A Novel TTP Donor Containing a PROXYL Radical for Magnetic Molecular Conductors

Fujiwara, Hideki; Lee, Ha-Jin; Kobayashi, Hayao; Fujiwara, Emiko; Kobayashi, Akiko

doi:10.1246/cl.2003.482

Cited by 19 publications

(7 citation statements)

References 17 publications

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“…Therefore many researchers have introduced organic radicals in organic conducting salts. For example, charge-transfer (CT) salts of free radical substituted organochalcogen donors [7][8][9][10][11][12][13][14][15][16], CT complexes of free radicals and acceptors [17][18], CT salts of free radical substituted cations and acceptors [19][20][21][22][23], have been reported.…”

mentioning

confidence: 99%

A novel BEDT-TTF-based purely organic magnetic conductor, α - (BEDT - TTF)2(TEMPO - N(CH3)COCH2SO3) ⋅ 3H2O

Akutsu

Yamada

Nakatsuji

et al. 2006

Solid State Communications

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confidence: 99%

A novel BEDT-TTF-based purely organic magnetic conductor, α - (BEDT - TTF)2(TEMPO - N(CH3)COCH2SO3) ⋅ 3H2O

Akutsu

Yamada

Nakatsuji

et al. 2006

Solid State Communications

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“…After the column-chromatographic separation of the resultant mixture, donor molecule 1 having a vinylene spacer was obtained as air-stable orange microcrystals in 53% yield. radical salts using bis-fused TTF (TTP = 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) donors and a PROXYL radical [14][15][16]. Furthermore, we have developed new TTF and TTP donors containing a 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical [17] because this radical part has an unsaturated 3-pyrroline ring with a C=C bond and smaller steric hindrance in comparison to the PROXYL radical having a saturated 3-pyrrolidine ring.…”

Section: Synthesis Of Donormentioning

confidence: 99%

“…On the other hand, the studies on molecular conductors using donor molecules substituted with stable organic radicals such as 2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) and nitronyl nitroxide radicals have been performed by several research groups [6][7][8][9] because cation radical salts of such stable radical-containing donors are expected to have strong intramolecular magnetic interactions between their π-cation radical spins and stable radicals and to show outstanding responses to the application of external magnetic fields [10]. Among them, we have also reported several tetrathiafulvalene (TTF)-based donor molecules containing stable organic radical parts such as TEMPO and 2,2,5,5-tetramethylpyrrolidin-1-yloxy (PROXYL) radicals [11][12][13], and discovered highly conducting cation radical salts using bis-fused TTF (TTP = 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) donors and a PROXYL radical [14][15][16]. Furthermore, we have developed new TTF and TTP donors containing a 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical [17] because this radical part has an unsaturated 3-pyrroline ring with a C=C bond and smaller steric hindrance in comparison to the PROXYL radical having a saturated 3-pyrrolidine ring.…”

Section: Introductionmentioning

confidence: 99%

New Ethylenedithio-TTF Containing a 2,2,5,5-Tetramethylpyrrolin-1-yloxyl Radical through a Vinylene Spacer and Its FeCl4− Salt—Synthesis, Physical Properties and Crystal Structure Analyses

Horikiri

Fujiwara

2017

Magnetochemistry

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Abstract:To develop novel magnetic conductors exhibiting conducting/magnetic bifunctionalities and peculiar responses to applied magnetic fields, we synthesized new EDT-TTF (ethylenedithiotetrathiafulvalene) donor containing a 2,2,5,5-tetramethylpyrrolin-1-yloxyl radical through a π-conjugated vinylene spacer 1 and examined its electronic and crystal structures, and physical properties. We also prepared its cation radical salts by an electrochemical oxidation method and successfully cleared the crystal structures and magnetic properties of the cation radical salts, 1·FeCl 4 and 1·GaCl 4 . These salts have strongly dimerized one-dimensional arrays of the fully oxidized donor molecules, giving rise to the formation of spin-singlet state of the π cation radical spins in the dimer. On the other hand, the FeCl 4 − anion locates on the side of the dimers with very short S-Cl contacts and mediates very strong π-d interaction between the donor and anion moieties, resulting in the antiferromagnetic behavior of the Weiss temperature of θ = −3.9 K through its d-π-d interaction.

