Preparation and structures of biferrocenes with alicyclic substituents: Order–disorder of substituents in the crystal structures of cyclohexenylbiferrocene and its charge-transfer salt

Mochida, Tomoyuki; Kobayashi, Takashi; Akasaka, Takahiro

doi:10.1016/j.jorganchem.2013.05.041

Cited by 7 publications

(5 citation statements)

References 30 publications

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“…The cations in the 1:1 salts exhibited valence-trapped states, resulting from the local Fe···NC electrostatic interactions between the cation and anion. The dependence of the cation valence states in the biferrocenium salts of F n TCNQ ( n = 0–4) has been reported in this and in related studies . On the basis of these relationships, the preparation of salts whose valence state is controllable by external stimuli is currently under progress in our laboratories.…”

Section: Discussionsupporting

confidence: 60%

“…Recently, we have investigated the preparation and properties of biferrocenium salts with F n TCNQ ( n = 0, 1, 4; TCNQ = tetracyanoquinodimethane) and [M(mnt) 2 ] anions (mnt = maleonitriledithiolate; M = Ni, Co), which contain mixed-valence monocations . These salts exhibit intriguing physical properties such as magnetism, dielectric properties, electrical conduction, and phase transition phenomena. , Several Mössbauer spectroscopy studies on biferrocene–TCNQ salts have been reported in the literature .…”

Section: Introductionmentioning

confidence: 99%

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Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Mochida

Funasako

Nagabuchi

et al. 2014

Crystal Growth & Design

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Charge-transfer salts of biferrocene derivatives bearing branched-alkyl substituents [1′-R1-1‴-R2-1,1″-biferrocene; R1 = R2 = isopropylthio (D1), isopropyl (D2), isobutyl (D3), neopentyl (D4), and R1 = isobutyl and R2 = neopentyl (D5)] were prepared and crystallographically characterized. F2- and F4-tetracyanoquinodimethane (TCNQ) produced salts with D/A ratios of 1:3 ([D1][F2TCNQ]3, [D2][F2TCNQ]3), 1:2 ([D2][F4TCNQ]2, [D3][F4TCNQ]2), 2:3 ([D1]2[F4TCNQ]3), and 1:1 ([D2][F4TCNQ], [D4][F2TCNQ], [D4][F4TCNQ], [D5][F4TCNQ]). [Ni(mnt)2] produced a 1:1 salt [D3][Ni(mnt)2]. Although the biferrocenium salts reported to date contain only monocations, the cation valence in these salts decreases as the donor/acceptor ratio increases; the 1:3 and 1:2 salts contain biferrocenium dications, the 1:1 salts contain mixed-valence biferrocenium monocations, and the intermediate 2:3 salt contains both the dication and monocation. The packing structures of the salts differ significantly despite being composed of donors and acceptors with very similar shapes. The salts are paramagnetic, and their magnetic susceptibility values are consistent with the valence state of the cations. The cations in the 1:1 salts exhibited valence-trapped states because of the local electrostatic interactions between the cation and anion.

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Section: Discussionsupporting

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Mochida

Funasako

Nagabuchi

et al. 2014

Crystal Growth & Design

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“…Indeed, they were found to dominate the charge distributions on the acceptors in the F 2 TCNQ and TCNQ salts 5 – 9 . Fe···NC arrangements of this particular type have also been observed in the alkylferrocenium and biferrocenium salts with [Ni(mnt) 2 ], , where they affected the valence states of these salts.…”

Section: Results and Discussionmentioning

confidence: 81%

Crystal Architectures and Magnetic Properties of Alkylferrocenium Salts with F_nTCNQ (n = 0, 2, 4): Effect of Substituents on the Self-Assembled Structures

Mochida

Akasaka

Funasako

et al. 2013

Crystal Growth & Design

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The crystal architecture and magnetic properties of the alkylferrocenium salts of tetracyanoquinodimethane (TCNQ) type acceptors have been investigated using 1,1′dimethyl-, 1,1′-diethyl-, 1,1′-diisopropyl-, tert-butyl-, and tert-pentyl-ferrocene as the donors. In all of the resulting salts, the donors and acceptors were stacked to form independent columns. The F4TCNQ salts had a D/A ratio of 1:1, and existed as hexagonal assembled structures composed of anion columns surrounded by cation columns. The F2TCNQ and TCNQ salts had a D/A ratio of 1:2, and existed as a rectangular arrangement of cation columns. Weak antiferromagnetic interactions were found to operate between the cations in these salts.

