The chemistry of 1,3-dithiole-2-thione-4,5-dithiolate (dmit)

Olk, Ruth‐Maria; Olk, B.; Dietzsch, W.; Kirmse, R.; Hoyer, Eberhard

doi:10.1016/0010-8545(92)80021-i

Cited by 220 publications

(69 citation statements)

References 213 publications

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“…244 The best fitting parameters for a simulation of the observed ESR spectra are comparable or consistent with those of related compounds. 195,197,241,242 The ESR spectra under dark conditions can be interpreted as follows. The signals observed for 13 in the dark originate from the spin delocalized over the [Cu(dmit) 2 ] 2¹ anions.…”

Section: Electrical Resistivity and Magnetic Susceptibilitymentioning

confidence: 99%

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Naito

2016

Bulletin of the Chemical Society of Japan

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This study concerns development of a non-destructive method to control conduction and magnetism of molecular solids such as single crystals of charge-transfer complexes. The method is named “optical doping”, where appropriate irradiation is utilized under ambient conditions. Owing to this feature, it can be applied to a wide range of substances while measuring the properties during the control. In addition, the method adds unique conduction and magnetic properties to common insulators. Unlike other doping methods, optical doping only affects the properties and/or structures of the irradiated part of a sample while leaving the rest of the sample unchanged. There are two patterns in the optical doping. Irreversible optical doping produces junction-structures on the single molecular crystals, which exhibit characteristic behavior of semiconductor devices such as diodes and varistors. Reversible optical doping produces “giant photoconductors” and “photomagnetic conductors” by realizing unprecedented metallic photoconduction. In the latter case, localized spins are also excited to produce a Kondo system, where carriers and localized spins interact with each other. Not only the control of conduction and magnetism, the optical doping has realized the observation of physical properties in molecular crystals hardly observed under any thermodynamic condition.

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Section: Electrical Resistivity and Magnetic Susceptibilitymentioning

confidence: 99%

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Naito

2016

Bulletin of the Chemical Society of Japan

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“…The splitting of the low frequency band is more discreet in the OA (and reflectance) spectra of the complexes in the solid state (see for example [29] and refs. [9][10][11] cited therein). Figure 15 shows the polarized reflectance spectra of (Bu 4 N)[Ni(dmit) 2 ] with the wavevector of the light parallel (R ║ ) and perpendicular (R ┴ ) to the needle axis of the crystal, as well as the OA spectra of the material in CS 2 solution and a suspension in CCl 4 .…”

Section: Optical Propertiesmentioning

confidence: 99%

“…From the crystallographic data and the transfer integrals the electronic band structure could be calculated [18,20,51]. Consequently, it is expected that there is also a wide variety in behavior, concerning electronic (see [7,18]) and other (see [2][3][4][6][7][8][9][10][11][12][13][14][15]17,) properties of M 1,2-DTs, in the solid state.…”

Section: Structural Propertiesmentioning

confidence: 99%

“…They are compared to those obtained from the corresponding TTFs and similar single component materials. More information concerning the ligands of Table 1 can be found in [6][7][8][9][10][11][12][13][14][15][16]20,21,24,[26][27][28]30,31,34,36,[48][49][50]53,[61][62][63][64]72,77,79,88,89,92,94,[100][101][102][103][104]. More information concerning the ligands of Table 2 can be found in the corresponding references for L1 [34], L2 [34,98], L3 [33,95,102], L4 …”

Section: Introductionmentioning

confidence: 99%

“…The donor (push) or acceptor (pull) ability of the additional groups, plays an important role in the behavior concerning optical, conducting and superconducting properties of these materials. For example, the complexes [M(mnt) 2 ] [5] and [M(dmit) 2 ] [6] (see also [8,11,12,20]), of which the molecular formulas are shown in Figure 2 L15a (X = Et, X' = Pent), L15b (X = X' = iPr) L16 **** L17 (R, R several groups) L18 * L4a (X = Me), L4b (X = Br), L4c (X = F), L4d (X = CF 3 ), L4e (X = NO 2 ), L4f (X = Cl), L4g (X = CN), L4h (X = H), L4i (X = OMe); ** L9a (X = H), L9b (X = Me), L9c (X = Et), L9d (X = F), L9e (X = CF 3 ), L9f (X = tBu), L9g (X = C 6 H 6 ), L9h (X = COOH), L9i (X = COOMe), L9ji (X = OMe), L9k (X = OC 4 H 9 ), L9l (X = OC 8 On the other hand, the complexes [Ni(dddt) 2 ] [5] and [Ni(edo) 2 ] [14], of which the molecular formulas are shown in Figure 3, are based on ligands with donor ability and give cationic salts, which are conducting materials [13][14][15]21]. 2 and Ni(edo) 2 .…”

