Synthesis of a Neutral Mixed‐Valence Diferrocenyl Carborane for Molecular Quantum‐Dot Cellular Automata Applications

Christie, John A.; Forrest, Ryan P.; Corcelli, Steven A.; Wasio, Natalie A.; Quardokus, Rebecca C.; Brown, Ryan; Kandel, S. Alex; Lu, Yuhui; Lent, Craig S.; Henderson, Kenneth W.

doi:10.1002/ange.201507688

Cited by 38 publications

(31 citation statements)

References 29 publications

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“…We believe that our work opens new possibilities for studying mixed-valence state molecular systems and quantum dissipation out of equilibrium on the single-molecular level using AFM, simulating in a controlled way key features of the dynamic environment that the molecular systems often experience. Strong coupling between the single-electron transfer within a single molecule and the dynamics of the macroscopic probe may also define novel single-molecular nanoelectromechanical systems 23 toward applications as molecular quantum-dot cellular automata [24][25][26][27] .…”

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confidence: 99%

Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy

et al. 2020

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Intramolecular charge transfer processes play an important role in many biological, chemical and physical processes including photosynthesis, redox chemical reactions and electron transfer in molecular electronics. These charge transfer processes are frequently influenced by the dynamics of their molecular or atomic environments, and they are accompanied with energy dissipation into this environment. The detailed understanding of such processes is fundamental for their control and possible exploitation in future technological applications. Most of the experimental studies of the intramolecular charge transfer processes so far have been carried out using time-resolved optical spectroscopies on large molecular ensembles. This hampers detailed understanding of the charge transfer on the single molecular level. Here we build upon the recent progress in scanning probe microscopy, and demonstrate the control of mixed valence state. We report observation of single electron transfer between two ferrocene redox centers within a single molecule and the detection of energy dissipation associated with the single electron transfer.

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confidence: 99%

Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy

et al. 2020

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“…Most counterion‐free neutral MV complexes are incapable of responding to external charges because the mobile charges in the metal centers are strongly coupled with the opposite charges of the ligands . Although a notable example of internalization of counteranions has been reported using a carborane anion bridge, the guest‐ion‐induced change in the MV electronic structure was not captured, with the exception of zwitterionization of a class III MV anionic complex series with one type of external cation (H + ) . This study represents the first reported example of zwitterionization of MV cationic species with different guest anions being used to modulate the IVCT properties and charge delocalization.…”

Section: Resultsmentioning

confidence: 99%

“…To overcome this problem, Lu and Lent proposed “self‐doping”, whereby opposite charges co‐existed through internalization of counterions, in relation to theoretical models of zwitterionic MV boron clusters. Notably, in an experimental study, Henderson and co‐workers found that a neutral MV diferrocenyl carborane acquires an electronic configuration that can represent the “null” state in QCA half‐cells. With the exception of the few reports cited above, the feasibility of counterion‐free MV systems has not been explored because of the limited availability of MV neutral radicals and zwitterions…”

Section: Introductionmentioning

confidence: 99%

Zwitterionic Mixed Valence: Internalizing Counteranions into a Biferrocenium Framework toward Molecular Expression of Half‐Cells in Quantum Cellular Automata

Tahara

Terashita

Tokunaga

et al. 2019

Chemistry A European J

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Realization of molecular quantum cellular automata (QCA), a promising architecture for molecular computing through current‐free processes, requires improved understanding and application of mixed‐valence (MV) molecules. In this report, we present an electrostatic approach to creating MV subspecies through internalizing opposite charges in close proximity to MV ionic moieties. This approach is demonstrated by unsymmetrically attaching a charge‐responsive boron substituent to a well‐known organometallic MV complex, biferrocenium. Guest anions (CN− and F−) bind to the Lewis acidic boron center, leading to unusual blue‐shifts of the intervalence charge‐transfer (IVCT) bands. To the best of our knowledge, this is the first reported example of a zwitterionic MV series in which the degree of positive charge delocalization can be varied by changing the bound anions, and serves to clarify the interplay between IVCT parameters. The key underlying factor is the variable zero‐level energy difference in the MV states. This work provides new insight into imbuing MV molecules with external charge‐responsiveness, a prerequisite of molecular QCA techniques.

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“…Information is then transmitted and computation can be performed through Coulombic interactions between adjacent cells . Among potential candidates, mixed‐valence organometallic complexes containing two or four metal centers have been proposed as potential single‐molecule QCA cells . In principle, if the metal centers have identical electron affinities, the molecule will have two degenerate charge configurations corresponding to different oxidation states on each metal center.…”

Section: One Electron Less: Toward Mixed‐valence Complexesmentioning

confidence: 99%

Electronic Properties of Poly‐Yne Carbon Chains and Derivatives with Transition Metal End‐Groups

et al. 2020

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During the last three decades, experimental chemists have forged a plethora of bimetallic molecular wires in which two redox‐active metal termini are linked by a carbon‐rich bridge. Their extensive redox chemistry with multiple, stepwise, one‐electron oxidation processes provide them with some interesting electronic and/or magnetic properties for potential applications. The nature of both the metal end‐groups and the carbon bridge has a significant effect on the redox process, which is of paramount importance for the design of these systems. Indeed, examples of mono‐oxidized complexes range from weakly coupled mixed‐valence species through more strongly coupled systems in which the bridging ligand can be intimately involved in electron transfer processes. Similarly, di‐oxidized species can encompass difference in magnetic behavior depending upon not only the nature of the framework of the systems but also the torsion angle between the terminal spin carriers, which allows the inversion of the singlet vs. triplet ground states. Theoretical quantum chemical computations have greatly assisted the development of this field of research. This review illustrates how, in synergy with experiments, computational results can provide additional valuable information on the nature of the localized vs. delocalized electronic communication in the mono‐oxidized mixed‐valence species, or the magnetic coupling differences and characteristics of the di‐oxidized complexes.

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Synthesis of a Neutral Mixed‐Valence Diferrocenyl Carborane for Molecular Quantum‐Dot Cellular Automata Applications

Cited by 38 publications

References 29 publications

Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy

Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy

Zwitterionic Mixed Valence: Internalizing Counteranions into a Biferrocenium Framework toward Molecular Expression of Half‐Cells in Quantum Cellular Automata

Electronic Properties of Poly‐Yne Carbon Chains and Derivatives with Transition Metal End‐Groups

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