Recent Progress in Hydrogen-Bonded π-Conjugated Systems Displaying J-Type Aggregates

Ávila‐Rovelo, Nelson Ricardo; Ruiz‐Carretero, Amparo

doi:10.1055/s-0040-1708502

Cited by 17 publications

(19 citation statements)

References 97 publications

(105 reference statements)

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“…After the serendipitous discovery of J-aggregates in the 1930s, − the interest in their photophysical properties has been emerging while finding practical applications, for instance in bioimaging, , dye chemistry, and other areas of materials chemistry. − The most well-known class of molecules forming J-aggregates is probably cyanine dyes, − but examples covering many other dye classes exist, including BODIPY dyes, − squaraine dyes, − and porphyrins, − among others. , Rylenes is a class of dyes based on fused naphthalenes, and J-aggregate-forming examples include mainly perylene bisimides. − …”

Section: Introductionmentioning

confidence: 99%

Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

Cravcenco

Edhborg

et al. 2021

J. Am. Chem. Soc.

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Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower the excited state energy, allowing for emission well into the near-infrared regime. However, as we show here, it is not only the excited state energy modifications that J-aggregates can provide. A bay-alkylated quaterrylene was synthesized, which was found to form J-aggregates in 1,1,2,2-tetrachloroethane. A combination of superradiance and a decreased nonradiative relaxation rate made the J-aggregate four times more emissive than the monomeric counterpart. A reduced nonradiative relaxation rate is a nonintuitive consequence following the 180 nm (3300 cm −1 ) red-shift of the J-aggregate in comparison to the monomeric absorption. However, the energy gap law, which is commonly invoked to rationalize increased nonradiative relaxation rates with increasing emission wavelength, also contains a reorganization energy term. The reorganization energy is highly suppressed in J-aggregates due to exciton delocalization, and the framework of the energy gap law could therefore reproduce our experimental observations. J-Aggregates can thus circumvent the common belief that lowering the excited state energies results in large nonradiative relaxation rates and are thus a pathway toward highly emissive organic dyes in the NIR regime.

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Section: Introductionmentioning

confidence: 99%

Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

Cravcenco

Edhborg

et al. 2021

J. Am. Chem. Soc.

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“…It was demonstrated that positively charged OPE used in 10:1 (protein:OPE) molar ratio are effective molecular taggants for selective sensing of the amyloid fibril of the model protein HEWL. Upon fibril formation OPEs forms superluminescent chiral J aggregates [92] and significant fluorescence enhancement is observed (Fig. 5).…”

Section: Oligo(arylene Ethynylene) Electrolytesmentioning

confidence: 96%

Well-defined Conjugated Macromolecules in Sensing

Krywko‐Cendrowska¹,

Szweda²,

Szweda³

2020

Preprint

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Macromolecules with well-defined structures in terms of molar mass and monomer sequence became interesting building blocks for modern materials. The precision of the macromolecular structure makes fine-tuning of the properties of resulting materials possible. Conjugated macromolecules exhibit excellent optoelectronic properties that make them exceptional candidates for sensors construction. The importance of chain length and monomer sequence is particularly important in conjugated systems. The sequence lengths, monomer sequence and structural modification often influence the energy bang gap between HOMO and LUMO orbitals of the molecules that reflect in their properties. Moreover, the supramolecular aggregation that is often observed in oligo-conjugated systems is usually strongly affected by even minor structural changes that are used for sensor designs. This review summarizes the examples of well-defined conjugated macromolecules based on oligo(arylene ethynylene)s skeleton used for sensor applications. The sensing mechanisms and importance of uniformity of structure are discussed.

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“…Upon fibril formation, OPEs form clusters with the fibrils, where the carboxyester terminal groups are isolated from water. In a non-water environment, they form superluminescent chiral J aggregates [94] and significant fluorescence enhancement is observed (Figure 5). It was found that due to the energy transfer the excitation at 280 nm characteristic for HEWL results in the emission of OPE only in solutions containing OPEs and HEWL amyloids that indicate amyloid formation.…”

Section: Oligo(arylene Ethynylene) Electrolytesmentioning

confidence: 99%

Well-Defined Conjugated Macromolecules Based on Oligo(Arylene Ethynylene)s in Sensing

Krywko‐Cendrowska

Szweda

2020

Processes

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Macromolecules with well-defined structures in terms of molar mass and monomer sequence became interesting building blocks for modern materials. The precision of the macromolecular structure makes fine-tuning of the properties of resulting materials possible. Conjugated macromolecules exhibit excellent optoelectronic properties that make them exceptional candidates for sensor construction. The importance of chain length and monomer sequence is particularly important in conjugated systems. The oligomer length, monomer sequence, and structural modification often influence the energy bang gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecules that reflect in their properties. Moreover, the supramolecular aggregation that is often observed in oligo-conjugated systems is usually strongly affected by even minor structural changes that are used for sensor designs. This review discusses the examples of well-defined conjugated macromolecules based on oligo(arylene ethynylene) skeleton used for sensor applications. Here, exclusively examples of uniform macromolecules are summarized. The sensing mechanisms and importance of uniformity of structure are deliberated.

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Recent Progress in Hydrogen-Bonded π-Conjugated Systems Displaying J-Type Aggregates

Cited by 17 publications

References 97 publications

Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

Well-defined Conjugated Macromolecules in Sensing

Well-Defined Conjugated Macromolecules Based on Oligo(Arylene Ethynylene)s in Sensing

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