Section: Introductionmentioning

confidence: 99%

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Neutral Metal 1,2-Dithiolenes: Preparations, Properties and Possible Applications of Unsymmetrical in Comparison to the Symmetrical

2012

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This paper is an overview concerning the preparations and properties as well as possible applications of neutral (one component) metal 1,2-dithiolenes (and selenium analogues). The structural, chemical, electrochemical, optical and electrical behavior of these complexes depend strongly on the nature of ligand and/or the metal. The results of unsymmetrical in comparison to those of symmetrical complexes related to the properties of materials in the solid state are primarily discussed. The optical absorption spectra exhibit strong bands in the near IR spectral region ca. 700 to ca. 1950 nm. X-ray crystal structure solutions show that the complexes usually have square-planar geometry with S-S and/or M-S contacts. Some of them behave as semiconductors or conductors (metals) and are stable in air. The cyclic voltammograms at negative potentials are different from the corresponding potentials of tetrathiafulvalenes (TTFs). As a consequence, the LUMO bands occur at much lower levels than those of TTFs. Consequently, electrical measurements under conditions of field effect transistors exhibit n-type or ambipolar behavior. Illumination of materials with high power lasers exhibits non-linear optical behavior. These properties enable metal 1,2-dithiolene complexes to be classified as promising candidates for optical and electronic applications, (e.g., saturable absorbers, ambipolar inverters). OPEN ACCESSCrystals 2012, 2 763

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Density Functional Derived Structures and Molecular Properties of Nickel Dithiolenes and Related Complexes

Lauterbach

Fabian²

1999

Eur. J. Inorg. Chem.

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The molecular and electronic structure of the planar nickel dithiolene (1c, R = H) and of related complexes derived from nickel dithiolene by replacement of Ni by Pd (palladium dithiolene, 2c, R = H) or by Pt (platinum dithiolene, 3c, R = H), or by replacement of S by NH (nickel diiminolene, 1a, R = H), O (nickel dioxylene, 1b, R = H) or Se (nickel diselenolene, 1d, R = H), were studied by density functional theory using the B3LYP functional and the valence triple‐zeta basis set 6‐311+G* for all atoms except Pd and Pt. For the latter atoms the quasirelativistic effective core potentials of the Stuttgart group were employed. The molecular structure of nickel dithiolene (1c, R = H) is satisfactorily reproduced by DFT calculations. The geometry of the corresponding platinum complexes 3a–3d is more sensitive to relativistic effects, resulting in the contraction of the X–Pt bonds. As shown with the metal dithiolenes, the two ligands are structurally related to mononegative ions of open shell structure. The C–C bond lengths of the complexes are close to those of aromatic and chain‐type polymethine structures (about 1.4 Å). The nickel dithiolene (1c, R = H) and related complexes have D2h symmetry and are 14 π‐electron systems with 10 π‐electrons at the ligands and 4 π‐electrons at the metal center. The natural population analysis has confirmed that metal M++ does accept electrons from the ligands but to a lesser extent than expected. The empty d‐orbitals of M++ are only partly occupied in the molecular ground state. The positive charge of the metal decreases in the order Ni > Pd > Pt. The 1H chemical shifts and the nucleus‐independent chemical shifts (NICSs) of the ring moieties calculated by GIAO‐DFT display a pronounced electron delocalization. In agreement with the calculated C–C bond lengths the 1H chemical shifts and the NICS values show a marked bond delocalization. The NICS values show a change of the aromatic delocalization in the order Ni > Pd < Pt and NH > O < S < Se. The wave numbers of the IR spectra of the complexes calculated by DFT are grouped in separate frequency regions. The very intense absorption of 1c (R = H) in the visible region of the spectrum is surprisingly well reproduced by ab initio single‐only configuration interaction calculations. While the color band of the palladium complex is predicted to be red‐shifted relative to the nickel complex, a blue shift is calculated on passing from the palladium to the platinum complex. The blue shift is, in part, due to the relativistic contraction of bond lengths in the Pt complexes.

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The chemistry of 1,3-dithiole-2-thione-4,5-dithiolate (dmit)

Cited by 220 publications

References 213 publications

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Neutral Metal 1,2-Dithiolenes: Preparations, Properties and Possible Applications of Unsymmetrical in Comparison to the Symmetrical

Density Functional Derived Structures and Molecular Properties of Nickel Dithiolenes and Related Complexes

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