Self-Assembly of Light-Harvesting Crystalline Nanosheets in Aqueous Media

Shahar, Chen; Baram, Jonathan; Tidhar, Yaron; Weissman, Haim; Cohen, Sidney R.; Pinkas, Iddo; Rybtchinski, Boris

doi:10.1021/nn400484y

Cited by 60 publications

(64 citation statements)

References 55 publications

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“…The interfiber spacing is (4.4 AE 0.7) nm (lighter contrast areas), which corresponds to partially folded PEG chains. [9] The fiber width and interfiber distances are in good agreement with the center-to-center spacing of 6.2 nm revealed by FFT (Figure 3 A). Rheological measurements indicate a low degree of interaction between the fibers (see Figure S11 in the Supporting Information), despite their alignment observed in cryo-TEM.…”

supporting

confidence: 81%

“…Femtosecond transient absorption studies were carried out to probe the excited state dynamics of 1 G and 1 P. Laserpower dependence of the excited state decay reveals dissimilar exciton annihilation [9] behavior for 1 P and 1 G (see Figure S12 in the Supporting Information). The 1 G nanofibers exhibit a superior exciton hopping as evidenced by stronger power dependence, and may be attributed to the contribution of the J-aggregation mode and longer exciton lifetimes in 1 G, thus favoring efficient exciton hopping.…”

Section: Tem (Seementioning

confidence: 99%

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Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

Baram¹,

Weissman²,

Tidhar³

et al. 2014

Angewandte Chemie

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In covalent polymerization, a single monomer can result in different polymer structures due to positional, geometric, or stereoisomerism. We demonstrate that strong hydrophobic interactions result in stable noncovalent polymer isomers that are based on the same covalent unit (amphiphilic perylene diimide). These isomers have different structures and electronic/photonic properties, and are stable in water, even upon prolonged heating at 100 8C. Such combination of covalent-like stability together with structural/functional variation is unique for noncovalent polymers, substantially advancing their potential as functional materials.

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confidence: 81%

Section: Tem (Seementioning

confidence: 99%

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

Baram¹,

Weissman²,

Tidhar³

et al. 2014

Angewandte Chemie

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“…3a), suggesting that charge screening allows CA molecules to pack into crystalline assemblies. While perylene-based crystalline nanosheets have been reported previously 21 , our system represents a unique example of chromophore crystallization within a hydrogel. To corroborate our solution phase X-ray scattering results, we carried out 2D grazing-incidence X-ray scattering (GIXS) on calcium-containing gels dried on silicon substrates (Fig.…”

Section: Resultsmentioning

confidence: 88%

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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“…Recently, tris-PBI 3-37 was designed to produce crystalline 2D nanostructures in aqueous media. 283 This highly ordered 2D array exhibited excellent solar light absorption and fast exciton transfer, thus being promising for light harvesting applications.…”

Section: Self-assembly Of Dye Arrays Composed Of Multiple Pbismentioning

confidence: 99%

Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials

et al. 2015

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CONTENTS 1. Introduction 962 1.1. Prologue 962 1.2. Parent Perylene Bisimide Chromophore 963 1.3. Core-Substituted Perylene Bisimides 964 1.4. Perylene Bisimides in the Solid State 966 1.5. Areas of Application 966 2. Linear, Dendritic, and Macrocyclic Covalent PBI Ensembles 968 2.1. Excitonic Coupling and Deactivation Processes of Photoexcited PBIs 969 2.2. Rigid PBI Dimers 971 2.3. Flexible PBI Ensembles 974 2.4. Cyclic PBI Ensembles 976 3. π-Stacked PBI Assemblies 979 3.1. Self-Assembly of Core-Unsubstituted PBIs in Solution 979 3.2. Organization of Core-Unsubstituted PBIs in the Bulk Solid State 984 3.3. Self-Assembly of Amphiphilic PBIs in Aqueous Media and Solid Bulk State 987 3.4. Self-Assembly of Core-Substituted PBIs 991 3.5. Self-Assembly of Dye Arrays Composed of Multiple PBIs 995 3.6. Self-Assembly of Multichromophoric PBI Conjugates Containing Other Dyes 996 4. Hydrogen-Bond Directed Self-Assembly 1000 4.1. Self-Assembly Directed by Imide−Imide H-Bonding Interactions 1000 4.2. Self-Assembly Directed by Side-Chain Amide−Amide H-Bonding Interactions 1003 4.3. Self-Assembly Directed by Other H-Bonding Interactions 1006 4.4. Coassembly Directed by Imide−Melamine H-Bonding Interactions 1008 4.5. Coassembly Directed by Melamine−Cyanurate/Barbiturate H-Bonding Interactions 1011

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Self-Assembly of Light-Harvesting Crystalline Nanosheets in Aqueous Media

Cited by 60 publications

References 55 publications

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials

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