A novel empirical method for quickly estimating the charge-transfer state of fullerene-donor derivatives

Liu, Xiaolong; Chai, Yongqiang; Wu, Bo; Liu, Liping; Wang, Chunru

doi:10.1039/c9cp05257g

Cited by 4 publications

(10 citation statements)

References 25 publications

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“…This yielded a relationship model between HOMO levels and molecular structures. 21 The model was further validated with 28 donor molecules, showing prediction errors within ±0.2 eV of DFT results, which reflects the rationality of the prediction model. This study offers crucial guidance for designing charge separation systems and selecting appropriate donors.…”

Section: G E E D E Amentioning

confidence: 64%

“…16 The G S term describes the extent to which the solvent influences the chargeseparation state energy. 21 There are two options for achieving stable CSs. One requires a lower 1 E ox or a higher HOMO of the donor, signifying a stronger electron-donating ability.…”

Section: G E E D E Amentioning

confidence: 99%

“…We designed two arylaminefullerene derivatives, DDPA and DA (Figure 1b). 21 The additional N atom in DDPA increases its electron-donating ability, thus producing a more stable CSs. Owing to the higher HOMO of DDPA (−4.35 eV), the energy level of CSs in C 60 -DDPA in toluene (1.49 eV) is lower than the singlet state of C 60 (1.76 eV), resulting in the thermodynamical feasibility of charge separation.…”

Section: Raising the Homo Level Of Donorsmentioning

confidence: 99%

“…Although fullerenes have the potential to attain long-lived CSs, not all fullerene-donor systems exhibit ideally long lifetimes. − In addition, simple and efficient strategies to regulate the CS kinetics of fullerene materials have long been lacking in systematicity and regularity. This necessitates the development of stable CSs design methods and long-lived CSs regulatory strategies.…”

Section: Introductionmentioning

confidence: 99%

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Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Wang,

Wu,

Wang

2024

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Photoinduced charge separation (CS) ensures efficient light-energy conversion. The stable and long-lived charge-separation state (CSs) is beneficial for suppressing charge recombination and facilitating the separation of highly reduction-active electrons or highly oxidation-active holes to participate in subsequent photoreactions. Accordingly, the construction of stable and long-lived charge-separation states has been an important goal for researchers. These results highlighted the importance of fullerene materials. Characterized by their well-defined and stable structures and exceptional electronic properties, fullerenes have emerged as prominent electron acceptors. The energy levels and excited-state electron transfer features can be modulated by altering the carbon cage (selecting diverse carbon-cage configurations), embedding clusters (metallofullerenes), or modifying the functional groups on the carbon cage (fullerene additive reactions). Importantly, the low electron reorganization energy of fullerenes makes them promising materials for constructing long-lived CSs. Therefore, researchers commonly employ fullerenes as acceptors to design photoelectric materials or investigate their fundamental charge separation mechanisms. The primary task is to construct stable CSs through system design and extend the lifetime of CSs according to appropriate regulations. However, critical challenges stem from the inadequate comprehension of CS patterns, unsuitable system choices, and lack of simple and efficient strategies for CS regulation. Therefore, our research approach, which originates from the inherent principles of CS, aims to explore strategies for constructing and regulating stable and long-lived CSs in fullerene derivatives.In this Account, we systematically summarize the following three aspects of charge separation in fullerene materials. (1) Construction of thermodynamically stable CSs. We established a mathematical correlation between the external modifying groups and the HOMO energy levels, enabling a rapid and straightforward prediction of the stability of CSs. Stable CSs can be successfully constructed by increasing the HOMO of the donor, lowering the LUMO of the acceptor, or altering the direction of the CSs. (2) Develop kinetic regulation strategies to extend CSs lifetime. We found that the meta-or ortho-substituted configuration determines the excited-state charge localization, effectively slowing charge recombination and thus prolonging the CSs lifetime. Additionally, our findings indicate that restricting molecular conformational changes can extend the CSs lifetime. Strategies for conformational regulation, including redox regulation and the introduction of steric hindrance, were subsequently designed. (3) Potential applications of stable and long-lived CSs. We primarily elucidated the applications of CSs in photovoltaics and photocatalysis (hydrogen production and NAD + regeneration). Stable and long-lived CSs ensures effective charge separation and ph...

