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1.
Faraday Discuss ; 250(0): 96-109, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-37986633

RESUMO

Organic electronic devices offer various advantages, such as low cost and tunability. However, the organic semiconductors used in these devices have significant drawbacks, including instability in air and low carrier mobility. To address these challenges, we recently introduced organic MISM and MISIM (M = metal, I = insulator, S = semiconductor) devices, which effectively generate photo-induced displacement current and exhibit ferroelectric behavior. In previous studies, the S layer consisted of an organic donor-acceptor (DA) bilayer. In the present research, we fabricated MISM and MISIM devices using DA-type single-component molecules as the S layer and examined their photocurrent and polarization hysteresis. While the performance of these devices does not surpass that of DA bilayer devices, we discovered that DA-type single-component molecules can be utilized for photoelectric conversion and polarization trapping.

2.
Chem Commun (Camb) ; 59(91): 13575-13578, 2023 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-37850231

RESUMO

Molecular and charge arrangements in the solid state were controlled by a new building block: a triad molecule. Owing to the appropriate flexibilities in both molecular structure and electron distribution of the triad, the apparently simple salt exhibits an unstable metallic phase, which is promising for superconducting transitions.

3.
ACS Appl Mater Interfaces ; 14(31): 35978-35984, 2022 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-35894872

RESUMO

Redox-active organic molecules are promising candidates for next-generation electrode materials. Nevertheless, finding low-molecular-weight organic materials with a long cycle life remains a crucial challenge. Herein, we demonstrate the application of tetrathiafulvalene and its vinyl analogue bearing triphenylamines as long-cycle-life electrodes for lithium-ion batteries (LIBs). These molecules were successfully synthesized using palladium-catalyzed C-H arylation. Electrochemical analysis revealed that a polymer formed on the electrode. LIBs comprising these molecules exhibited noteworthy charge-discharge properties with a long cycle life (the capacity after 100 cycles was greater than 90% of the discharge capacity in the third cycle) and a high utilization ratio (approximately 100%). "In-cell" polymerization during the first charge process is considered to contribute to the effect. This study indicates new avenues for the creation of organic materials for rechargeable batteries.

4.
Inorg Chem ; 61(20): 7754-7764, 2022 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-35549245

RESUMO

The tetramethyl derivative of bis-fused tetrathiafulvalene, 2,5-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (TMTTP), has been successfully synthesized. Most of the radical cation salts consisting of TMTTP feature a high electrical conductivity of σrt = 101 to 102 S cm-1 on a single crystal. The anion shape and size of TMTTP conductors modulate the electrical properties. The PF6- and AsF6- salts exhibit metallic conductivity down to 10 K, while the ReO4- and AuI2- salts show metal-to-insulator (MI) transition at 126 and 11 K, respectively. Single-crystal X-ray structure analysis of (TMTTP)2X (X = PF6, AsF6, BF4, and ReO4) and (TMTTP)3AuI2 reveals that the donor packing motif is categorized as the so-called ß-type. The tight-binding band calculations of (TMTTP)2X (X = ReO4, BF4, PF6, and AsF6) suggest these salts are characterized by quasi-one-dimensional Fermi surfaces. The band calculation based on X-ray structure analysis of (TMTTP)2ReO4 at 100 K demonstrates that the MI transition of this salt is associated with the charge ordering with the zigzag stripe pattern.

5.
Beilstein J Org Chem ; 16: 974-981, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32509028

RESUMO

Novel multistage redox tetrathiafulvalenes (TTFs) bearing 6-aryl-1,4-dithiafulvene moieties were synthesized by palladium-catalyzed direct C-H arylation. In the presence of a catalytic amount of Pd(OAc)2, P(t-Bu3)·HBF4, and an excess of Cs2CO3, the C-H arylation of TTF with several aryl bromides bearing 1,3-dithiol-2-ylidenes took place efficiently to produce the corresponding π-conjugated molecules. We also succeeded in the estimation of the oxidation potentials and number of electrons involved in each oxidation step of the obtained compounds by digital simulations.

