Frontispiece: Design and Control of Perylene Supramolecular Polymers through Imide Substitutions

Wilson-Kovacs, Robert Stefan; Fang, Xue; Hagemann, Maximilian J. L.; Symons, Henry E.; Faul, Charl F. J.

doi:10.1002/chem.202280361

Cited by 9 publications

(7 citation statements)

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“…That steric effects do indeed influence the nature and extent of π-π stacking was already recognized, with a special focus on core-unsubstituted PDIs (ideally flat also in the gas phase). [23] An alternative interpretation for PDI core flattening can be however put forward: "axial" aromatic residues may act as paddles, where additional packing forces arise, overcoming the M!P interconversion barrier. However, as flattening in the solid state occurs also for a swinging, nonrigid, residue (the propylacetate in WUFKIT), this effect, if present, must be of second order.…”

Section: Methodsmentioning

confidence: 99%

Forcing Twisted 1,7‐Dibromoperylene Diimides to Flatten in the Solid State: What a Difference an Atom Makes

Konidaris,

Zambra,

Giannici

et al. 2023

Angew Chem Int Ed

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Perylene‐diimides (PDI) are workhorses in the field of organic electronics, owing to their appealing n‐semiconducting properties. Optimization of their performances is widely pursued by bay‐atom substitution and diverse imide functionalization. Bulk solids and thin‐films of these species crystallize in a variety of stacking configurations, depending on the geometry of the stable conformation of the polyaromatic core. We here demonstrate that 1,7‐dibromo‐substituted perylene‐diimides, PDI(H2Br2), possessing a heavily twisted conformation in the gas phase, in solution and in the solids, can be easily flattened in the solid state into centrosymmetric molecules if the polyaromatic cores form p‐p stabilized chains. This is achieved by using axial residues with low stereochemical hindrance, as guaranteed by a single CH2/NH spacer directly linked to the imide function. Structural powder diffraction and DFT calculations on four newly designed species of the PDI(H2Br2) class coherently show that, thanks to the flexibility of the N‐X‐Ar link (X = CH2/NH), flat cores are indeed obtained by overcoming the interconversion barrier between twisted atropoisomers, of only 26.5 kJ mol‐1. This strategy may then be useful to induce “anomalously flat” polyaromatic cores of different kinds (substituted acenes/rylenes) in the solid state, towards suitable crystal packing and orbital interactions for improved electronic performances.

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Section: Methodsmentioning

confidence: 99%

Forcing Twisted 1,7‐Dibromoperylene Diimides to Flatten in the Solid State: What a Difference an Atom Makes

Konidaris,

Zambra,

Giannici

et al. 2023

Angew Chem Int Ed

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“…(Figure S2, Supporting Information) Oppositely, the absorption spectrum of film was blue-shifted ≈3 nm compared to the absorption of the solution for the PBDFCl-2, indicating that the amount of H-aggregation was enhanced. [48][49][50][51] Meanwhile, the maximum and shoulder peaks were assigned to the 0-1 and 0-0 vibronic transitions of the polymer π-π* transition, respectively. The 0-0/0-1 intensity ratio can reveal the type of molecular packing, and 0-0/0-1 intensity ratio decrease suggest H-aggregation enhancement.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

An Efficient One‐Arrow‐Two‐Hawks Strategy Achieves High Efficiency and Stable Batch Variance for Benzodifuran‐based Polymer Solar Cells

Zheng

Yue

et al. 2023

Adv Funct Materials

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With the development of organic solar cells (OSCs), the high-performance and stable batch variance are becoming a new challenge for designing polymer donors. To obtain high photovoltaic performance, adopting polymers with high molecular weight as donors is an ordinary strategy. However, the high molecular weight need to subtly control the reaction time and state, inevitably caused batch-to-batch variations. Herein, a strategy of steric effect is applied to benzodifuran (BDF)-based polymer by introducing different positions of Cl atom, producing two polymers PBDFCl-1 and PBDFCl-2. The more twisted side chains conformation not only achieve the control of moderate molecular weight for PBDFCl-2, but also easily form molecular stacking through adopting BDF unit and maintain sufficient polymeric crystallinity. Due to the optimized stacking mode and good blend miscibility, PBDFCl-2-based device exhibitsa more elegant power conversion efficiency (PCE) of 17.00% compared to PBDFCl-1-based device. This is the highest efficiency record for BDF-based binary OSCs. Meanwhile, the PCE device variation of the different molecular weights for PBDFCl-2 is little, indicating the reduction of the batch variation. Therefore, smartly using steric effect of Cl atom in strong crystalline BDF unit can form efficient molecular stacking regulations and realize the coordination of high-performance and stable batch variance.

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“…The HOMO-LUMO gap is strongly dependent on geometry and the extent of overlap in the π-orbitals. [93] The ωB97xD functional provides an accurate account of energy and geometry, although it has been found to overestimate the excitation energies, [88] whereas B3LYP-D3 functional provides a better agreement with the experimental vertical excitation energies. Hence, the HOMO-LUMO energies from B3LYP-D3 calculations are reported here.…”

Section: Frontier Molecular Orbitalsmentioning

confidence: 99%

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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Frontispiece: Design and Control of Perylene Supramolecular Polymers through Imide Substitutions

Cited by 9 publications

References 0 publications

Forcing Twisted 1,7‐Dibromoperylene Diimides to Flatten in the Solid State: What a Difference an Atom Makes

Forcing Twisted 1,7‐Dibromoperylene Diimides to Flatten in the Solid State: What a Difference an Atom Makes

An Efficient One‐Arrow‐Two‐Hawks Strategy Achieves High Efficiency and Stable Batch Variance for Benzodifuran‐based Polymer Solar Cells

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

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