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Section: G E E D E Amentioning

confidence: 64%

Section: G E E D E Amentioning

confidence: 99%

Section: Raising the Homo Level Of Donorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Wang,

Wu,

Wang

2024

Acc. Mater. Res.

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“…The C 60 , Sc 3 N@C 80 , and Y 3 N@C 80 dumbbell conjugates were synthesized by means of 1,3-dipolar cycloaddition reaction (Scheme S1). − Details regarding the synthesis, isolation, and characterization are gathered in the Supporting Information. The absorption spectra of the as-prepared fullerene dumbbells in toluene are presented in Figure S12.…”

mentioning

confidence: 99%

Interfullerene Electronic Interactions and Excited-State Dynamics in Fullerene Dumbbell Conjugates

Chai

Liu

et al. 2023

J. Am. Chem. Soc.

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Several dumbbell conjugates featuring M3N@I h -C80 (M = Sc, Y) and C60 were prepared to systematically investigate interfullerene electronic interactions and excited state dynamics. From electrochemical investigations, we concluded that the redox potentials of our M3N@I h -C80 (M = Sc, Y) dumbbells depend largely on the interfullerene electronic interactions. Assisted by DFT calculation, the unique role of metal atoms was highlighted. Most importantly, ultrafast spectroscopy experiments revealed symmetry-breaking charge separation in Sc3N@C80-dumbbell to yield an unprecedented (Sc3N@C80)•+-(Sc3N@C80)•– charge separated state. This is, to the best of our knowledge, the first time that symmetry-breaking charge separation following photoexcitation is corroborated in a fullerene system. As such, our work shed light on the significance of interfullerene electronic interactions and their uniqueness for modulating excited state properties.

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Enhancing Built‐in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C₆₀ Fullerene into Zirconium‐Based Metal‐Organic Frameworks

et al. 2023

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High‐efficiency photocatalysts based on metal‐organic frameworks (MOFs) are often limited by poor charge separation and slow charge‐transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C60 into a nano‐sized zirconium‐based MOF, NU‐901. By virtue of host‐guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set‐up in C60@NU‐901. The direct consequence is a robust built‐in electric field, which tends to be 10.7 times higher in C60@NU‐901 than that found in NU‐901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g−1 h−1 for C60@NU‐901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host‐guest interactions constitutes a promising strategy to design photocatalysts for efficient solar‐to‐chemical energy conversion.

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A novel empirical method for quickly estimating the charge-transfer state of fullerene-donor derivatives

Abstract: A new convenient equivalent conjugated electron number technique is put forward to predict the charge-transfer state in fullerene-donor derivatives.

Cited by 4 publications

References 25 publications

Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Interfullerene Electronic Interactions and Excited-State Dynamics in Fullerene Dumbbell Conjugates

Enhancing Built‐in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C₆₀ Fullerene into Zirconium‐Based Metal‐Organic Frameworks

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A novel empirical method for quickly estimating the charge-transfer state of fullerene-donor derivatives

Abstract: A new convenient equivalent conjugated electron number technique is put forward to predict the charge-transfer state in fullerene-donor derivatives.

Cited by 4 publications

References 25 publications

Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Rational Construction and Efficient Regulation of Stable and Long-Lived Charge-Separation State in Fullerene Materials

Interfullerene Electronic Interactions and Excited-State Dynamics in Fullerene Dumbbell Conjugates

Enhancing Built‐in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C60 Fullerene into Zirconium‐Based Metal‐Organic Frameworks

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Enhancing Built‐in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C₆₀ Fullerene into Zirconium‐Based Metal‐Organic Frameworks