EPR-Einkristall-Untersuchungen an (n-Bu4N)2[Cu(dmit)2] im antiferromagnetisch gekoppelten Wirtsgitter (n-Bu4N)2[(dmit)Cu(tto)Cu(dmit)]: Ein Beitrag zur Aufklärung der sogenannten „paramagnetischen Verunreinigung“ im Wirtsgitter / A Single Crystal EPR Investigation on (n-Bu4N)2[Cu(dmit)2] in the Antiferromagnetically Coupled Host Lattice (n-Bu4N)2[(dmit)Cu(tto)Cu(dmit)]: A Contribution to the Natur

Teschmit, Grit; Strauch, Peter; Barthel, André; Reinhold, J.; Kirmse, R.

doi:10.1515/znb-1999-0702

Cited by 3 publications

(3 citation statements)

References 2 publications

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“…This trend is slightly observed in the dark states of 1-3 and is more evident in the M(dmit) 2 radical anions (M = Ni, Pd, Pt, etc.) under dark conditions, where the hybridization between ligands' πand metals' d-orbitals (π-d mixing) is less important than that in the [Cu(dmit) 2 ] 2´a nions (Table S14 in the Supplementary Materials) [68,[72][73][74][75][76][77][78][79]. In contrast, whether under dark or UV irradiated conditions, the SOMOs of [Cu(dmit) 2 ] 2´a nions have a much higher degree of π-d mixing than that in other metal-dithiolene complex anions.…”

Section: Electron Spin Resonance Under Uv Irradiationmentioning

confidence: 99%

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

2016

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Electrical and magnetic properties are dominated by the (de)localization and the anisotropy in the distribution of unpaired electrons in solids. In molecular materials, these properties have been indirectly controlled through crystal structures using various chemical modifications to affect molecular structures and arrangements. In the molecular crystals, since the energy band structures can be semi-quantitatively known using band calculations and solid state spectra, one can anticipate the (de)localization of unpaired electrons in particular bands/levels, as well as interactions with other electrons. Thus, direct control of anisotropy and localization of unpaired electrons by locating them in selected energy bands/levels would realize more efficient control of electrical and magnetic properties. In this work, it has been found that the unpaired electrons on Cu(II)-complex anions can be optically controlled to behave as anisotropically-delocalized electrons (under dark) or isotropically-localized electrons like free electrons (under UV), the latter of which has hardly been observed in the ground states of Cu(II)-complexes by any chemical modifications. Although the compounds examined in this work did not switch between conductors and magnets, these findings indicate that optical excitation in the [Cu(dmit) 2 ] 2´s alts should be an effective method to control spin distribution and anisotropy.

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Section: Electron Spin Resonance Under Uv Irradiationmentioning

confidence: 99%

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

2016

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“…There is a one (2 and 3) or a half (1) 2¹ are reported using solution 234 or magnetically diluted single-crystalline samples. 232,233 Under dark conditions, the ESR spectra measured for the single crystals of 13 were symmetric without (hyper)fine structures. The g-values were approximately estimated from the maxima of the integrated ESR spectra.…”

Section: Electrical Resistivity and Magnetic Susceptibilitymentioning

confidence: 99%

“…They are comparable with that of free electrons (³2.0023) irrespective of the relative direction of H. 244 In fact all of the ESR spectra under UV-irradiation for 13 completely overlapped with those of DPPH (1,1-Diphenyl-2-picrylhydrazyl; 2¹ anions have much higher degree of πd mixing than that in other metaldithiolene complex anions. 232,233,241244,253257 Some of the excited MOs (Figure 78) are localized around the Cu atoms with rather spherical geometries as a result of the πd mixing. Thus the orbital angular momentum is practically quenched, which makes spinorbit coupling negligible.…”

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

Wenzel

Wehse

Schilde

et al. 2004

Zeitschrift anorg allge chemie

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Indium(III)‐chlorid bildet in wäßriger Lösung mit Kalium‐1,2‐Dithiooxalat (dto) und Kalium‐1,2‐Dithioquadratat (dtsq) stabile Koordinationsverbindungen. Während aufgrund der ausgeprägteren Brückenbildungstendenz mit 1,2‐Dithiooxalat in allen untersuchten Fällen thiooxalatverbrückte Zweikernkomplexe gebildet werden, können mit 1,2‐Dithioquadratat bei identischem Donoratomsatz einkernige Trischelatkomplexe isoliert werden. Mit (BzlMe3N)4[(dto)2In(dto)In(dto)2] (1), (BzlPh3P)4[(dto)2In(dto)In(dto)2] (2), (BzlMe3N)3[In(dtsq)3] (3), (Bu4N)3[In(dtsq)3] (4) und (Ph4P)[In(dtsq)2(DMF)2] (5) konnten fünf Komplexe kristallin isoliert und mittels Röntgenkristallstrukturanalyse charakterisiert werden. In Abhängigkeit vom Typ der Komplexe und dem jeweiligen Kation kristallisieren die Verbindungen in unterschiedlichen Raumgruppen. Strukturparameter s. Abstract.

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Cited by 3 publications

References 2 publications

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light

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

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

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