6.
ChemSusChem ; 13(9): 2312-2320, 2020 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-32096607

RESUMO

Fused donor-acceptor triads composed of two tetrathiafulvalenes (TTFs) and benzoquinone (BQ; 1) or naphthoquinone (NQ; 2) were successfully synthesized. X-ray structure analysis of the bis(n-butylthio) derivative revealed that the molecules are stacked in a head-to-tail manner. The bis(n-hexylthio)-1 exhibited six-pairs of one-electron transfer waves in the cyclic voltammogram, corresponding to the formation of both reduction and oxidation states from -2 to +4. The unsubstituted and bis(methylthio) derivatives of 1 and 2 were active materials in positive electrodes for rechargeable batteries, several of which displayed energy densities exceeding 800 mWh g-1 . The bis(methylthio)-2 also functions as a positive electrode material for a rechargeable sodium-ion battery.

7.
Dalton Trans ; 48(34): 12858-12866, 2019 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-31317979

RESUMO

The Au(iii)-complex anions in a newly synthesised compound BPY[Au(dmit)2]2 (BPY = N,N'-ethylene-2,2'-bipyridinium, dmit = 1,3-dithiole-2-thione-4,5-dithiolate) reversibly exhibit a molecular distortion in the solid state under UV-radiation. The photoexcited state is maintained for a week at 298 K, during which time molecules relax to their original structures and energy is gradually released as heat without decomposition or light emission. Most Au atoms adopt square planar (SP) coordination geometries, but some anions have unusual non-planar (NP) coordination geometries that produce disorder at the Au sites. The total (Gibbs) energy of the system depends on the proportion of Au atoms of NP geometry, which is directly determined from the occupancy (Occ (%)) by X-ray diffractometry. Due to phase transition, Occ substantially changes at a critical temperature (TC) of ∼280 K without other structural changes; however it remains almost constant in each phase. In addition, due to UV-promoted charge-transfer transitions between BPY and Au(dmit)2, Occ can be controlled by UV irradiation (∼250-450 nm). The UV-excited states have unprecedentedly long relaxation times (t1/2 > 36 h at 298 K), which is attributed to the close connection between the degrees of freedom on charge, spin, and molecular structures.

8.
Chemistry ; 25(19): 4984-4991, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30636026

RESUMO

[5]Radialene with quintuple 4,5-benzo-1,3-dithiol-2-ylidenes (DTs) easily forms a stable polycationic salt (1)4+ (BF4 - )4 owing to its aromatic character in the central cyclopentadienide ring. In this work, it was found that the polycationic salt (1)4+ underwent a hydration reaction in moist polar solvent to give several unexpected products, namely, an oxygen adduct dicationic salt (2)2+ , a tetrathiafulvalene (TTF) vinylogue (3) with 1,4-dithiine-2(3H)-one moieties, and an oxygen adduct of π-extended TTF with a cyclopentenone core (4). Their molecular structures were fully determined by X-ray crystal-structure analysis. In this reaction, irreversible hydration to the polycationic salt might either initiate the ring expansion and lead to the successive hydration at the specific cationic DT ring (for 3), or promote the transannular reactions to the next DT ring followed by elimination of the DT ring (for 4). Cyclic voltammetry and differential pulse voltammetry measurements for compound 3 indicated the occurrence of multi redox process resulting from electronic delocalization on the vinylogous TTF moiety. The electronic structures of the cationic species of 3 were also investigated by electronic spectra.

9.
Org Lett ; 20(17): 5121-5125, 2018 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-30129770

RESUMO

Derivatives of a new bis-fused donor composed of TTF and extended TTF with an anthraquinoid spacer (TTFAQ) (2) were successfully synthesized. X-ray structure analysis of the tetrakis(methylthio) derivative 2Aa and its I3- salt revealed that the TTFAQ moieties of both 2Aa and 2Aa•+ adopt the so-called saddle conformation similar to most neutral TTFAQs. The results obtained from the X-ray structure analysis and cyclic voltammetry suggest that a positive charge in 2Aa•+ is unevenly distributed on the TTF moiety, while both positive charges of 22+ are mainly located on the TTFAQ moiety. In the first two-electron redox processes, an extra cathodic wave attributed to the coexistence of a different reduction process from the oxidation process was observed for most of the derivatives.

