Novel Bis-fused π-Electron Donor Composed of Tetrathiafulvalene and Tetraselenafulvalene

Ashizawa, Minoru; Ishidzu, Ken-ichi; Watanabe, Masaki; Tanahashi, Tetsuhiko; Shirahata, Takashi; Kawamoto, Tadashi; Mori, Takehiko; Misaki, Yohji

doi:10.1246/cl.2010.1093

Cited by 10 publications

(6 citation statements)

References 20 publications

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“…The stronger intramolecular charge localization in the donor molecule at low temperatures is indicative of charge disproportionation, as has been suggested for π-extended donors. 42,43 Stronger charge gradation is expected to alter the electronic structure at low temperatures, although π-dimerization was not observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family

Onozuka,

Fujino,

Kameyama

et al. 2023

J. Am. Chem. Soc.

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Modern organic conductors are typically lowmolecular-weight or polymer-based materials. Low-molecularweight materials can be characterized using crystallographic information, allowing structure−conductivity relationships to be established and conduction mechanisms to be understood. However, controlling their conductive properties through molecular structural modulation is often challenging because of their relatively narrow conjugate areas. In contrast, polymer-based materials have highly π-conjugated structures with wide molecular-weight distributions, and their structural inhomogeneity makes characterizing their structures difficult. Thus, we focused on the less-explored intermediate, i.e., single-molecular-weight oligomers that model doped poly(3,4-ethylenedioxythiophene) (PEDOT). The dimer and trimer models provided clear structures; however, the short oligomers led to much lower conductivities (<10 −3 S cm −1 ) than that of doped PEDOT. Herein, we elongated the oligomer to a tetramer through geometrical tuning based on a mixed sequence. The "P−S−S−P" sequence (S: 3,4-ethylenedithiothiophene; P: 3,4-(2′,2′-dimethypropylenedioxy)thiophene) with twisted S−S enhanced the solubility and chemical stability. The subsequent oxidation process planarized the oligomer and expanded the conjugate area. Interestingly, the sequence involving sterically bulky outer P units allowed the doped oligomer to form a pitched π-stack in the single-crystal form. This enabled the inclusion of excess counter anions, which modulated the band filling. The combined effects of conjugate area expansion and band-filling modulation significantly increased the room-temperature conductivity to 36 S cm −1 . This is the highest value reported for a single-crystalline oligomer conductor. Furthermore, a metallic state was observed above room temperature in a single-crystalline oligoEDOT for the first time. This unique mixed-sequence strategy for oligomer-based conductors enabled the precise control of conductive properties.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family

Onozuka,

Fujino,

Kameyama

et al. 2023

J. Am. Chem. Soc.

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“…A new very interesting donor compound, 2-(1,3-diselenole-2-ylidene)-5-(1,3-dithiol-2-ylidene)-1,3-diselena-4,6-dithiapentalene 146 , containing tetrathiafulvalene structure condensed with the tetraselenafulvalene scaffold, was synthesized in 49% yield ( Scheme 44 ) [ 95 ]. The TSF derivative 147 was sequentially treated with CsOH·H 2 O, with ZnCl 2 , n -Bu 4 NBr, and then with triphosgene to obtain compound 148 (40% yield).…”

Section: The 14-diselenafulvene and 1458-tetraselenafulvalene Derivat...mentioning

confidence: 99%

“…The cross-coupling reaction between 148 and 4,5-bis(methoxycarbonyl)-1,3-dithiol-2-thione ( 149 , two equivalents) in the presence of trimethyl phosphite at reflux in toluene gave bis(methoxycarbonyl) derivative 150a in 79% yield. The product 146 was obtained in 49% yield by demethoxycarbonylation of compound 150a with excess LiBr·H 2 O in hexamethylphosphorous triamide ( Scheme 44 ) [ 95 ]. The radical cationic salt ( 146 )ReO 4 exhibited low conductivity with a high activation energy.…”

Section: The 14-diselenafulvene and 1458-tetraselenafulvalene Derivat...mentioning

confidence: 99%

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Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

