Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function

Symons, Henry E.; Hagemann, Maximilian J. L.; Harniman, Robert L.; Faul, Charl F. J.

doi:10.1039/d1tc04518k

Cited by 8 publications

(7 citation statements)

References 64 publications

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“…However, this stabilization energy does not keep up in the higher oligomers of t‐PDI compared with those of the PDI oligomers (Figure 9), possibly due to the inter‐layer steric repulsion of (3p) lone‐pair electrons of sulphur atoms further reinforced by the shorter d S ‐ S distance in the higher oligomers. This may be one of the possible causes of t‐PDIs to follow the isodesmic pathway for the self‐assembly process [40] …”

Section: Resultsmentioning

confidence: 99%

“…This may be one of the possible causes of t-PDIs to follow the isodesmic pathway for the self-assembly process. [40] Figure 10 provides a comparative view of the components of the interaction energies plotted against the number of monomers in the perylene, PDI, and t-PDI oligomers. For all three systems, it is evident that the dispersion energy plays the most significant role in stabilizing the oligomers, followed by the orbital energy terms, which provide additional stabilization, albeit to a smaller extent.…”

Section: Chemphyschemmentioning

confidence: 99%

“…Furthermore, the hetero atom (sulphur) substitution at PDI core significantly enhances their rate of charge‐separation in the organic photovoltaic devices and influences other properties, such as improved electron mobility, electron affinity, and rapid access to the triplet excited states via intersystem crossing [36–39] . A recent study on the supramolecular activity of the trans‐thio‐PDIs shows a strong tendency to aggregate into SMPs via isodesmic assembly mechanism [40] . These intermolecular short‐range and long‐range interactions govern the ground state properties of perylene‐based π ‐conjugated SMPs [41–43] …”

Section: Introductionmentioning

confidence: 99%

“…[36][37][38][39] A recent study on the supramolecular activity of the trans-thio-PDIs shows a strong tendency to aggregate into SMPs via isodesmic assembly mechanism. [40] These intermolecular short-range and long-range interactions govern the ground state properties of perylenebased π-conjugated SMPs. [41][42][43] Although the properties of PDI-derivatives have been extensively studied, [14] the understanding of the fundamental non-covalent interactions [44] that control the structure and property of their supramolecular assemblies require a comprehensive analysis of the electronic structure and bonding in their oligomeric assembly.…”

Section: Introductionmentioning

confidence: 99%

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Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions

2022

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The π-conjugated supramolecular polymers (SMP) have gained vast popularity in materials chemistry and biomedicine due to their spectacular self-assembling behaviour. A detailed account of the electronic structure and bonding through quantum theory of atoms-in-molecules, non-covalent interactions, and energy decomposition analysis (EDA) in the oligomers of perylene, perylene diimide (PDI), and thionated-PDI (t-PDI) is presented. The oligomers of all three molecules show a slip angle of θ � 62°thus forming H-aggregates. The stacking pattern in perylene oligomers prefers a slip-stacked brick-layer order, while the bulkier PDI and t-PDI prefer a parallel step-wise pattern in their oligomers. Successive addition of monomers leads to a consequent rise in the association energy, although to a much greater extent in PDI and t-PDI than in perylene. While the major contribution to this association energy comes from the dispersion interactions in all three systems, the steric interactions in t-PDI quench the cooperativity in its SMP formation. A detailed analysis of the non-covalent interactions reveals the presence of π-π, π-hole•••O=C, and π-hole•••S=C electrostatic interactions playing a crucial role in the selfassembly process, which can be further implemented on developing force field-based methods for understanding the self-assembling mechanism in higher degree of oligomers.

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Section: Resultsmentioning

confidence: 99%

Section: Chemphyschemmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions

2022

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“…One approach is to introduce covalently bulky substituents at the bay, imide, and/or ortho position to suppress aggregation . It should be noted that the substitution at the bay position twists the perylene-based planar conformation usually more than a substitution at the imide position. , Molecular insulation is another effective strategy to disrupt stacking by incorporating PD phosphors into films or supramolecular assemblies such as poly(ethylene glycol) (PEG), polyglycerol (PG) dendrons, and dendritic carbohydrate derivatives.…”

Section: Introductionmentioning

confidence: 99%

An Unlimited Color Palette from Perylene Derivative Molecules Dispersed within Hybrids

Guo

Boyer

Réverêt

et al. 2022

ACS Appl. Opt. Mater.

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Subject to the aggregation-caused quenching mechanism in the solid state, perylene and its derivatives turn out to be fascinating organic fluorophores when separated from each other by their cointercalation within a layered double hydroxide host structure. Such accommodation with surfactant spacers limits their stacking usually caused by π–π interaction between neighboring cores. For each series of fluorophores having substitution in bay or diimide positions, an optimized composition is selected based on optical performances and in particular on the absolute photoluminescence quantum yield. The optimal relative quantity of phosphor is very low from 0.001 to 0.1% of the total anionic capacity. When dispersed into a silicone matrix, the loaded films cover from green (510 nm) to red (625 nm) emission depending on the perylene derivative molecules. With loaded films overlaid on a blue chip, a warm white light (color-correlated temperature = 3890 K) with a color-rendering index as high as 91.1 is reached. In such a light-emitting diode configuration, the superposition of films for each fluorophore is preferred to the powder mixture or to the cointercalation of organic phosphors within the same structure in order to avoid too strong and nonpredictable reabsorption phenomena between emitting centers.

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Lighting up aggregate emission of perylene diimide by leveraging polymerization-mediated through-space charge transfer and π-π stacking

Ye,

Füglistaller,

Tian

et al. 2024

Sci. China Chem.

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The molecular engineering of fluorescent organic/polymeric materials, specifically those emitting in the deep red to near-infrared spectrum, is vital for advancements in optoelectronics and biomedicine. Perylene diimide (PDI), a well-known fluorescent scaffold, offers high thermal and photophysical stability but suffers from fluorescence quenching in solid or aggregate states due to intense π-π interactions. To mitigate this, simple and versatile methods for strong PDI aggregate emission without extensive synthetic demands are highly desirable but still lacking. Here, we report a straightforward strategy to enhance the solid-state emission of PDI by introducing certain degree of through-space charge transfer (TSCT) via controlled radical polymerization, which can efficiently distort the typical face-to-face PDI stacking, enabling greatly enhanced deep red emission. This is achieved by growing electron-donating star-shape styrenic (co)polymers from a multidirectional electron-accepting PDI initiator. The incorporation of polycyclic aromatic monomers further shifted the emission into the near-infrared region, albeit with a reduced intensity. Overall, the emission of the PDI-based TSCT polymers can be systematically manipulated by leveraging the balance between PDI stacking and the TSCT degree, as confirmed by both experimental study and theoretical calculations. Our approach circumvents complex synthetic procedures, offering highly emissive materials with large Stokes shifts and showing broad potential for optoelectronic technology.

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Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function

Abstract: Thionation of a model perylene diimide has a significant impact on its self-assembly behaviour. This approach provides a facile route to simultaneously exert control over the mechanism, morphology and functionality of self-assembled PDI materials.

Cited by 8 publications

References 64 publications

Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions

Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions

An Unlimited Color Palette from Perylene Derivative Molecules Dispersed within Hybrids

Lighting up aggregate emission of perylene diimide by leveraging polymerization-mediated through-space charge transfer and π-π stacking

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