Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C<sub>60</sub> Fullerene

George, Gibu; Stasyuk, Olga A.; Voityuk, Alexander A.; Stasyuk, Anton J.; Solà, Miquel

doi:10.1002/chem.202300503

Cited by 2 publications

(3 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We considered four stereoisomers of each nanohoop and found that the most symmetric isomer (AAAA in Figure 5) is the most stable. 41 However, all isomers are found within a narrow energy range (less than 2 kcal/mol), suggesting that all of them could be present in the reaction mixture. The calculated energy barriers for the rotation of a monomer unit around the C−C bond are relatively high, 26.3 and 28.5 kcal/mol at the CAM-B3LYP-D3(BJ)/def2-TZVP level for [4]DHPP and [4]PP, respectively.…”

Section: Effects Of Aromaticity/antiaromaticitymentioning

confidence: 99%

“…The modeled [4]DHPP and [4]PP nanohoops can exist in several diastereomeric forms, which are achieved by the rotation of one or more monomer units around single C–C bonds. We considered four stereoisomers of each nanohoop and found that the most symmetric isomer (AAAA in Figure ) is the most stable . However, all isomers are found within a narrow energy range (less than 2 kcal/mol), suggesting that all of them could be present in the reaction mixture.…”

Section: Effects Of Aromaticity/antiaromaticitymentioning

confidence: 99%

Section: Effects Of Aromaticity/antiaromaticitymentioning

confidence: 99%

See 2 more Smart Citations

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Stasyuk,

Voityuk,

Stasyuk

et al. 2023

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Metrics & MoreArticle Recommendations CONSPECTUS: Photoinduced electron transfer (PET) in carbon materials is a process of great importance in light energy conversion. Carbon materials, such as fullerenes, graphene flakes, carbon nanotubes, and cycloparaphenylenes (CPPs), have unusual electronic properties that make them interesting objects for PET research. These materials can be used as electron−hole transport layers, electrode materials, or passivation additives in photovoltaic devices. Moreover, their appropriate combination opens up new possibilities for constructing photoactive supramolecular systems with efficient charge transfer between the donor and acceptor parts. CPPs build a class of molecules consisting of para-linked phenylene rings. CPPs and their numerous derivatives are appealing building blocks in supramolecular chemistry, acting as suitable concave receptors with strong host−guest interactions for the convex surfaces of fullerenes. Efficient PET in donor−acceptor systems can be observed when charge separation occurs faster than charge recombination. This Account focuses on selected inclusion complexes of carbon nanohoops studied by our group. We modeled charge separation and charge recombination in both previously synthesized and computationally designed complexes to identify how various modifications of host and guest molecules affect the PET efficiency in these systems. A consistent computational protocol we used includes a time-dependent density-functional theory (TD-DFT) formalism with the Tamm− Dancoff approximation (TDA) and CAM-B3LYP functional to carry out excited state calculations and the nonadiabatic electron transfer theory to estimate electron-transfer rates. We show how the photophysical properties of carbon nanohoops can be modified by incorporating additional π-conjugated fragments and antiaromatic units, multiple fluorine substitutions, and extending the overall π-electron system. Incorporating π-conjugated groups or linkers is accompanied by the appearance of new charge transfer states. Perfluorination of the nanohoops radically changes their role in charge separation from an electron donor to an electron acceptor.Vacancy defects in π-extended nanohoops are shown to hinder PET between host and guest molecules, while large fully conjugated π-systems improve the electron-donor properties of nanohoops. We also highlight the role of antiaromatic structural units in tuning the electronic properties of nanohoops. Depending on the aromaticity degree of monomeric units in nanohoops, the direction of electron transfer in their complexes with C 60 fullerene can be altered. Nanohoops with aromatic units usually act as electron donors, while those with antiaromatic monomers serve as electron acceptors. Finally, we discuss why charged fullerenes are better electron acceptors than neutral C 60 and how the charge location allows for the design of more efficient donor−acceptor systems with an unusual hypsochromic shift of the charge transfer band in polar solvents.

show abstract

Section: Effects Of Aromaticity/antiaromaticitymentioning

confidence: 99%

Section: Effects Of Aromaticity/antiaromaticitymentioning

confidence: 99%

See 1 more Smart Citation

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Stasyuk,

Voityuk,

Stasyuk

et al. 2023

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

show abstract

Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C₁₈ to C₁₆

Stasyuk,

Voityuk,

Stasyuk

2024

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Recent advances in synthetic methods, combined with tip‐induced on‐surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C16 and C18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron‐withdrawing ability of cyclocarbon molecules. The vdW complexes of C16 and C18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from the donor partner to the cyclocarbons that occurs on a picosecond time scale. The lower reorganization energy of C16 compared to C18 leads to a significant acceleration of the ET reactions.

show abstract

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C₆₀ Fullerene

Cited by 2 publications

References 55 publications

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C₁₈ to C₁₆

Contact Info

Product

Resources

About

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C60 Fullerene

Cited by 2 publications

References 55 publications

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Photoinduced Electron Transfer in Inclusion Complexes of Carbon Nanohoops

Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C18 to C16

Contact Info

Product

Resources

About

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C₆₀ Fullerene

Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C₁₈ to C₁₆