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“…Previously, we reported that the cation charge tended to reside on the Fe atom closer to the electronegative atoms of the anions. 22,37 Figure 7a,b shows the structures of the cation and four surrounding anions for the RT and LT phases, respectively, where the order−disorder of the anions was also observed. The negative charge of the Tf 2 N anion is delocalized over the N(SO 2 ) 2 moiety, and several O atoms of the anions are located near the Fe atoms at distances shorter than 4.5 Å in both phases, as indicated by the dashed lines in Figure 7.…”

Section: ■ Introductionmentioning

confidence: 99%

Anion-Ordering Phase Transitions in Biferrocenium and Ferrocenium Salts with the Bis(trifluoromethanesulfonyl)amide Anion

2021

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The bis(trifluoromethanesulfonyl)amide anion (Tf 2 N), which is a common component of ionic liquids, often exhibits disorder in the solid state. In this study, the phase transitions and crystal structures of the Tf 2 N salts of 1,1‴-dineopentyl-1′,1″-biferrocene (=npBifc), 1′,1″-biferrocene (=Bifc), ferrocene, and cobaltocene (1− 4, respectively) were compared. All the salts exhibited phase transitions at low temperatures, which are accompanied by anion ordering, though the ordering was not complete in 2 and 3. X-ray crystallographic investigation revealed that the cations and anions in 1 and 2 adopted alternating arrangements and segregated columnar arrangements, respectively. The cation in 1 exhibited a symmetrical, average-valence structure in the room-temperature phase owing to rapid valence tautomerization, whereas the cation exhibited an unsymmetrical structure in the low-temperature phase. The cation in 2 exhibited an unsymmetrical, trapped-valence structure in both phases. The cation valence states in these salts were accounted for by the electrostatic interactions between the cations and anions. The crystal structures and phase behavior of the ferrocenium salt 3 were very different from those of 4.

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Preparation and structures of biferrocenes with alicyclic substituents: Order–disorder of substituents in the crystal structures of cyclohexenylbiferrocene and its charge-transfer salt

Abstract: Preparation and structures of biferrocenes with alicyclic substituents: Order-disorder of substituents in the crystal structures of cyclohexenylbiferrocene and its charge-transfer salt

Cited by 7 publications

References 30 publications

Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Crystal Architectures and Magnetic Properties of Alkylferrocenium Salts with F_nTCNQ (n = 0, 2, 4): Effect of Substituents on the Self-Assembled Structures

Anion-Ordering Phase Transitions in Biferrocenium and Ferrocenium Salts with the Bis(trifluoromethanesulfonyl)amide Anion

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Preparation and structures of biferrocenes with alicyclic substituents: Order–disorder of substituents in the crystal structures of cyclohexenylbiferrocene and its charge-transfer salt

Abstract: Preparation and structures of biferrocenes with alicyclic substituents: Order-disorder of substituents in the crystal structures of cyclohexenylbiferrocene and its charge-transfer salt

Cited by 7 publications

References 30 publications

Charge-Transfer Salts of Biferrocene Derivatives with F2- and F4-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Charge-Transfer Salts of Biferrocene Derivatives with F2- and F4-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Crystal Architectures and Magnetic Properties of Alkylferrocenium Salts with FnTCNQ (n = 0, 2, 4): Effect of Substituents on the Self-Assembled Structures

Anion-Ordering Phase Transitions in Biferrocenium and Ferrocenium Salts with the Bis(trifluoromethanesulfonyl)amide Anion

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Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Charge-Transfer Salts of Biferrocene Derivatives with F₂- and F₄-Tetracyanoquinodimethane: Correlation Between Donor–Acceptor Ratios and Cation Valence States

Crystal Architectures and Magnetic Properties of Alkylferrocenium Salts with F_nTCNQ (n = 0, 2, 4): Effect of Substituents on the Self-Assembled Structures