10.
Org Lett ; 18(22): 5868-5871, 2016 11 18.
Artigo em Inglês | MEDLINE | ID: mdl-27934508

RESUMO

Bis- and tris-fused π-electron donors composed of extended tetrathiafulvalene with anthraquinoid spacers (4 and 5) were successfully synthesized. X-ray structure analysis of tetrakis(methylthio)-5 (5a) revealed that the molecule adopted a transoid-cisoid conformation. The cyclic voltammogram of 4a is composed of two pairs of two-electron redox waves, while the cyclic voltammogram of tetrakis(hexylthio) derivative 5b consists of one pair of four-electron redox waves and one pair of two-electron redox waves, respectively. Spectroelectrochemistry of 4a and 1H NMR spectrum of a 4b salt revealed that two positive charges in 42+ are distributed mainly on one TTFAQ (9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene) moiety.

11.
Chemistry ; 22(29): 10090-101, 2016 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-27282147

RESUMO

Understanding the details of the electronic structure in face-to-face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (-S(CH2 )n S-, n=1-4) as models of triple- and quadruple-decker TTF arrays. Single-crystal X-ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi-electron transfers, depending on the length of the -S(CH2 )n S- units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630-1850 nm), attributed to a mixed valence (MV) state of the triple- and quadruple-decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent-dependent redox processes were observed. Moreover, π-trimers and π-tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.

12.
Int J Mol Sci ; 15(3): 4550-64, 2014 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-24642878

RESUMO

The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole-2-selenone 6-9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-s-indacene-6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a-d to amino 11a-d then dibenzylamine 12a-d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.


Assuntos
Benzeno/química , Condutividade Elétrica , Eletroquímica/métodos , Compostos Heterocíclicos/química , Compostos Heterocíclicos/síntese química , Espectroscopia de Ressonância Magnética , Modelos Químicos , Estrutura Molecular
13.
Phys Rev Lett ; 109(14): 147005, 2012 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-23083272

RESUMO

We report the molecular dipole effect on conduction electrons in the title superconductor. The angular-dependent magnetoresistance has a peak for fields nearly parallel to the conducting layer, and the peak width scales as the field component perpendicular to the layer, indicating incoherent interlayer transport. However, two closed Fermi surfaces are observed in quantum oscillation. Accordingly, crystallographically independent layers have different charge densities in a bulk single crystal. The electric dipole of tetrahydrofuran gives rise to interlayer charge disproportionation.

14.
J Am Chem Soc ; 134(42): 17452-5, 2012 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-23039338

RESUMO

We report the first observation of spin-flop-induced sharp positive magnetoresistance as large as 100% and nonvolatile magnetoresistive memory in a π-d hybrid molecular conductor, (DIETSe)(2)FeCl(4) [DIETSe = diiode(ethylenedithio)tetraselenafulvalene]. The unprecedented magnetotransport phenomena originate from the coexistence of the spin density wave (SDW) of the quasi-one-dimensional (Q1D) π electrons and the antiferromagnetic order of d-electron spins, indicating the interplay between the electronic instability of Q1D π electrons and local moments of antiferromagnetic d-electron spins. These findings offer new possibilities in molecular electronics/spintronics.

15.
J Am Chem Soc ; 134(32): 13330-40, 2012 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-22812374

RESUMO

A series of quasi-one-dimensional molecular conductors (DMEDO-TTF)(2)XF(6) (X = P, As, and Sb), where DMEDO-TTF is dimethyl(ethylenedioxy)tetrathiafulvalene, undergo characteristic structural transitions in the range of 130-195 K for the PF(6) salt and 222-242 K for the AsF(6) salt. The dramatic structural transition is induced by the order of the ethylenedioxy moiety, and the resulting anion rotation leads to the reconstruction of the H···F interaction between the methyl groups and the anions. The unique hydrogen bonds play a crucial role in the transition. As a result, the molecular packing is rearranged entirely; the high-temperature molecular stacks with an ordinary quasi-triangular molecular network transforms to a quasi-square-like network, which has never been observed among organic conductors. Nonetheless, the low-temperature phase exhibits a good metallic conductivity as well, so the transition is a metal-metal (MM) transition. The resistivity measured along the perpendicular direction to the conducting ac-plane (ρ(⊥)) and the calculation of the Fermi surface demonstrate that the high-temperature metal phase is a one-dimensional metal, whereas the low-temperature metal phase has considerable interchain interaction. In the SbF(6) salt, a similar structural transition takes place around 370 K, so that the quasi-square-like lattice is realized even at room temperature. Despite the largely different MM transition temperatures, all these salts undergo metal-insulator (MI) transitions approximately at the same temperature of 50 K. The low-temperature insulator phase is nonmagnetic, and the reflectance spectra suggest the presence of charge disproportionation with small charge difference (0.14).

