |
terminal C3=C4 | 1.358 | terminal C11=C12 | 1.345 |
terminal C7=C8 | 1.365 | terminal C11=C12 | 1.345 |
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Kushch, N.D.; Shilov, G.V.; Buravov, L.I.; Yagubskii, E.B.; Zverev, V.N.; Canadell, E.; Yamada, J.-i. New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion. Magnetochemistry 2021, 7, 54. https://doi.org/10.3390/magnetochemistry7040054
Kushch ND, Shilov GV, Buravov LI, Yagubskii EB, Zverev VN, Canadell E, Yamada J-i. New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion. Magnetochemistry. 2021; 7(4):54. https://doi.org/10.3390/magnetochemistry7040054
Chicago/Turabian StyleKushch, Nataliya D., Gennady V. Shilov, Lev I. Buravov, Eduard B. Yagubskii, Vladimir N. Zverev, Enric Canadell, and Jun-ichi Yamada. 2021. "New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion" Magnetochemistry 7, no. 4: 54. https://doi.org/10.3390/magnetochemistry7040054
APA StyleKushch, N. D., Shilov, G. V., Buravov, L. I., Yagubskii, E. B., Zverev, V. N., Canadell, E., & Yamada, J. -i. (2021). New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion. Magnetochemistry, 7(4), 54. https://doi.org/10.3390/magnetochemistry7040054