Multi‐Electron‐Acceptor Dyad and Triad Systems Based on Perylene Bisimides and Fullerenes

Chamberlain, Thomas W.; Davies, E. Stephen; Khlobystov, Andrei N.; Champness, Neil R.

doi:10.1002/chem.201003092

Cited by 36 publications

(33 citation statements)

References 45 publications

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“…In line with reductions of other related symmetric C 60 -dimers and triads, 50,30 each of the fullerene reduction waves is in 2ac commensurate with a two-electron uptake. The peak current of these reductions is thus higher than for those associated with the PMDI reductions, indicating that the latter correspond to a one-electron uptake.…”

Section: Resultssupporting

confidence: 62%

“…[18][19][20] In accord with the discussion, dumbbell-like molecules ( Figure 1) consisting of two π-bridged fullerenes (C 60 -π system-C 60 ) have been of an interest to both chemists and materials scientists. 30 Naphtalenetetracarboxylic diimide (NTCDI), as another representative, have been employed to act as a component of fullerene-based rotaxanes. In addition, the 29 Interestingly, only few systems have been made to carry an electron-accepting central unit.…”

Section: Fig 1 Dumbbell Designmentioning

confidence: 99%

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Fulleropyrrolidine molecular dumbbells act as multi-electron-acceptor triads. Spectroscopic, electrochemical, computational and morphological characterizations

et al. 2015

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a We synthesized three dumbbell-like compounds 2a-c, each containing two C60 groups at the periphery and pyromellitic diimide (PMDI) in the middle, and examined their electronic as well as assembly characteristics with both experimental and computational methods. Cyclic voltammetry (CV) measurements revealed that each of three electron-accepting (AAA) triads could accommodate up to eight electrons. Computational studies (density functional theory, DFT) of 2a-c at PBEPBE/6-311G(d,p) level of theory, with B3LYP/6-31G(d) optimized geometries, revealed that HOMO-LUMO energy gaps are similar to those of the model compound [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Compounds 2a-c were also found to assemble into vesicles and nanoparticles on the copper grid (100-300 nm, TEM), while giving more sizeable aggregates after a deposition on the glass (SEM, > 5 µm). Understanding the packing of 2a-c on various solid substrates, as well as the assembly characteristics in general, is important for tuning the properties and fabrication of electronic/optical devices. On the basis of the results of conformational analysis (MM and DFT calculations), we deduced that different alkyl spacers in 2a-c ought to play a role in π-π interactions between the aromatic components of the triad to guide the packing and therefore morphology of the material.Three novel fulleropyrrolidine dumbbells consisting three electron acceptor moieties joined by alkyl linker displaying tunable electrical and morphological properties were synthesized and characterized.

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Section: Resultssupporting

confidence: 62%

Section: Fig 1 Dumbbell Designmentioning

confidence: 99%

Fulleropyrrolidine molecular dumbbells act as multi-electron-acceptor triads. Spectroscopic, electrochemical, computational and morphological characterizations

et al. 2015

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“…This notwithstanding, fullerene cages are excellent electron acceptors and can support up to six electrons per fullerene cage to form species containing one or more unpaired electrons, in which overall charge and the spin state can be controlled precisely by applied potential [9]. In addition, combining two fullerene cages within the same molecule increases the total spin-carrying capacity and introduces a mechanism of spin-tuning while retaining the intrinsic properties of each of the fullerene cages [10]. The synthesis of such fullerene–bridge–fullerene triads, though not straightforward, has been reported [11], the simplest involving species where the fullerene cages are connected directly by a C–C bond [12], a bridging O-atom [13], or by a transition metal atom [14].…”

Section: Introductionmentioning

confidence: 99%

Tuning the interactions between electron spins in fullerene-based triad systems

Lebedeva¹,

Chamberlain²,

Davies³

et al. 2014

Beilstein J. Org. Chem.

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SummaryA series of six fullerene–linker–fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate, acetate or terephthalate) and enabling precise control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken up per molecule in the potential range between −2.3 and 0.2 V (vs Fc+/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron–electron interactions in the electrochemically generated dianions of these triads, with one electron per fullerene cage were studied by EPR spectroscopy. The nature of electron–electron coupling observed at 77 K can be described as an equilibrium between doublet and triplet state biradicals which depends on the inter-fullerene spacing. The shorter oxalate-bridged triads exhibit stronger spin–spin coupling with triplet character, while in the longer terephthalate-bridged triads the intramolecular spin–spin coupling is significantly reduced.

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“…Beside heavy atoms, efficient ISC of fullerene C 60 is particularly interesting and more promising for PDT application. Photoexcitation of C 60 and its derivatives induces a singlet excited state that is transformed to the corresponding triplet excited state via intersystem energy crossing, with nearly quantitative efficiency [45][46][47][48][49][50][51].…”

Section: Bodipy Bearing C 60mentioning

confidence: 99%

Boron‐Fluorine Photosensitizers for Photodynamic Therapy

Yao

Xiao

Dan

2013

Journal of Chemistry

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Photodynamic therapy (PDT) has been recognized as a promising treatment for cancers and tumors, in which photosensitizer is one of the most important issues. As a class of excellent fluorescent dyes, boron-fluorine derivatives (typically 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene, BODIPY) have preferable ability of generating singlet oxygen and have been under extensive study for PDT sensitizers. In this review, we summarize the recent progress of design and applications of boron-fluorine-based photosensitizers for PDT.

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Multi‐Electron‐Acceptor Dyad and Triad Systems Based on Perylene Bisimides and Fullerenes

Cited by 36 publications

References 45 publications

Fulleropyrrolidine molecular dumbbells act as multi-electron-acceptor triads. Spectroscopic, electrochemical, computational and morphological characterizations

Fulleropyrrolidine molecular dumbbells act as multi-electron-acceptor triads. Spectroscopic, electrochemical, computational and morphological characterizations

Tuning the interactions between electron spins in fullerene-based triad systems

Boron‐Fluorine Photosensitizers for Photodynamic Therapy

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