16.
Org Lett ; 13(12): 3122-5, 2011 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-21591724

RESUMO

New dimeric and trimeric TTF derivatives with methylenedithio spacers (1a,b, 2a, and 2b) have been synthesized. X-ray structure analysis revealed that TTF units of the dimer 1b adopted distorted face-to-face overlapping arrangement both in intra- and intermolecular stacking. Cyclic voltammetric study indicated that trimeric 2a was in favor of taking di- and tetracationic states, while the dimeric 1a was in favor of taking a monocation. The absorption spectroscopic study suggested an existence of the strong face-to-face interaction particularly in di-, tri-, and tetracationic state of the trimeric TTF derivatives.

17.
Chemistry ; 13(27): 7619-30, 2007.
Artigo em Inglês | MEDLINE | ID: mdl-17610218

RESUMO

The unsymmetrical pi donor dimethyl(ethylenedioxy)tetraselenafulvalene (DMEDO-TSeF) has provided six new organic superconductors with a monovalent square-planar [Au(CN)(4)](-) ion and cyclic ethers as solvent of crystallization. The six new organic superconductors kappa-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) [solv.=1,3-dioxolane (DOL), 2,5-dihydrofuran (DHF), tetrahydropyran (THP), 1,3-dioxane (1,3-DOX), 3,4-dihydro-2H-pyran (DHP), or 1,4-dioxane (1,4-DOX)] are classified into two subphases kappa(L) and kappa' according to the differences in their space group symmetry. kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL, DHF, THP, 1,3-DOX or DHP) crystallizes in the orthorhombic space group Pnma, and T(c) of the kappa(L) phase varies by 1.7-5.3 K according to the size and shape of the solvent of crystallization. On the other hand, kappa'-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL or 1,4-DOX) crystallizes in the noncentrosymmetric monoclinic space group Cc. The kappa'-phase containing 1,4-DOX shows superconductivity at 4.2 K, but the kappa'-phase containing DOL does not show superconductivity down to 1.4 K. Systematic investigation of the six new organic superconductors, together with the two previously reported superconductors kappa(H)- and kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](THF), revealed that the T(c) of the present system is finely tunable by utilizing the effect of the solvent of crystallization.

18.
Chem Commun (Camb) ; (15): 1592-4, 2006 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-16582989

RESUMO

We have developed two novel organic superconductors kappa H- and kappa L-(DMEDO-TSeF)2[Au(CN)4](THF) (DMEDO-TSeF = dimethyl(ethylenedioxy)tetraselenafulvalene) with the onset transition temperatures of 4.8 K for the kappa H-phase and 3.0 K for the kappa L-phase at ambient pressure, where DMEDO-TSeF is the second example following tetramethyltetraselenafulvalene (TMTSF) after an interval of 25 years as a sulfur-free donor providing a bulk organic superconductor.

19.
Chem Commun (Camb) ; (14): 1590-1, 2004 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-15263932

RESUMO

Bis(ethylenedioxy)tetraselenafulvalene (BEDO-TSeF) has been synthesized using elemental selenium as the only source of the selenium atoms, and its crystal structure and electrochemical properties are examined and compared with its sulfur analogues.

20.
Org Biomol Chem ; 2(12): 1685-7, 2004 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-15188033

RESUMO

Novel selenium analogues of diiodo(ethylenedithio)diselenadithiafulvalene (DIETS) have been successfully derived from 1,3-diselenole-2-thione, which could be synthesized without the use of the highly toxic reagent CSe(2).

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