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“…5,6 The black crystals of (TTP-PROXYL)MCl 4 (M ¼ Fe and Ga) were prepared electrochemically. The X-ray crystal structure analyses revealed that the FeCl 4 salt was isostructural to the GaCl 4 salt and belonged to the triclinic system.…”

Section: K Emu Molmentioning

confidence: 99%

A Magnetic Organic Conductor Based on a π Donor with a Stable Radical and a Magnetic Anion—A Step to Magnetic Organic Metals with Two Kinds of Localized Spin Systems

Otsubo¹,

Cui²,

Lee³

et al. 2005

Chemistry Letters

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(TTP-PROXYL)FeCl 4 , where TTP-PROXYL is 2,5-bis-(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (TTP) incorporating the 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PROXYL) radical, is a semiconductor with two kinds of localized spin systems, that is, the systems of organic radical spins and 3d spins of magnetic FeCl 4 À ions. The spin of the TTP-PROXYL radical cation disappears due to dimerization but the T-value of 4.65 K emu mol À1 indicates the coexistence of high-spin Fe However, if the organic conductors based on donors with localized radical spins and magnetic anions such as FeCl 4 À can be prepared, the magnetic interaction between organic radical spin and magnetic moment of Fe 3þ ions would occur, which will open a way to realize a new type of the magnetic organic conductors such as ferrimagnetic organic conductors. In this paper, we report the crystal structures and physical properties of (TTP-PROXYL)FeCl 4 and isostructural (TTP-PROXYL)GaCl 4 .TTP-PROXYL was prepared according to the literature. 5,6The black crystals of (TTP-PROXYL)MCl 4 (M ¼ Fe and Ga) were prepared electrochemically. The X-ray crystal structure analyses revealed that the FeCl 4 salt was isostructural to the GaCl 4 salt and belonged to the triclinic system. 7 The crystals have the donor:anion ratio of 1:1. As shown Figure 1, there are two crystallographically independent donors (A and B) and anions (C and D). Unlike usual organic conductors, the crystal of (TTP-PROXYL)MCl 4 has not two-dimensional donor layer. Two TTP-PROXYL molecules interrelated by inversion symmetry are dimerized in a head-to-tail manner (Figure 2). There are many intradimer short SÁÁÁS contacts. The TTP-PROXYL dimers A and B are loosely stacked to form columns along the b and a directions, respectively, and the TTP-PROXYL columns and MCl 4 À anions are arranged alternately along the a and b

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A Novel TTP Donor Containing a PROXYL Radical for Magnetic Molecular Conductors

Abstract: A TTP donor containing a stable PROXYL radical was synthesized to develop conducting-magnetic bifunctional materials and its structure and physical properties were investigated. Furthermore its cation radical salts were prepared and revealed their conducting and magnetic properties.

Cited by 19 publications

References 17 publications

A novel BEDT-TTF-based purely organic magnetic conductor, α - (BEDT - TTF)2(TEMPO - N(CH3)COCH2SO3) ⋅ 3H2O

A novel BEDT-TTF-based purely organic magnetic conductor, α - (BEDT - TTF)2(TEMPO - N(CH3)COCH2SO3) ⋅ 3H2O

New Ethylenedithio-TTF Containing a 2,2,5,5-Tetramethylpyrrolin-1-yloxyl Radical through a Vinylene Spacer and Its FeCl4− Salt—Synthesis, Physical Properties and Crystal Structure Analyses

A Magnetic Organic Conductor Based on a π Donor with a Stable Radical and a Magnetic Anion—A Step to Magnetic Organic Metals with Two Kinds of Localized Spin Systems

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