Photoinduced electron transfer in mechanically interlocked suit[3]ane systems

Solà

et al. 2022

J Nanostruct Chem

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The chemistry of hoop-shaped π-conjugated molecules has increased dramatically in recent years. We present here a computational modeling of photoinduced electron transfer processes in a series of host–guest complexes of Twin1, Twin2, and Twin3 double nanohoops with C60 fullerene. According to our findings, charge transfer from cycloparaphenylene (CPP) fragments to C60 is energetically favorable and occurs on a sub-nanosecond time scale. The slow decay of the generated charge-separated state suggests that the complexes may be of interest for organic photovoltaics. Graphical abstract

Section: Complexmentioning

confidence: 99%

Photoinduced electron transfer in host–guest complexes of double nanohoops

Solà

et al. 2022

J Nanostruct Chem

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“…Note that the rates of ET and CR processes were computed in the Franck‐Condon region. We have previously shown that the effect of internal geometry reorganization on ΔG 0 is rather small for large conjugated systems such as fullerenes and their inclusion complexes [48,49] . The use of the FCD model, based on the unitary transformation of adiabatic states into diabatic ones, makes it possible to estimate the coupling beyond the crossing point.…”

Section: Resultsmentioning

confidence: 99%

“…We have previously shown that the effect of internal geometry reorganization on ΔG 0 is rather small for large conjugated systems such as fullerenes and their inclusion complexes. [48,49] The use of the FCD model, based on the unitary transformation of adiabatic states into diabatic ones, makes it possible to estimate the coupling beyond the crossing point. The FCD method provides good estimates of the coupling and is recommended for extended molecular systems.…”

Section: Electron Transfer Ratesmentioning

confidence: 99%

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

George

Voityuk

et al. 2023

Chemistry A European J

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An approach to modulating the properties of carbon nanorings by incorporating pyrrolo[3,2‐b]pyrrole units is of particular interest due to the combined effect of heteroatom and antiaromatic character on electronic properties. The inclusion of units other than phenylene leads to the formation of stereoisomers. In this work, we computationally study how the spatial orientation of monomeric units in the ring affects the properties of cyclic dibenzopyrrolo[3,2‐b]pyrroles and their complexes with C60 fullerene. For [4]PP and [4]DHPP, the most symmetrical AAAA isomer is the most stable and forms stronger interactions with fullerene than the isomers where one or two monomeric units are flipped, mostly due to less Pauli repulsion. π‐Electron delocalization in the monomeric unit is crucial for directing the electron transfer (from or to nanoring). The energy of excited states with charge transfer depends on the HOMO–LUMO gap, which varies from one stereoisomer to another only for [4]DHPP⊃C60 with aromatic 1,4‐dihydropyrrolo[3,2‐b]pyrrole units. The rates of electron transfer and charge recombination reactions are relatively weakly dependent of the spatial isomerism of nanorings.

“…For large conjugated systems, the effect of internal geometry reorganization on DG 0 is rather small and can be safely neglected. 61,62 However, in the studied complexes, the Bowl fragment is relatively small, and the relaxation effect can be signicant. Thus, we studied the effect of geometry relaxation on the rate of charge recombination in DCM for rim-NCorIC 60 , hub-NCorIC 60 , PP-bowlIC 60 , Hyd-bowlIC 60 , Cyc-bowlIC 60 , and SumIC 60 (Table 4).…”

Section: Electron Transfer Rates and The Effect Of Excited State Geom...mentioning

confidence: 94%

Nitrogen-doped molecular bowls as electron donors in photoinduced electron transfer reactions

Solà

et al. 2022

Nanoscale Adv.

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