Crystal Structure and Physical Properties of π–dSystem κ-(BDH-TTP)2FeBr4

Sugii, Kaori; Takai, Kazuyuki; Uji, S.; Terashima, Taichi; Akutsu, Hiroki; Wada, Atsushi; Ichikawa, S.; Yamada, Jun−ichi; Mori, Takehiko; Enoki, Toshiaki

doi:10.7566/jpsj.82.054706

Cited by 8 publications

(18 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Meanwhile, the molecular orbital (MO) calculation based on the mean field approximation has suggested that the Br substitution with Cl causes the suppression of the exchange interactions and that the FeCl 4 salt consequently shows an AF transition at a lower temperature of T calc N ¼ 1:34 K than the FeBr 4 salt. 22,23) This calculation prompts further investigation of the electronic state of the FeCl 4 salt. In addition, the comparative studies between the FeBr 4 and FeCl 4 salts will provide us with a deeper understanding of the role of the -d interaction in the electron state.…”

Section: Introductionmentioning

confidence: 84%

“…The lattice parameters and unit cell volume of this salt are slightly smaller than those of the FeBr 4 salt. 21,22) The space group of the crystal structure is Pnma with an inversion center. Schematics of the FeCl 4 anion structures are drawn in Fig.…”

Section: Methodsmentioning

confidence: 99%

“…ethylenedioxy-tetrathiafulvalenoquinone-1,3dithiolemethide), 16) (EDO-TTFVODS) 2 FeBr 4 (EDO-TTFVODS: ethylenedioxy-tetrathiafulvalenoquinone-1,3diselenolemethide), 17) (EDT-DSDTFVSDS) 2 FeBr 4 (EDT-DSDTFVSDS: ethylenedithio-diselenadithiafulvalenothioquinone-1,3-diselenolemethide), 18) (EDT-DSDTFVO) 2 FeX 4 (X: Br, Cl) (EDT-DSDTFVO: ethylenedithio-diselenadithiafulvalenoquinone-1,3-dithiolemethide), 19) 00 -(EDO-TTFVODS) 2 FeBr 4 (SCE) 0:15 , 20) -(BDA-TTP) 2 FeCl 4 [BDA-TTP: 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene], 21) and -(BDH-TTP) 2 FeX 4 (X: Br, Cl) [BDH-TTP: 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] 21,22) have been successfully synthesized so far.…”

Section: Introductionmentioning

confidence: 99%

“…21,22) The FeCl 4 salt shows paramagnetic behavior down to 1.5 K without any magnetic transition, whereas the FeBr 4 salt undergoes an antiferromagnetic (AF) transition at 3.9 K. 22) We have revealed that some of the characteristic physical properties of the FeBr 4 salt are ascribed to the -d interaction, 22) but no detailed studies of the isostructural FeCl 4 salt have been performed yet. Meanwhile, the molecular orbital (MO) calculation based on the mean field approximation has suggested that the Br substitution with Cl causes the suppression of the exchange interactions and that the FeCl 4 salt consequently shows an AF transition at a lower temperature of T calc N ¼ 1:34 K than the FeBr 4 salt.…”

Section: Introductionmentioning

confidence: 99%

“…In this paper, we report the resistance, MR, and magnetic torque measurements in a wide temperature range down to lower temperatures, in addition to the magnetic susceptibility and ESR measurements, and compare the data with those of the FeBr 4 salt. 22) …”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

et al. 2013

Self Cite

View full text Add to dashboard Cite

Resistance, magnetic susceptibility, magnetic torque, and ESR measurements have been performed to investigate the electronic state of the two-dimensional organic conductor -(BDH-TTP) 2 FeCl 4 . The temperature dependence of the resistance shows monotonic metallic behavior down to 30 mK, and the magnetic susceptibility, arising mainly from the Fe 3d spins, follows the Curie-Weiss law down to 2 K. At low temperatures below 0.4 K, the magnetic torque steeply changes at low magnetic fields, associated with a sign change. The systematic measurements elucidate that the 3d spins undergo an antiferromagnetic order at about 0.4 K and that the torque sign change is caused by a spin-flop transition. A rapid decrease of the magnetoresistance at the spin-flop field provides clear evidence of a finite -d interaction.Characteristic temperature dependences of the magnetic susceptibility and ESR g-value are found in the paramagnetic phase, which are explained in terms of the single-ion anisotropy effect.

