The Intermolecular Interaction of Tetrathiafulvalene and Bis(ethylenedithio)tetrathiafulvalene in Organic Metals. Calculation of Orbital Overlaps and Models of Energy-band Structures

Mori, Takehiko; Kobayashi, Akiko; Sasaki, Yukiyoshi; Kobayashi, Hayao; Saito, Gunzi; Inokuchi, Hiroo

doi:10.1246/bcsj.57.627

Cited by 711 publications

(282 citation statements)

References 15 publications

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“…Figure 24a shows the donor packing motif of κ-(DHOT-TTP) 2 PF 6 , in which the DHOT-TTP molecule has orientational disorder among four outer chalcogen atoms in the oxathiolane and dithiolane rings: Occupancy factors for the oxygen sites are 0.28, 0.27, 0.23 and 0. 22. There are several short S· · · S contacts (less than the van der Waals distance of 3.70 Å) between donor pairs, whereas no short S· · · S contact is observed within a donor pair.…”

Section: Structures Of κ-Type Dhot-ttp Saltsmentioning

confidence: 94%

“…At 7.5 kbar, the conformation of BDA-TTP is slightly different from that at ambient pressure ( Figure 6c): The dihedral angles around the intramolecular sulfur-to-sulfur axes in two outer dithiane rings are 51.3° and 29.2°, respectively, whereas the corresponding dihedral angles at ambient pressure are 50.9° and 32.0°, respectively. To gain further information on the electronic structure of β-(BDA-TTP) 2 I 3 , we calculated the overlap integrals between the HOMO's (highest occupied molecular orbitals) of adjacent donor molecules by the extended Hückel method using the reported parameters [22] at ambient pressure and at 7. …”

Section: Effect Of Hydrostatic Pressurementioning

confidence: 99%

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Chemical Modifications of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene]: Control of Electron Correlation

Yamada

Akutsu

2012

Crystals

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Organic molecular conductors with a strongly correlated electron system, in which the itinerancy of electrons (or holes) and the electron correlation (U/W, U, the on-site Coulomb repulsion, W, the bandwidth) compete with each other, are promising candidates for achieving superconductivity and also for exploring remarkable physical properties induced by external stimuli such as pressure, light, voltage and current. Our synthetic approach to the construction of strongly correlated organic electron systems is based on chemical modifications to the donor molecule BDH-TTP [2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] capable of producing metallic CT (charge-transfer) salts stable down to low temperatures (4.2-1.5 K). This aims at enhancing the electron correlation in the itinerant electron system by decreasing the bandwidth. Chemical modifications of BDH-TTP such as ring expansion of two outer dithiolane rings, replacement of one sulfur atom in an outer dithiolane ring with an oxygen atom and introduction of two methyl substituents into an outer ditiolane ring led to BDA-TTP [2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene], DHOT-TTP [2-(1,3-dithiolan-2-ylidene)-5-(1,3-oxathiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] and DMDH-TTP [2-(4,5-dimethyl-1,3-dithiolan-2-ylidene)-5-(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene], respectively. In this review, the physical properties and the crystal and electronic structures of molecular conductors derived from these donor molecules will be described. OPEN ACCESSCrystals 2012, 2 813

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Section: Structures Of κ-Type Dhot-ttp Saltsmentioning

confidence: 94%

Section: Effect Of Hydrostatic Pressurementioning

confidence: 99%

Chemical Modifications of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene]: Control of Electron Correlation

Yamada

Akutsu

2012

Crystals

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“…In molecular solids, the roles played by atomic orbitals in inorganics are replaced with those by molecular orbitals, whereby the transfer integrals are the overlaps of molecular orbitals often provided by the extended Hückel method [9]. These empirical values were successful in reproducing the band structures of the first principle calculations in the first place [10], but often turned out to differ from the experimentally extracted values [11].…”

Section: Classification Of Modelsmentioning

confidence: 99%

“…However, if either of these sites are empty, the exchange process is absent. Therefore, the antiferroelectric alignment, P z m P z n < 0, enhances J eff mn , as is seen from the second term in Equation (9). When the adjacent dimers have 2:1 site connections, the linear combination, W z = J − J, is adopted.…”

Section: (V'-v) + V=2v'-v E=mentioning

confidence: 99%

Theories on Frustrated Electrons in Two-Dimensional Organic Solids

Hotta

2012

Crystals

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Two-dimensional quarter-filled organic solids are a promising class of materials to realize the strongly correlated insulating states called dimer Mott insulator and charge order. In their conducting layer, the molecules form anisotropic triangular lattices, harboring geometrical frustration effect, which could give rise to many interesting states of matter in the two insulators and in the metals adjacent to them. This review is concerned with the theoretical studies on such issue over the past ten years, and provides the systematic understanding on exotic metals, dielectrics, and spin liquids, which are the consequences of the competing correlation and fluctuation under frustration.

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“…The electronic band dispersions and Fermi surfaces were calculated using the intermolecular transfer integrals under the tight-binding approximation [16].…”

Section: Electronic Band Calculationsmentioning

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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The Intermolecular Interaction of Tetrathiafulvalene and Bis(ethylenedithio)tetrathiafulvalene in Organic Metals. Calculation of Orbital Overlaps and Models of Energy-band Structures

Cited by 711 publications

References 15 publications

Chemical Modifications of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene]: Control of Electron Correlation

Chemical Modifications of BDH-TTP [2,5-Bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene]: Control of Electron Correlation

Theories on Frustrated Electrons in Two-Dimensional Organic Solids

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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