Махаева¹,

Амосова²,

Потапов³

2022

Molecules

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The first organic metals were obtained based on tetrathiafulvalene. The most significant advance in the field of organic metals was the discovery of superconductivity. The first organic superconductors were obtained based on tetramethyltetraselenafulvalene. These facts demonstrate great importance of tetraselenafulvalenes and their precursors, diselenafulvenes, for materials sciences. Derivatives of 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene are useful building blocks for organic synthesis and donor units for the preparation of charge-transfer complexes and radical ion salts, the construction of organic metals, superconductors, organic Dirac materials, semiconductors, ferromagnets, and other conductive materials. This review covers the literature on the design, synthesis, and application of 1,4,5,8-tetraselenafulvalenes and 1,4-diselenafulvenes and their tellurium analogs over the past 15–20 years. These two classes of compounds are interconnected, since the main part of methods for the synthesis of tetraselenafulvalenes is based on the diselenafulvene derivatives as starting compounds. Special attention is paid to the development of novel efficient synthetic approaches to these classes of compounds. Conducting properties and distinguishing features of materials based on tetraselenafulvalenes and their tellurium analogs as well as examples of materials with high conductivity are discussed.

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“…No tetraselenapentalene-type donor has been synthesized so far because of synthetic difficulty. We have recently reported the synthesis of diselenadithiapentalene (STP) donor, 2-(1,3-diselenol-2-ylidene)-5-(1,3-dithio-2-ylidene)-1,3-deselena-4,6-dithiapentalene (ST-STP) [8,9]. In this paper, we report herein the synthesis and properties of new STP donors containing a series of chalcogenopyran-4-ylidene moiety, 2-(1,3-diselenol-2-ylidene)-5-(pyran-4-ylidene)-1,3-deselena-4,6-dithiapentalene (PDS-STP, 1a), 2-(1,3-diselenol-2-ylidene)-5-(thiopyran-4-ylidene)-1,3-deselena-4,6-dithiapentalene (TPDS-STP, 2a), and their bis(methylthio) derivatives (TM-PDS-STP 1b and TM-TPDS-STP 2b) (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures and Properties of Molecular Conductors Based on Bis-Fused Donors Composed of (Thio)Pyran-4-ylidene-1,3-dithiole and Tetraselenafulvalene

et al. 2012

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Bis-fused donors composed of (thio)pyran-4-ylidene-1,3-dithiole and tetraselenafulvalene (1a, 2a) and their bis(methylthio) derivatives (1b, 2b) were synthesized. Cyclic voltamograms of all the donors consisted of four pairs of one-electron redox waves, and it was suggested that a positive charge of 1 +• and 2 +• distributed mainly on the (thio)pyran-4-ylidene-1,3-dithiole moiety. X-ray structure analysis revealed that (1b)PF 6 (C 6 H 5 Cl) 0.5 and (2b)PF 6 (C 6 H 5 Cl) formed one-dimensional conducting stacks in which the donors were dimerized or tetramerized. In those salts, intramolecular charge disproportionation of the donors was suggested by X-ray structure analysis and density functional theory (DFT) calculation with UB3LYP/6-31G(d) basis function. A tightbinding band calculation suggested that these materials were band insulators. All the donors gave highly conducting TCNQ (7,7,8,8-tetracyanoquinodimethane) complexes and I 3 − salts (σ rt = 0.3-19 S cm −1 on a compressed pellet) with very low activation energies of 0.017-0.040 eV, while single crystals of (1b)PF 6 (C 6 H 5 Cl) 0.5 and (2b)PF 6 (C 6 H 5 Cl) exhibited semiconductive behavior with large activation energies (E a = 0.16-0.22 eV).

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Novel Bis-fused π-Electron Donor Composed of Tetrathiafulvalene and Tetraselenafulvalene

Cited by 10 publications

References 20 publications

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family

Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

Synthesis, Structures and Properties of Molecular Conductors Based on Bis-Fused Donors Composed of (Thio)Pyran-4-ylidene-1,3-dithiole and Tetraselenafulvalene

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