A New Synthesis of Tetrathiooxalate and Its Conversion to C3S52- and C4S62-

Breitzer, Jonathan G.; Chou, Jun Hong; Rauchfuss, Thomas B.

doi:10.1021/ic971327c

Cited by 22 publications

(15 citation statements)

References 14 publications

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“…The β -type crystals (black hexagonal plates) were obtained as a single phase. The 13 C-enriched dmit ligand for 13 C-NMR measurements was synthesized from tetrachloroethylene-13 C 1 (99 atom %, Sigma-Aldrich) that was converted to tetrathiooxalate for the reaction with CS 2 [18]. The 13 C-enriched single crystals of β -EtMe 3 Sb[Pd(dmit) 2 ] 2 (No.…”

Section: Methodsmentioning

confidence: 99%

A Discrepancy in Thermal Conductivity Measurement Data of Quantum Spin Liquid β′-EtMe3Sb[Pd(dmit)2]2 (dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)

et al. 2022

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A molecular Mott insulator β′-EtMe3Sb[Pd(dmit)2]2 is a quantum spin liquid candidate. In 2010, it was reported that thermal conductivity of β′-EtMe3Sb[Pd(dmit)2]2 is characterized by its large value and gapless behavior (a finite temperature-linear term). In 2019, however, two other research groups reported opposite data (much smaller value and a vanishingly small temperature-linear term) and the discrepancy in the thermal conductivity measurement data emerges as a serious problem concerning the ground state of the quantum spin liquid. Recently, the cooling rate was proposed to be an origin of the discrepancy. We examined effects of the cooling rate on electrical resistivity, low-temperature crystal structure, and 13C-NMR measurements and could not find any significant cooling rate dependence.

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Section: Methodsmentioning

confidence: 99%

A Discrepancy in Thermal Conductivity Measurement Data of Quantum Spin Liquid β′-EtMe3Sb[Pd(dmit)2]2 (dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)

et al. 2022

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“…The M 2 TTO monomer is unstable, as demonstrated by its rare crystal structure, 11,24 low direct synthesis yields, 25 and troublesome chemical synthesis. [26][27][28] To address this, M 2 TTO was prepared from TEA 2 TTO by a counterion exchange in methanol with the desired alkali salt of tetraphenylborate, as shown in Figure 3. 16 This reaction scheme exploits both the increased solubility of M 2 TTO and the insolubility of tetraethylammonium tetraphenylborate in methanol.…”

Section: Resultsmentioning

confidence: 99%

Thermoelectric Performance of n‐Type Poly(Ni‐tetrathiooxalate) as a Counterpart to Poly(Ni‐ethenetetrathiolate): NiTTO versus NiETT

Wolfe

Menon

Marder

et al. 2019

Adv Elect Materials

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The synthesis of the metal-coordination polymer poly(nickel tetrathiooxalate) (NiTTO) is presented, which represents an alternative route to n-type thermoelectric materials similar in nature to nickel ethenetetrathiolate (NiETT) polymers. The TTO monomer is synthesized through an electrochemical reduction of carbon disulfide, followed by coordination polymerization with a nickel(II) salt to yield a coordination complex polymer with a neutral repeat unit. An alkali metal counterion exchange and polymerization optimization are performed, and a thermoelectric power factor of 6 µW/m-K 2 (electrical conductivity of over 10 S/cm) is achieved for NiTTO-PVDF composite films. This is significantly higher than other reported n-type polymers (and to within a factor of two of NiETT) and demonstrates the potential of NiTTO as a new thermoelectric material. Elemental analysis indicates a nearly neutral backbone structure in NiTTO with minimal charge balancing alkali ions, indicating that these polymers are more oxidized than NiETTs. XPS reveals a different coordination environment for NiTTO compared to NiETTs with the same alkali counterion, indicating that -despite their structural similarity in theory -these two materials are indeed different.

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“…[22] The reaction must be run cold (~ 0 °C) in the presence of a tetraethylammonium salt to trap the desired intermediate as bis(tetraethylammonium)-tetrathiooxalate. [63][64] Tetrathiooxalate will continue to react if not trapped and an equal charge must be passed at the counter electrode. In practice, a murky yellow solid is formed in the counter electrode compartment that is believed to be tetraethylammonium tribromide from the color.…”

Section: Nitto As An Alternative To Niettmentioning

confidence: 99%

“…An alternate chemical route, which does not rely on the reduction of carbon disulfide, was reported in which the authors use sodium persulfide (Na 2 S 2 ) on tetrachloroethylene to generate TTO. [64] Although there are multiple reports of the TTO monomer synthesis, few reports continue to the formation of the NiTTO polymer and investigation of its thermoelectric behavior.…”

Section: Nitto As An Alternative To Niettmentioning

confidence: 99%

Progress in Nickel‐Coordinated Polymers as Intrinsically Conducting n‐Type Thermoelectric Materials

Menon

Wolfe

Kommandur

et al. 2019

Adv Elect Materials

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Organic thermoelectrics have witnessed rapid development in the past decade for low temperature energy harvesting applications. While high performance p-type polymers have been demonstrated, ntype materials have lagged behind due to the limited number of stable n-dopants and low doping efficiencies. Nickel-coordination polymers are a promising class of n-type polymers as they are conducting without extrinsic doping, thus overcoming a major challenge. However, advantages in thermoelectric properties are outweighed by a complicated synthesis and a poorly understood reaction mechanism that has resulted in a large variation in literature for the same material. This progress report provides a comprehensive and critical overview of syntheses and thermoelectric property optimization approaches for two coordination polymers, namely Ni-ethenetetrathiolate (NiETT) and Nitetrathiooxalate (NiTTO). In particular, material characterization and thin film fabrication techniques are discussed, and the importance of reporting statistically relevant thermoelectric properties is highlighted to ensure reproducibility among different groups. A short discussion on prototype devices based on NiETT is presented, and finally, directions for future development of these and other n-type metal-coordinated polymers are suggested.

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A New Synthesis of Tetrathiooxalate and Its Conversion to C₃S₅^2- and C₄S₆^2-

Abstract: New chemical relationships have been established for C2-based carbon sulfides, as shown in the illustration below.

Cited by 22 publications

References 14 publications

A Discrepancy in Thermal Conductivity Measurement Data of Quantum Spin Liquid β′-EtMe3Sb[Pd(dmit)2]2 (dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)

A Discrepancy in Thermal Conductivity Measurement Data of Quantum Spin Liquid β′-EtMe3Sb[Pd(dmit)2]2 (dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)

Thermoelectric Performance of n‐Type Poly(Ni‐tetrathiooxalate) as a Counterpart to Poly(Ni‐ethenetetrathiolate): NiTTO versus NiETT

Progress in Nickel‐Coordinated Polymers as Intrinsically Conducting n‐Type Thermoelectric Materials

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