Cross‐Hyperconjugation: An Unexplored Orbital Interaction between π‐Conjugated and Saturated Molecular Segments

Emanuelsson, Rikard; Wallner, Andreas; Ng, Eugene A. M.; Smith, Joshua R.; Nauroozi, Djawed; Ott, Sascha; Ottosson, Henrik

doi:10.1002/ange.201206030

Cited by 10 publications

(3 citation statements)

References 47 publications

(21 reference statements)

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“…One of the most common examples of such behaviour is the Si–Si bond, which is characterized by high polarizability and efficient σ–π conjugation 10. Moreover, effective hyper‐cross‐conjugation was recently reported in molecules containing a saturated –Si(SiMe 3 ) 2 – bridge 11. Compounds containing this structural motif have found application in materials science as chemical sensors for aromatic compounds,12 or as efficient electron‐transport materials for LEDs 13.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Optical Properties of 1,1′‐Biphospholes by Chemical Alterations of the P–P Bridge

2014

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Keywords: Phosphorus heterocycles / Charge transfer / Conjugation / Pi interactions / Aromaticity 2,5-Di(1-naphthyl)-1-phenylphosphole (2) was prepared from phenylphosphine and dinaphthylbutadiyne in 70 % yield, and oxidized to its oxide 3. Treatment of 2 with a solution of potassium naphthalide results in selective formation of phospholide anion 4, which can be oxidized with iodine to afford biphosphole 5. The crystal structure of 5 exhibits an unusual s-trans conformation across the P-P bridge that is most stabilized by π-π stacking of the naphthyl substituents. Biphosphole 5 can be oxidized to its mono-oxidized 6 and dioxide 7. Generally, all phosphole oxidations lead to de-

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Section: Introductionmentioning

confidence: 99%

Tuning the Optical Properties of 1,1′‐Biphospholes by Chemical Alterations of the P–P Bridge

2014

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“…Once the device has reached its OFF-state, it remains there even after the power is turned off. [13] When the voltage applied to the molecular circuit is either high enough (>5.35 V) or low enough (<-4.50 V), PVMSiF-based device is irreversibly turned to OFF state, which breaks the circuit and stops the electrical conduction. After reverse sweeps (3 rd and 4 th sweeps) was applied, the device remains at its low conductivity (OFF) state, suggesting a WORM memory behavior.…”

Section: Materials Design Synthesis and Characterizationmentioning

confidence: 99%

“…As a typical example, silafluorene, formed by replacing the sp 3 hybridized carbon of fluorene with silicon, was reported to be an excellent building block for OLEDs with high stability, [12a] for OPV with improved cell efficiency, [12b] and for chemosensors with high sensitivity, [12c] by taking advantage of the particular orbital interactions between the Si (σ*-π* conjugation etc.) [13] Encouraged by these merits brought by Si incorporation, we intend to introduce Si into the π-stacked polymers; this may offer new opportunities to control the optoelectronic properties and electrons and/or holes flows for the improved or, more importantly, the innovated device performances. [13] Encouraged by these merits brought by Si incorporation, we intend to introduce Si into the π-stacked polymers; this may offer new opportunities to control the optoelectronic properties and electrons and/or holes flows for the improved or, more importantly, the innovated device performances.…”

Section: Introductionmentioning

confidence: 99%

Manipulating charge transport in a π-stacked polymer through silicon incorporation

Wang

Song

et al. 2014

J. Mater. Chem. C

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Given the fundamental importance in charge transport engineering for device operation in molecular electronics, the manipulating strategies and material design principles for a desired application are highly expected. In stark contrast to conventional organic electronic devices, designing organic semiconductors that perform effectively as molecular nanofuse remains a challenge. Based on a novel silicon-containing π-stacked polymer of silafluorene (PVMSiF), we successfully fabricated a molecular nanofuse device with high ON/OFF ratio up to 4×10 6 for the first time. Using a combination of absorption and photoluminescence (PL) spectra, X-ray techniques (XRD), and micro-PL analysis supported by theoretical insights into unit and backbone geometries and wave function delocalizations provided by density functional theory (DFT) and molecular dynamics (MD) simulations, we demonstrate the fundamental correlations between the polymer structures and the spectacular fuse-like resistive switching behaviors. It was shown that the manipulation of charge transport in π-stacked polymer is applicable via silicon incorporation to realize the molecular nanofuse device of the π-stacked polymers, following a silicon-stimulated filament mechanism with breakable π-π stacking at charged states. These findings may have important consequences on future material studies and device applications.

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Predicting an Antiaromatic Benzene Ring in the Ground State Caused by Hyperconjugation

Zhao

Xie

Sun

et al. 2019

Chemistry An Asian Journal

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Benzene, the prototype of aromatics, has six equivalent C−C bonds (1.397 Å), which are intermediate between a C−C double bond and a C−C single bond. For over 80 years, chemists have spent much effort on freezing a localized structure to obtain a distorted bond‐length alternating benzene ring in the ground state, leading to various localized trisannelated benzene rings. However, most of the central benzene rings are still aromatic or nonaromatic. Here we report an antiaromatic benzene ring caused by hyperconjugation. Specifically, symmetric annulation of 5,5‐difluorocyclopentadiene results in an antiaromatic benzene ring, which is supported by various aromaticity indices, including nucleus‐independent chemical shift, anisotropy of the induced current density, π‐separated electron‐localization function and heat of hydrogenation. Our findings highlight a strong power of hyperconjugation, a “weak” interaction in organic chemistry, paving the way for designing and realizing more novel (anti)aromatics.

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Cross‐Hyperconjugation: An Unexplored Orbital Interaction between π‐Conjugated and Saturated Molecular Segments

Cited by 10 publications

References 47 publications

Tuning the Optical Properties of 1,1′‐Biphospholes by Chemical Alterations of the P–P Bridge

Tuning the Optical Properties of 1,1′‐Biphospholes by Chemical Alterations of the P–P Bridge

Manipulating charge transport in a π-stacked polymer through silicon incorporation

Predicting an Antiaromatic Benzene Ring in the Ground State Caused by Hyperconjugation

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