Paramagnetic ionic plastic crystals containing the octamethylferrocenium cation: counteranion dependence of phase transitions and crystal structures
In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C Me...
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| Published in | Physical chemistry chemical physics : PCCP Vol. 20; no. 5; pp. 3019 - 3028 |
|---|---|
| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
07.02.2018
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| Subjects | |
| Online Access | Get full text |
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| Abstract | In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C
Me
H)
]X ([1]X; X
= B(CN)
, C(CN)
, N(CN)
, FSA (= (SO
F)
N
), FeCl
, GaCl
and CPFSA (= CF
(SO
CF
)
N
)) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [1][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature (T
= 298-386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [1][CPFSA]. [1][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [1][N(CN)
] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [1][GaCl
] and [1][FeCl
] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures. |
|---|---|
| AbstractList | In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C5Me4H)2]X ([1]X; X- = B(CN)4-, C(CN)3-, N(CN)2-, FSA (= (SO2F)2N-), FeCl4-, GaCl4- and CPFSA (= CF2(SO2CF2)2N-)) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [1][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature (TC = 298-386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [1][CPFSA]. [1][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [1][N(CN)2] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [1][GaCl4] and [1][FeCl4] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures. In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C Me H) ]X ([1]X; X = B(CN) , C(CN) , N(CN) , FSA (= (SO F) N ), FeCl , GaCl and CPFSA (= CF (SO CF ) N )) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [1][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature (T = 298-386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [1][CPFSA]. [1][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [1][N(CN) ] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [1][GaCl ] and [1][FeCl ] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures. In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C5Me4H)2]X ([1]X; X− = B(CN)4−, C(CN)3−, N(CN)2−, FSA (= (SO2F)2N−), FeCl4−, GaCl4− and CPFSA (= CF2(SO2CF2)2N−)) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [1][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature (TC = 298–386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [1][CPFSA]. [1][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [1][N(CN)2] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [1][GaCl4] and [1][FeCl4] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures. In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C 5 Me 4 H) 2 ]X ([ 1 ]X; X − = B(CN) 4 − , C(CN) 3 − , N(CN) 2 − , FSA (= (SO 2 F) 2 N − ), FeCl 4 − , GaCl 4 − and CPFSA (= CF 2 (SO 2 CF 2 ) 2 N − )) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [ 1 ][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature ( T C = 298–386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [ 1 ][CPFSA]. [ 1 ][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [ 1 ][N(CN) 2 ] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [ 1 ][GaCl 4 ] and [ 1 ][FeCl 4 ] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures. |
| Author | Takahashi, Kazuyuki Ohta, Hitoshi Tominaga, Takumi Sakurai, Takahiro Mochida, Tomoyuki Ishida, Mai |
| Author_xml | – sequence: 1 givenname: Tomoyuki orcidid: 0000-0002-3446-2145 surname: Mochida fullname: Mochida, Tomoyuki email: tmochida@platinum.kobe-u.ac.jp organization: Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan. tmochida@platinum.kobe-u.ac.jp – sequence: 2 givenname: Mai surname: Ishida fullname: Ishida, Mai email: tmochida@platinum.kobe-u.ac.jp organization: Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan. tmochida@platinum.kobe-u.ac.jp – sequence: 3 givenname: Takumi surname: Tominaga fullname: Tominaga, Takumi email: tmochida@platinum.kobe-u.ac.jp organization: Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan. tmochida@platinum.kobe-u.ac.jp – sequence: 4 givenname: Kazuyuki orcidid: 0000-0002-1776-4416 surname: Takahashi fullname: Takahashi, Kazuyuki email: tmochida@platinum.kobe-u.ac.jp organization: Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Nada, Hyogo 657-8501, Japan. tmochida@platinum.kobe-u.ac.jp – sequence: 5 givenname: Takahiro surname: Sakurai fullname: Sakurai, Takahiro organization: Research Facility Center for Science and Technology, Kobe University, Kobe, Hyogo 657-8501, Japan – sequence: 6 givenname: Hitoshi surname: Ohta fullname: Ohta, Hitoshi organization: Department of Physics, Graduate School of Science, Kobe University, Kobe, Hyogo 657-8501, Japan and Molecular Photoscience Research Center, Kobe University, Kobe, Hyogo 657-8501, Japan |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/28561120$$D View this record in MEDLINE/PubMed |
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| Snippet | In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase... |
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| Title | Paramagnetic ionic plastic crystals containing the octamethylferrocenium cation: counteranion dependence of phase transitions and crystal structures |
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