Metal‐to‐Ligand Charge Transfer Induced Valence Tautomeric Forms of Non‐Innocent 2,2′‐Azobis(benzothiazole) in Ruthenium Frameworks

Singh, Anil Kumar; Panda, Sanjib; Dey, Sanchaita; Lahiri, Goutam Kumar

doi:10.1002/ange.202100979

Cited by 7 publications

(2 citation statements)

References 41 publications

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“…Ferroelectrics − and pyroelectrics − are important materials, which are widely applied to memory and sensors, owing to a change in their spontaneous electric polarization. − The current challenge is to synthesize new compounds that exhibit an electron transfer-based polarization switching − compared to the more typical mechanism of ion displacement or molecular motion. Molecules that exhibit stimulated electron transfer , behavior (e.g., valence tautomeric VT) complexes − are good candidates for such purposes. Once the compounds that exhibit electron transfer form a polar structure, polarization switching is realized.…”

Section: Introductionmentioning

confidence: 99%

Polar Crystals Using Molecular Chirality: Pseudosymmetric Crystallization toward Polarization Switching Materials

Kanegawa,

Wu,

Zhou

et al. 2024

J. Am. Chem. Soc.

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Polar compounds with switchable polarization properties are applicable in various devices such as ferroelectric memory and pyroelectric sensors. However, a strategy to prepare polar compounds has not been established. We report a rational synthesis of a polar CoGa crystal using chiral cth ligands cth = 5,7,7,12,14,4,8,. Both the original homo metal Co crystal and Ga crystal exhibit a centrosymmetric isostructure, where the dipole moment of metal complexes with the SS-cth ligand and those with the RR-cth ligand are canceled out. To obtain a polar compound, the Co valence tautomeric complex with SS-cth in the homo metal Co crystal is replaced with the Ga complex with SS-cth by mixing Co valence tautomeric complexes with RR-cth and Ga complexes with SS-cth. The CoGa crystal exhibits polarization switching between the pseudononpolar state at a low temperature and the polar state at a high temperature because only Co complexes exhibit changes in electric dipole moment due to metal-to-ligand charge transfer. Following the same strategy, the polarization-switchable CoZn complex was synthesized. The CoZn crystal exhibits polarization switching between the polar state at a low temperature and the pseudononpolar state at a high temperature, which is the opposite temperature dependence to that of the CoGa crystal. These results revealed that the polar crystal can be synthesized by design, using a chiral ligand. Moreover, our method allows for the control of temperature-dependent polarization changes, which contrasts with typical ferroelectric compounds, in which the polar ferroelectric phase typically occurs at low temperatures.

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Section: Introductionmentioning

confidence: 99%

Polar Crystals Using Molecular Chirality: Pseudosymmetric Crystallization toward Polarization Switching Materials

Kanegawa,

Wu,

Zhou

et al. 2024

J. Am. Chem. Soc.

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“…In this regard, valence tautomeric (VT) molecules are ideal structural motifs exhibiting variable electronic configurations responsive to temperature, pressure, and external fields. 13–48 Furthermore, for crystalline materials with switchable macroscopic polarization, it is imperative that the target molecules crystallize in polar space groups so that their dipole moments will not be canceled. To date, there have been only a few non-ferroelectric molecular crystals exhibiting macroscopic polarization switching via electron transfer owing to the difficulties in crystal engineering to align molecules in polar space groups.…”

Section: Introductionmentioning

confidence: 99%

Solvent-dependent valence tautomerism and polarization switching in a heterodinuclear [CrCo] complex

Zheng,

Zhang,

Shui

et al. 2024

Inorg. Chem. Front.

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Synthese eines Kupfer(I)‐Komplexes mit zwei ungepaarten Elektronen durch Oxidation eines Kupfer(II)‐Komplexes mit zwei redoxaktiven Liganden

et al. 2021

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Zwei homoleptische Kupfer(II)-Komplexe [Cu-(L1) 2 ]und [Cu(L2) 2 ]mit anionischen redoxaktiven Liganden wurden synthetisiert, einer mit dem Harnstoffazin-Ligand (L1) und der andere mit Thioharnstoffazin-Ligand (L2). Die Einelektronen-Oxidation der Komplexe lçst einen seltenen redox-induzierten Elektronentransferprozess aus,w elcher zu den monokationischen Kupfer(I)-Komplexen [Cu(L1) 2 ] + und [Cu(L2) 2 ] + mit zwei oxidierten Liganden führt. Während [Cu(L1) 2 ] + am besten als Cu I -Komplex mit zwei neutralen, radikalischen und antiferromagnetischg ekoppelten Liganden beschrieben werden sollte,ist [Cu(L2) 2 ] + ein Cu I -Komplex mit zwei deutlichu nterschiedlichen Ligandeneinheiten im festen Zustand und mit einer magnetischen Suszeptibilitätnahe einer diamagnetischen Verbindung.E ine weitere Einelektronen-Oxidation des Komplexes mit L1-Liganden führt zu einem Dikation [Cu(L1) 2 ] 2+ ,das sich am besten als Cu I -Komplex mit einem zweifacho xidierten, monokationischen Liganden und einem neutralen radikalischen Liganden beschreiben lässt. Die Stabilitäti nm indestens drei Redoxzuständen, die Akkumulation der Spindichtea uf den Liganden und der ungehinderte Ligand-Metall-Elektronentransfer machen diese Komplexefür eine Vielzahl von Anwendungen äußerst attraktiv;h ier testen wir die katalytische aerobe Oxidation von Alkoholen zu Aldehyden. 2021 Die Autoren. AngewandteChemie verçffentlichtv on Wiley-VCH GmbH. Dieser Open Access Beitrag steht unter den Bedingungen der Creative Commons AttributionN on-CommercialL icense, die eine Nutzung, Verbreitung und Vervielfältigung in allen Medien gestattet, sofern der ursprünglicheBeitrag ordnungsgemäß zitiert und nicht fürkommerzielle Zwecke genutzt wird.

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Metal‐to‐Ligand Charge Transfer Induced Valence Tautomeric Forms of Non‐Innocent 2,2′‐Azobis(benzothiazole) in Ruthenium Frameworks

Cited by 7 publications

References 41 publications

Polar Crystals Using Molecular Chirality: Pseudosymmetric Crystallization toward Polarization Switching Materials

Polar Crystals Using Molecular Chirality: Pseudosymmetric Crystallization toward Polarization Switching Materials

Solvent-dependent valence tautomerism and polarization switching in a heterodinuclear [CrCo] complex

Synthese eines Kupfer(I)‐Komplexes mit zwei ungepaarten Elektronen durch Oxidation eines Kupfer(II)‐Komplexes mit zwei redoxaktiven Liganden

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