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Long-lived triplet charge-separated state in naphthalenediimide based donor-acceptor systems.

ABSTRACT: 1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor-acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π-π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet-triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor-acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment.

SUBMITTER: Aster A

PROVIDER: S-EPMC8179635 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Long-lived triplet charge-separated state in naphthalenediimide based donor-acceptor systems.

Aster Alexander A Rumble Christopher C Bornhof Anna-Bea AB Huang Hsin-Hua HH Sakai Naomi N Šolomek Tomáš T Matile Stefan S Vauthey Eric E

Chemical science 20210226 13

1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor-acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. ...[more]

PMID: 34168763

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Project description:A new set of [Cu(phen)2]+ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide-alkyne cycloaddition reaction (the "click" or CuAAC reaction) with Sauvage's metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C60 radical anion (C60˙-) and either one-electron oxidized porphyrin (ZnP˙+) or one-electron oxidized ferrocene (Fc˙+) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)2]2+ (τ < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc˙+; τ = 380-560 ns), or ZnP˙+ (τ = 2.3-8.4 μs), and C60˙- have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.

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Long-lived triplet charge-separated state in naphthalenediimide based donor-acceptor systems.

Publications

Long-lived triplet charge-separated state in naphthalenediimide based donor-acceptor systems.

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