1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Wenzel, Barbara; Wehse, Burkhard; Schilde, Uwe; Strauch, Peter

doi:10.1002/zaac.200400143

Cited by 19 publications

(8 citation statements)

References 13 publications

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“…All solvents are freshly distilled over appropriate drying agents under nitrogen. Starting materials, HDAniF 72 and Mo 2 (DAniF) 3 (O 2 CCH 3 ), 73 and dipotassium 1,2-dithiooxlate 74 and tetraethylammonium tetrathiooxalate (Et 4 N) 2 tto 75 were synthesized according to published methods.…”

Section: ■ Conclusionmentioning

confidence: 99%

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

et al. 2017

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Three symmetric Mo 2 dimers [Mo 2 (DAniF) 3 ](µ-E 2 CCE 2)[Mo 2 (DAniF) 3 ] (DAniF = N, Nʹ-di(p-anisyl)formamidinate) with oxalate (E = O) or the thiolated derivatives (E = O or S) as bridging ligands have been synthesized, and the optical properties of the mixed-valence (MV) derivatives obtained by one-electron oxidation studied within the framework of the vibronic two-state model. These Mo 2 −Mo 2 systems are effective models for testing electron transfer theories, with the δ electrons of the Mo 2 fragments that are responsible for the redox and optical properties of the MV complex being well isolated from other metal d and ligand π-type orbitals. This in turn gives rise to unique, well-resolved metal to ligand (MLCT) and intervalence charge transfer (IVCT) absorption bands that permit accurate analyses based on band-shape. In the series [Mo 2 (DAniF) 3 ](µ-E 2 CCE 2)[Mo 2 (DAniF) 3 ], the extent of electron delocalization between the Mo 2 cores increases with increasing number of sulfur atoms, E, in the bridge. Higher energy IVCT absorption bands are observed for the more strongly coupled complex, but in contrast to the predictions from the two-state model, the IVCT band becomes more symmetric in shape as the electronic coupling constant increases beyond the Class III border and 2H ab /λ >> 1. Thus, the oxalate-bridged complex (E 2 = O 2) is situated on the Class II-III borderline, while the two thiolated 2 species are well placed deep into Class III, where novel optical behavior can be observed. The electronic coupling matrix elements (H DA) estimated from the transition energy E IT (H DA = E IT /2, 2000-2500 cm − 1) are in excellent agreement with data (H ab , 2400-3000 cm − 1) calculated from the modified Mulliken-Hush expression for Class III systems. DFT calculations show that linear combinations of the δ orbitals of the Mo 2 centers generate the HOMO (out-of-phase, δ−δ) and HOMO-1 (in-phase, δ+δ), with the energy difference corresponding to the E IT. This study illustrates a systematic transition from strongly coupled MV complex near the Class II-III border, to Class III and to systems in which the underlying ground state is better described in terms of simple delocalized electronic states rather evolving from strongly coupled diabatic states which define Class III.

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Section: ■ Conclusionmentioning

confidence: 99%

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

et al. 2017

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“…General comments: All chemicals used in this study are commercially available and were used as received. K 2 S 2 C 2 O 2 ,20 [(Ph 3 P) 2 Cu(NO 3 )],21 (NEt 4 )[InCl 4 ],22 (NH 2 Et 2 )(S 2 CNEt 2 ),23 and K 2 [Sn(S 2 C 2 O 2 ) 3 ]24 were prepared by using published procedures. Thermogravimetric analyses (TGA) were carried out with a TG‐209‐F1 instrument (Netzsch) at a heating rate of 10 K min –1 in aluminum crucibles under an argon atmosphere.…”

Section: Methodsmentioning

confidence: 99%

1,2‐Dithiooxalato‐Bridged Heterobimetallic Complexes as Single‐Source Precursors for Ternary Metal Sulfide Semiconductors

et al. 2014

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The new 1,2‐dithiooxalato‐bridged bimetallic Cu–Ga, Cu–In, and Cu–Sn complexes [{(Ph3P)2Cu(μ‐S2C2O2)}3Ga] (1), [{(Ph3P)2Cu(μ‐S2C2O2)}3In] (2), [(Ph3P)2Cu(μ‐S2C2O2)In(S2CNEt2)2] (3), and [{(Ph3P)2Cu(μ‐S2C2O2)}2Sn(S2C2O2)] (4) were prepared and spectroscopically fully characterized. The crystal structures of 2–4 are presented. Complexes 3 and 4 are potential molecular single‐source precursors (SSP) for the ternary semiconductors CuInS2 and Cu2SnS3, respectively, which can be manipulated under ambient conditions. Indeed, a study of the thermal degradation of 3 and 4 revealed that 3 affords pure nanoscaled CuInS2 (mean diameter ca. 2 nm) when the decomposition is carried out in an oleylamine solution by using a hot‐injection or arrested‐precipitation technique at temperatures well below 250 °C. In contrast, 4 decomposes under the same reaction conditions in an ambiguous manner and forms mixed binary chalcogenide phases. This can be explained by a subtle influence of the relative stability of possible SnII and SnIV intermediates in the case of SSP [{(Ph3P)2Cu(μ‐S2C2O2)}2Sn(S2C2O2)] (4).

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“…This situation is in full agreement with other bis(1,2-dithiosquarato)metalates. [76][77][78][79][80][81][82][83] The bite distances (S-S) in the ligands differ only very slightly. Figures 2 and 4 show the crystal packing of both compounds, which are determined by the cations (BuPh 3 P) + and (HexPh 3 P) + .…”

Section: X-ray Structuresmentioning

confidence: 99%

Bis(1,2-dithiosquarato)nickelates(II) – Synthesis, Structure, EPR and Thermal Behavior

Strauch

Neumann

Kelling

et al. 2015

ACSi

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Dedicated to the memory of Prof. Dr. Jurij V. Bren~i~. Abstract1,2-Dithiosquaratonickelates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. The synthesis and characterization, including mass spectrometry, of a series 1,2-dithios-, with several "onium" cations is reported and the X-ray structures of two diamagnetic complexes, (HexPh 3 P) 2 [Ni(dtsq) 2 ] and (BuPh 3 P) 2 [Ni(dtsq) 2 ] with sterically demanding counter ions are presented. The diamagnetic nickel complexes have been doped as host lattices with traces of Cu(II) to measure EPR for additional structural information. The thermal behavior of this series is studied by thermogravimetry and differential thermal analysis (TG/DTA). The thermolysis in air as well as under nitrogen atmosphere of these complexes results in nickel oxide nano-particles in all cases, which are characterized by X-ray powder diffraction.

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1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Cited by 19 publications

References 13 publications

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

1,2‐Dithiooxalato‐Bridged Heterobimetallic Complexes as Single‐Source Precursors for Ternary Metal Sulfide Semiconductors

Bis(1,2-dithiosquarato)nickelates(II) – Synthesis, Structure, EPR and Thermal Behavior

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1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Cited by 19 publications

References 13 publications

Optical Behaviors and Electronic Properties of Mo2–Mo2 Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo2–Mo2 Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

1,2‐Dithiooxalato‐Bridged Heterobimetallic Complexes as Single‐Source Precursors for Ternary Metal Sulfide Semiconductors

Bis(1,2-dithiosquarato)nickelates(II) – Synthesis, Structure, EPR and Thermal Behavior

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Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model