Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family
New organic (super)conductors of the β″-(BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]G family, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene; M is Fe; A is the monovalent c...
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MDPI AG
2021-06-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/7/6/83 |
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| author | Tatiana G. Prokhorova Eduard B. Yagubskii Andrey A. Bardin Vladimir N. Zverev Gennadiy V. Shilov Lev I. Buravov |
| author_facet | Tatiana G. Prokhorova Eduard B. Yagubskii Andrey A. Bardin Vladimir N. Zverev Gennadiy V. Shilov Lev I. Buravov |
| author_sort | Tatiana G. Prokhorova |
| collection | DOAJ |
| description | New organic (super)conductors of the β″-(BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]G family, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene; M is Fe; A is the monovalent cation NH<sub>4</sub><sup>+</sup>; G is 2-fluoropyridine (2-FPy) (1); 2,3-difluoropyridine (2,3-DFPy) (2); 2-chloro-3-fluoropyridine (2-Cl-3-FPy) (3); 2,6-dichloropyridine (2,6-DClPy) (4); 2,6-difluoropyridine (2,6-DFPy) (5), have been prepared and their crystal structure and transport properties were studied. All crystals have a layered structure in which the conducting layers of BEDT-TTF radical cations alternate with paramagnetic supramolecular anionic layers {A<sup>+</sup>[Fe<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sup>3−</sup>G<sup>0</sup>}<sup>2−</sup>. Crystals <b>1</b> undergo a structural phase transition from the monoclinic (<i>C</i>2/<i>c</i>) to the triclinic (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mn>1</mn><mo stretchy="true">¯</mo></mover></mrow></semantics></math></inline-formula>) symmetry in the range 100–150 K, whereas crystals <b>2</b>–<b>5</b> have a monoclinic symmetry in the entire range of the X-ray experiment (100–300 K). The alternating current (ac) conductivity of salts <b>1</b>–<b>4</b> exhibits metallic behavior down to 1.4 K, whereas the salt <b>5</b> demonstrates the onset of a superconducting transition at 3.1 K. The structures and conducting properties of <b>1</b>–<b>5</b> are compared with those of the known monoclinic phases of the family containing different monohalopyridines as “guest” solvent molecules G. |
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| last_indexed | 2024-03-10T10:42:34Z |
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| spelling | doaj.art-062d1591a0db4c36bfa785309dc596d62023-11-21T22:50:45ZengMDPI AGMagnetochemistry2312-74812021-06-01768310.3390/magnetochemistry7060083Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G FamilyTatiana G. Prokhorova0Eduard B. Yagubskii1Andrey A. Bardin2Vladimir N. Zverev3Gennadiy V. Shilov4Lev I. Buravov5Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, RussiaInstitute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, RussiaInstitute of Microelectronics Technology and High Purity Materials, Russian Academy of Sciences, 142432 Chernogolovka, RussiaInstitute of Solid State Physics, Russian Academy of Sciences, 142432 Chernogolovka, RussiaInstitute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, RussiaInstitute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, RussiaNew organic (super)conductors of the β″-(BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]G family, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene; M is Fe; A is the monovalent cation NH<sub>4</sub><sup>+</sup>; G is 2-fluoropyridine (2-FPy) (1); 2,3-difluoropyridine (2,3-DFPy) (2); 2-chloro-3-fluoropyridine (2-Cl-3-FPy) (3); 2,6-dichloropyridine (2,6-DClPy) (4); 2,6-difluoropyridine (2,6-DFPy) (5), have been prepared and their crystal structure and transport properties were studied. All crystals have a layered structure in which the conducting layers of BEDT-TTF radical cations alternate with paramagnetic supramolecular anionic layers {A<sup>+</sup>[Fe<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sup>3−</sup>G<sup>0</sup>}<sup>2−</sup>. Crystals <b>1</b> undergo a structural phase transition from the monoclinic (<i>C</i>2/<i>c</i>) to the triclinic (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mn>1</mn><mo stretchy="true">¯</mo></mover></mrow></semantics></math></inline-formula>) symmetry in the range 100–150 K, whereas crystals <b>2</b>–<b>5</b> have a monoclinic symmetry in the entire range of the X-ray experiment (100–300 K). The alternating current (ac) conductivity of salts <b>1</b>–<b>4</b> exhibits metallic behavior down to 1.4 K, whereas the salt <b>5</b> demonstrates the onset of a superconducting transition at 3.1 K. The structures and conducting properties of <b>1</b>–<b>5</b> are compared with those of the known monoclinic phases of the family containing different monohalopyridines as “guest” solvent molecules G.https://www.mdpi.com/2312-7481/7/6/83BEDT-TTFmolecular paramagnetic (super)conductorsradical cation saltstris(oxalato)metallate anions |
| spellingShingle | Tatiana G. Prokhorova Eduard B. Yagubskii Andrey A. Bardin Vladimir N. Zverev Gennadiy V. Shilov Lev I. Buravov Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family Magnetochemistry BEDT-TTF molecular paramagnetic (super)conductors radical cation salts tris(oxalato)metallate anions |
| title | Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family |
| title_full | Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family |
| title_fullStr | Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family |
| title_full_unstemmed | Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family |
| title_short | Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)<sub>4</sub>A<sup>+</sup>[M<sup>3+</sup>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·G Family |
| title_sort | influence of the size and shape of halopyridines guest molecules g on the crystal structure and conducting properties of molecular super conductors of bedt ttf sub 4 sub a sup sup m sup 3 sup c sub 2 sub o sub 4 sub sub 3 sub ·g family |
| topic | BEDT-TTF molecular paramagnetic (super)conductors radical cation salts tris(oxalato)metallate anions |
| url | https://www.mdpi.com/2312-7481/7/6/83 |
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