Self-Assembly, Dynamics, and Phase Transformation Kinetics of Donor−Acceptor Substituted Perylene Derivatives

Tasios, Nikos; Grigoriadis, Christos; Hansen, Michael Ryan; Wonneberger, Henrike; Li, Chen; Spiess, Hans Wolfgang; Müllen, Kläus; Floudas, G.

doi:10.1021/ja102150g

Cited by 56 publications

(53 citation statements)

References 41 publications

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“…3a inset). The short dimension of the unit cell is consistent with known π-π stacking distances for perylene imides (0.35 nm) 20 , while the long dimension corresponds to the edge-to-edge distance between adjacent perylene moieties (0.83 nm). CA solutions without added electrolytes showed weaker diffraction peaks than those of the gels (Fig.…”

Section: Resultssupporting

confidence: 79%

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

et al. 2014

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Integration in a soft material of all molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles such as plant chloroplasts which co-localize molecules involved in light absorption, charge transport, and catalysis to create chemical bonds with light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports. The development of soft materials that integrate all necessary molecular components to generate storable fuels in the presence of sunlight is an unexplored area of chemistry with potential impact in renewable energy. Such systems could have advantages over the use of large volumes of liquids, dispersions of expensive or toxic inorganic particles, or complex devices. The use of such soft materials with integrated functions and high water content is bioinspired by the internal structure of chloroplasts in plants. These photosynthetic organelles have evolved to co-localize within stacked lipid bilayers in their stroma the protein machinery which integrates light-absorption, charge transport, and the catalytic functions necessary to convert light energy into chemical bonds1,2. Efforts to emulate natural photosynthetic systems over the past several decades have concentrated on the development of efficient catalysts for water oxidation and proton reduction3-7. In other recent work, catalysts have been coupled to light absorbing CdSe quantum dots8, Si microrods9, and organic dyes10,11 to create artificial photosynthetic systems. Also functional devices capable of performing water-splitting and fuel-generating reactions using earth-abundant resources have been demonstrated12. The development of bionspired soft materials that can be shaped into forms and integrate light-harvesting, charge transport, and catalytic functions to produce solar fuels is an obvious gap. This gap can be addressed through self-assembly strategies for materials in which a bottom-up approach fine tunes all functional aspects of a catalytic system13. Organic systems may have shorter lifetimes than their inorganic counterparts, but could have their own niche in sustainable energy given their soft matter nature and low energy requirements for production. We report here on a strategy to create supramolecular hydrogels that integrate both light-absorbing chromophores and catalysts into a m...

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Section: Resultssupporting

confidence: 79%

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

et al. 2014

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“…Solid-state NMR is a unique method that offers access to molecular packing details for polymers and other organic-based materials [29][30][31][32][33] and to details about the donor-acceptor packing in CDT-BTZ polymers [34,35]. For CDT-BTZ-C16, we were able to show from a combination of X-ray diffraction and solid-state NMR that the CDT-BTZ polymer chains self-assemble into π-stacks, where the single polymer chain includes alternating CDT units, pointing in opposite directions (packing in a staggered fashion) and BTZ moieties stacked in an antiparallel configuration along the π-stacking direction [13].…”

Section: Resultsmentioning

confidence: 99%

Solid-State Organization and Ambipolar Field-Effect Transistors of Benzothiadiazole-Cyclopentadithiophene Copolymer with Long Branched Alkyl Side Chains

et al. 2013

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Abstract:The solid-state organization of a benzothiadiazole-cyclopentadithiophene copolymer with long, branched decyl-tetradecyl side chains (CDT-BTZ-C14,10) is investigated. The C14,10 substituents are sterically demanding and increase the π-stacking distance to 0.40 nm from 0.37 nm for the same polymer with linear hexadecyls (C16). Despite the bulkiness, the C14,10 side chains tend to crystallize, leading to a small chain-to-chain distance between lamellae stacks and to a crystal-like microstructure in the thin film. Interestingly, field-effect transistors based on solution processed layers of CDT-BTZ-C14,10 show ambipolar behavior in contrast to CDT-BTZ-C16 with linear side chains, for which hole transport was previously observed. Due to the increased π-stacking distance, the mobilities are only 6 × 10

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“…This is especially important in the case of PMI sensitizers as the flat, rigid and relatively large perylene cores show a strong tendency to aggregate. [54] Another important tool for molecular design is a spacer between donor and acceptor or the deliberate avoidance of one. Spacer molecules are used for fine tuning of absorption and orbital energies.…”

Section: Perylene Monoimides In Bulk Heterojunction Cellsmentioning

confidence: 99%

“…This is particularly relevant for perylene imide or anhydride sensitizers, as perylene show a high tendency to aggregate due to their large and flat core. [54] On the other hand it is desirable for DSCs to achieve a high dye concentration on the semiconductor surface. Related to these two antagonistic aims a study was carried out comparing the unsubstituted PMA 82 with the phenoxy-substituted PMA 83 and a (tetraphenyl)phenyl-phenoxy-substituted PMA 84.…”

Section: Perylene Monoimides In Dye-sensitized Solar Cellsmentioning

confidence: 99%

Perylene Imides for Organic Photovoltaics: Yesterday, Today, and Tomorrow

Li¹,

Wonneberger²

2012

Advanced Materials

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Perylene imides have been an object of research for 100 years and their derivatives are key n-type semiconductors in the field of organic electronics. While perylene diimides have been applied in many electronic and photonic devices, their use can be traced back to the first efficient organic solar cell. By functionalizing different positions of the in total 12 positions (four peri, four bay, and four ortho-positions) on the perylene core, perylene imides with significantly different optical, electronic and morphological properties may be prepared. Perylene imides and their derivatives have been used in several types of organic photovoltaics, including flat-, and bulk-heterojunction devices as well as dye-sensitized solar cells. Additionally perylene imides-based copolymers or oligomers play an important role in single junction devices. In this review, the relationship between the photovoltaic performance and the structure of perylene imides is discussed.

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Self-Assembly, Dynamics, and Phase Transformation Kinetics of Donor−Acceptor Substituted Perylene Derivatives

Cited by 56 publications

References 41 publications

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

Solid-State Organization and Ambipolar Field-Effect Transistors of Benzothiadiazole-Cyclopentadithiophene Copolymer with Long Branched Alkyl Side Chains

Perylene Imides for Organic Photovoltaics: Yesterday, Today, and Tomorrow

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