Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand

Dale, Sarah; Bonanno, Nico M.; Pelaccia, Mark; Lough, Alan J.; Miyawaki, Atsuhiro; Takahashi, Kazuyuki; Lemaire, Martin T.

doi:10.1039/c9dt01788g

Cited by 9 publications

(8 citation statements)

References 38 publications

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“…Despite the introduction of strong coordinating sites, this synthetic protocol is often challenged by longer reaction times. 24,31,32 Although this generalized synthetic approach has been used to functionalize PLY-based ligands for the last two decades, it has resulted invariably in the formation of mononuclear metal complexes so far. Our group has recently gained interest in robust PLYbased systems and reported the first Cu(II)-PLY complex and explored its catalytic behavior for the oxidation of polycyclic aromatic hydrocarbons (PAHs).…”

Section: Introductionmentioning

confidence: 99%

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell

Kamboj,

Dey,

Lama

et al. 2023

Dalton Trans.

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Section: Introductionmentioning

confidence: 99%

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell

Kamboj,

Dey,

Lama

et al. 2023

Dalton Trans.

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“…We initiated our study by synthesizing a phenalenyl-based ligand with Dip groups attached to the nitrogen atoms, i.e., (DipN-PLY)H ( 3 ) (Scheme ). Treatment of 9-methoxyphenalenone with 2,6-diisopropylaniline (Dip-NH 2 ) at 120 °C afforded the monoaminated derivative 2 , which was then treated with the Meerwein reagent, followed by the addition of Dip-NHLi to provide ligand 3 . With ligand 3 in hand, the germanium center was introduced by reacting lithiated 3 with GeCl 2 ·dioxane to give chlorogermylene 4 in a 78% yield .…”

Section: Resultsmentioning

confidence: 99%

Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand

et al. 2023

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An open-shell germylene 1 stabilized by a phenalenyl-based bidentate ligand was synthesized and characterized. Because of the high thermal stability originating from spin delocalization over the phenalenyl moiety, it was possible to isolate compound 1 in crystalline form by sublimation at ca. 300 °C. Electron spin resonance (ESR) spectra, crystallographic analysis, theoretical calculations, and reactivities with carbon radicals suggest that the spin of 1 is distributed on the phenalenyl moiety, while 1 reacted with C 2 Cl 6 , PhSSPh, and p-benzoquinone at the germanium center to form Ge−E (E = Cl, S, O) bonds. Furthermore, compound 1 is featured by its reactivity as a "formal germylyne", which allows for the formation of three new σ-bonds or one σ-bond with metal complexation on the germanium center.

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“…TMCs derived from electro-active phenalenyl-based ligands are well-known in the literature. − Haddon, in 1975, introduced the importance of the phenalenyl (PLY) molecule in the modern semiconductor industry and regarded PLY as one of the graphene fragments . The past studies have made it evident that the delocalized carbon-based charged species with unpaired spin in the PLY redox motif have exhibited many promising molecular device properties. − Raman et al used the zinc(II) metal ion complex containing a cationic PLY unit as an electro-active material for constructing a spin-based memory device .…”

Section: Introductionmentioning

confidence: 99%

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies

et al. 2023

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We herein report a novel square-planar complex [Co II L], which was synthesized using the electronically interesting phenalenyl-derived ligand LH 2 = 9,9′-(ethane-1,2-diylbis-(azanediyl))bis(1H-phenalen-1-one). The molecular structure of the complex is confirmed with the help of the single-crystal X-ray diffraction technique. [Co II L] is a mononuclear complex where the Co(II) ion is present in the square-planar geometry coordinated by the chelating bis-phenalenone ligand. The solid-state packing of [Co II L] complex in a crystal structure has been explained with the help of supramolecular studies, which revealed that the π•••π stacking present in the [Co II L] complex is analogous to the one present in tetrathiafulvalene/tetracyanoquinodimethane charge transfer salt, well-known materials for their unique charge carrier interfaces. The [Co II L] complex was employed as the active material to fabricate a resistive switching memory device, indium tin oxide/Co II L/Al, and characterized using the write-read-erase-read cycle. The device has interestingly shown a stable and reproducible switching between two different resistance states for more than 2000 s. Observed bistable resistive states of the device have been explained by corroborating the electrochemical characterizations and density functional theory studies, where the role of the Co II metal center and π-conjugated phenalenyl backbone in the redox-resistive switching mechanism is proposed.

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Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand

Abstract: Neutral Fe3+ and Co3+ complexes are reported featuring mixed-valent open- and closed-shell ligands, low energy IVCT bands and electrical conductivity.

Cited by 9 publications

References 38 publications

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell

Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies

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Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand

Abstract: Neutral Fe3+ and Co3+ complexes are reported featuring mixed-valent open- and closed-shell ligands, low energy IVCT bands and electrical conductivity.

Cited by 9 publications

References 38 publications

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H2O2 fuel cell

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H2O2 fuel cell

Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies

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A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell

A closed-shell phenalenyl-based dinuclear iron(iii) complex as a robust cathode for a one-compartment H₂O₂ fuel cell