show abstract

Section: Introductionmentioning

confidence: 84%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

New Family of Six Stable Metals with a Nearly Isotropic Triangular Lattice of Organic Radical Cations and Diluted Paramagnetic System of Anions: κ(κ_⊥)-(BDH-TTP)₄MX₄·Solv, where M = Co^II, Mn^II; X = Cl, Br, and Solv = (H₂O)₅, (CH₂X₂)

Bardin

Akutsu

Yamada

2016

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

A new family of six paramagnetic metals, namely, κ-(BDH-TTP)4CoCl4·(H2O)5 (I), κ-(BDH-TTP)4Co0.54Mn0.46Cl4·(H2O)5 (II), κ-(BDH-TTP)4MnCl4·(H2O)5 (III), κ⊥-(BDH-TTP)4CoBr4·(CH2Cl2) (IV), κ⊥-(BDH-TTP)4MnBr4·(CH2Cl2) (V), and κ⊥-(BDH-TTP)4MnBr4·(CH2Br2) (VI), has been synthesized and characterized by X-ray crystallography, four-probe conductivity measurements, SQUID magnetometry, and calculations of electronic structure. The newly discovered κ⊥-type packing motif of organic layers differs from the parent κ-type by a series of longitudinal shifts of BDH-TTP radical cations in the crystal structure. Salts I–VI form two isostructural groups: I–III (κ) and IV–VI (κ⊥). Salts I–III are isostructural to the previously discovered κ-(BDH-TTP)2FeIIIX4 (X = Cl, Br) even though the charge of FeX4 – anions is half that of the MX4 2– (M = Co, Mn) anions. The tetrahedral anions are disordered in I–III but completely ordered in IV–VI. The type of included solvent molecule is solely determined by the anion size. The paramagnetic subsystem is effectively spin diluted either by anion disorder (I–III) or by spatial separation (IV–VI). The Weiss constants are virtually zero for all compounds (e.g., θ(III) = 0.0056 K, θ(V) = −0.076 K). Curie constants are dominated by anion paramagnetic centers indicating high spin states 5/2 for MnII and 3/2 for CoII with large spin–orbital coupling. All compounds retain metallic properties down to 4.2 K. There is a magnetic breakdown gap of width (w) in the chiral salts IV–VI: w(IV) > w(V) ≈ w(VI) but no gap in the centrosymmetric salts I–III. Electronic structure calculations at room temperature revealed a nearly isotropic triangular lattice in I–III and a honeycomb lattice in IV–VI with an extreme geometric spin frustration exceeding the level reported for the quantum “spin liquid” κ-(BEDT-TTF)2Cu2(CN)3.

show abstract

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)₂⁻

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

Crystal Structure and Physical Properties of π–dSystem κ-(BDH-TTP)₂FeBr₄

Cited by 8 publications

References 52 publications

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

New Family of Six Stable Metals with a Nearly Isotropic Triangular Lattice of Organic Radical Cations and Diluted Paramagnetic System of Anions: κ(κ_⊥)-(BDH-TTP)₄MX₄·Solv, where M = Co^II, Mn^II; X = Cl, Br, and Solv = (H₂O)₅, (CH₂X₂)

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)₂⁻

Contact Info

Product

Resources

About

Crystal Structure and Physical Properties of π–dSystem κ-(BDH-TTP)2FeBr4

Cited by 8 publications

References 52 publications

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)2FeCl4

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)2FeCl4

New Family of Six Stable Metals with a Nearly Isotropic Triangular Lattice of Organic Radical Cations and Diluted Paramagnetic System of Anions: κ(κ⊥)-(BDH-TTP)4MX4·Solv, where M = CoII, MnII; X = Cl, Br, and Solv = (H2O)5, (CH2X2)

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)2−

Contact Info

Product

Resources

About

Crystal Structure and Physical Properties of π–dSystem κ-(BDH-TTP)₂FeBr₄

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

Magnetic and Transport Properties of π–d System κ-(BDH-TTP)₂FeCl₄

New Family of Six Stable Metals with a Nearly Isotropic Triangular Lattice of Organic Radical Cations and Diluted Paramagnetic System of Anions: κ(κ_⊥)-(BDH-TTP)₄MX₄·Solv, where M = Co^II, Mn^II; X = Cl, Br, and Solv = (H₂O)₅, (CH₂X₂)

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)₂⁻