Organometallics in molecular junctions: conductance, functions, and reactions

Tanaka, Yuya

doi:10.1039/d4dt00668b

Cited by 4 publications

(1 citation statement)

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“…metal electrode-molecule-metal electrode composites, being a minimum component of molecular electronics. Although the relationship between MV complexes and molecular junctions is complicated, as discussed by Launay, recent interest has shifted toward these metal complexes being directly used as components in molecular junctions. − Therefore, investigation of charge-delocalized properties of MV complexes themselves remains of fundamental importance for both models and components in molecular electronics.…”

Section: Introductionmentioning

confidence: 99%

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

Murai,

Ono,

Tanaka

et al. 2024

ACS Org. Inorg. Au

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Four dinuclear organometallic molecular wire complexes with diethynylmetalloporphyrin linkers 1 MM' ,[5,20diarylporphinato]M' (Cp* = η 5 -C 5 Me 5 ; dppe = 1,2-bis(diphenylphosphino)ethane; M/M' = Fe/Zn (1 FeZn ), Ru/Zn (1 RuZn ), Fe/Ni (1 FeNi ), Ru/Ni (1 RuNi ); aryl = 3,5-di-tert-butylphenyl), are synthesized and characterized by NMR, CV, UV−vis-NIR, and ESI-TOF mass spectrometry techniques. Electrochemical investigations combined with electronic absorption spectroscopic studies reveal strong interactions among the electron-donating, redox-active MCp*(dppe) termini and the metalloporphyrin moieties. The monocationic species of the four complexes obtained by chemical oxidation have been characterized as mixedvalence Class II/III or Class III compounds according to the Robin-Day classification despite the long molecular dimension (>1.5 nm), as demonstrated by their intense intervalence charge transfer bands (IVCT) in the near IR region. DFT calculations indicate large spin densities on the metalloporphyrin moieties. Furthermore, the wirelike performance can be finely tuned by coordination of appropriate nitrogen donors to the axial sites of the metalloporphyrin.

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Section: Introductionmentioning

confidence: 99%

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

Murai,

Ono,

Tanaka

et al. 2024

ACS Org. Inorg. Au

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The Many Facets of Ru^II(dppe)₂ Acetylide Compounds

Rigaut,

Galangau

2024

Chemistry A European J

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In this contribution, we describe the various research domains in which RuII alkynyl derivatives are involved. Their peculiar molecular properties stem from a strong and intimate overlap between the metal centered d orbitals and the p system of the acetylide ligands, resulting in plethora of fascinating properties such as strong and tunable visible light absorption with a strong MLCT character essential for sensing, photovoltaics, light‐harvesting applications or non‐linear optical properties. Likewise, the d/p mixing results in tunable redox properties at low potential due to the raising of the HOMO level, and making those compounds particularly suited to achieve redox switching of various properties associated to the acetylide conjugated ligand, such as photochromism, luminescence or magnetism, for charge transport at the molecular level and in field effect transistor devices, or charge storage for memory devices. Altogether, we show in this review the potential of RuII acetylide compounds, insisting on the molecular design and suggesting further research developments for this class of organometallic dyes, including supramolecular chemistry.

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Molecular Break Junction: A Stage for Redox Transformations

Neogi,

Sebastian

et al. 2024

Eur J Org Chem

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An exceptionally brilliant strategy to miniaturize electronic devices is to employ a single‐molecule between two electrodes for carrier conduction at single‐molecule break junctions (SMBJ). To understand the intrinsic mechanisms of operation at these junctions, extremely crucial is to study physical, chemical, and electrochemical properties employing single‐molecules at SMBJs. Further, redox‐based transformations at the nano‐junction could be achieved electrochemically to allow efficient switching between different redox states of a single‐molecule, showcasing the possibility of maneuvering transport properties with on‐off states of the molecule. Herein, are presented the fundamentals of SMBJs, and the electrochemically influenced transformations or switching of organic molecules pursued at SMBJs. Such an understanding of electrochemical phenomena at the nanoscale dimension could bridge the knowledge gap between macroscopic electronic circuits and single‐molecule electronic circuits, whereby the feasibility of switching between the states could maneuver the electronic properties as well as other photophysical parameters.

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Organometallics in molecular junctions: conductance, functions, and reactions

Abstract: Molecular junctions, which involve sandwiching molecular structures between electrodes, play a crucial role in molecular electronics. Recent advances in this field have revealed the vital role of organometallic chemistry in...

Cited by 4 publications

References 98 publications

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

The Many Facets of Ru^II(dppe)₂ Acetylide Compounds

Molecular Break Junction: A Stage for Redox Transformations

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Organometallics in molecular junctions: conductance, functions, and reactions

Abstract: Molecular junctions, which involve sandwiching molecular structures between electrodes, play a crucial role in molecular electronics. Recent advances in this field have revealed the vital role of organometallic chemistry in...

Cited by 4 publications

References 98 publications

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

Controlling Redox and Wirelike Charge-Delocalization Properties of Dinuclear Mixed-Valence Complexes with MCp*(dppe) (M = Fe, Ru) Termini Bridged by Metalloporphyrin Linkers

The Many Facets of RuII(dppe)2 Acetylide Compounds

Molecular Break Junction: A Stage for Redox Transformations

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The Many Facets of Ru^II(dppe)₂ Acetylide Compounds