Comparing the microstructure and photovoltaic performance of 3 perylene imide acceptors with similar energy levels but different packing tendencies

Adel, R.; Gala, Elena; Alonso‐Navarro, Matías J.; Gutiérrez, Edgar; Martı́n, Jaime San; Stella, Marco; Martínez‐Ferrero, Eugenia; Peña, Alejandro de la; Harbuzaru, Alexandra; Ramos, Mar; Ortiz, Rocío Ponce; Segura, José L.; Campoy‐Quiles, Mariano

doi:10.1039/d1tc05037k

Cited by 8 publications

(5 citation statements)

References 66 publications

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“…When the dimers are compared to PDI, both the 0–0 and 0–1 peaks are blue-shifted in all cases. The ratio between the absorbance of the 0–1 transition and the 0–0 transition ( ( A 0 − 1 A 0 − 0 ) is used to characterize π–π aggregation in heavily conjugated molecules, like perylene compounds. ,− A decrease in this ratio represents an increase in aggregation and, therefore, an increase in the π–π interactions between molecules in solution. Here, the A 0–1 / A 0–0 ratio decreases from d-BZ to d-ANH with a value of 0.97, 0.77, and 0.65 for d-BZ, d-NPH, and d-ANH, respectively (Figure S37a).…”

Section: Resultsmentioning

confidence: 99%

Linker-Derived Contortion Controls Performance in Organic Polymer Pseudocapacitors

Gray,

Posey,

Orchanian

et al. 2024

Chem. Mater.

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Pseudocapacitors offer a unique strategy to combine the rapid charging rates of capacitors with the high energy density of batteries, potentially offering a unique solution to energy storage challenges. Bending and twisting aromatic building blocks to form contorted aromatics have emerged as a new strategy to create organic materials with unique and tunable properties. This paper studies the union between these two concepts: molecular contortion and organic pseudocapacitors. The recent development of fully organic pseudocapacitors, including high-performing devices based on perylene diimide organic redox units, introduces the added benefit of low cost, synthetic tunability, and increased flexibility. We synthesize a series of polymers by joining perylene diimide with various linkers that incorporate a helical moiety from [4]helicene to [6]helicene into the molecular backbone. We prepare three new electroactive polymers that incorporate benzene, naphthalene, and anthracene linkers and study their pseudocapacitive performance to infer key design principles for organic pseudocapacitors. Our results show that the naphthalene linker results in the most strongly coupled redox centers and displays the highest pseudocapacitance of 292 ± 47 F/g at 0.5 A/g. To understand the pseudocapacitive behavior, we synthesized dimer model compounds to further probe the electronic structure of these materials through electronic absorption spectroscopy and first-principles calculations. Our results suggest that the identity of the aromatic linker influences the contortion between neighboring perylene diimide units, the coupling between redox centers, and their relative angles and distances. We find that competing molecular design factors must be carefully optimized to generate highperformance devices. Overall, this study provides key insights into molecular design strategies for generating high-performing organic pseudocapacitor materials.

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Section: Resultsmentioning

confidence: 99%

Linker-Derived Contortion Controls Performance in Organic Polymer Pseudocapacitors

Gray,

Posey,

Orchanian

et al. 2024

Chem. Mater.

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“…[15] Thus, for the synthesis of the target compounds, we used as starting material the dithienothiophen[3,2-b]-pyrrolobenzothiadiazole (1), [16] which was subsequently reduced with nonactivated zinc dust in acetic acid at 140 °C for 30 min to yield the diamino derivative 2, which was in situ reacted with the corresponding functionalized 1,2-diketone ryleneimides 3 or 4. Naphthalimide [17] and peryleneimide-based [18] 1,2-diketones were first described by Segura and co-workers and successfully used as versatile electron-withdrawing building blocks for the synthesis of small molecules, [17] macromolecular, [19] linear, [20] 2D, [21] 3D, [22] and amphiphilic [23] organic semiconductors with applications in organic field effect transistors (OFETs), [24] organic solar cells (OSCs), [25] and as photo- [26] and photoelectrocatalysts. [27] The remaining synthesis steps for the target compounds are commonly used in the synthesis of NFAs and involve first the formylation of 5 and 6 via the Vilsmeier-Haack reaction to yield the corresponding dialdehydes 7 and 8.…”

Section: Resultsmentioning

confidence: 99%

Tailoring the Electron‐Deficient Central Core on Fused‐Ring Nonfullerene Acceptors: Deciphering the Relationships Between Structure, Property, and Photovoltaic Performance

Suárez‐Blas,

Pandolfi,

Alonso‐Navarro

et al. 2024

Adv Energy and Sustain Res

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In the field of organic solar cells, organic semiconductors with Y6‐based chemical structure and their corresponding quinoxaline‐based assemblies are settled down as promising materials in the field of OSCs. However, the chemical structure of Y6 derivatives does not allow an expansion in the electron‐withdrawing central core, in contrast to their quinoxaline‐based analogues. For this reason, herein, two different quinoxaline‐based A–D–A′–D–A derivatives with 2D π‐extended cores endowed with electroactive rylenimide moieties, named as Y6‐1Napht and Y6‐1Pery, are designed and synthesized. These enlarged fused‐ring electron acceptors (FREAs) allow to study the influence of the length of the ryleneimide moiety on its structural, optical, electrochemical, and thermal properties as well as the tailoring of the frontier molecular orbitals. These results are also supported by quantum chemical calculations and photoluminescence measurements that provide additional information about their thermal stability and the microstructure of the films. Finally, as a proof of concept and to study the influence of these chemical modifications on the central core, solar cells based on these π‐conjugated nonfullerene acceptors are fabricated.

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“…Thermograms of BzDI 0.17 -COF and NDI 0.17 -COF revealed a weight loss of 24% at around 380 °C and showed a progressive mass decrease of 15% until 700 °C according to the degradation of the COF skeleton. 44 Meanwhile, PDI 0.17 -COF displayed three weight losses at around 252 °C (4%) and 425 °C (21%) which corresponds to the degradation of the long aliphatic chains that bear PDI 46 and the COF network, respectively. Finally, a mass decrease of 12% was observed until 700 °C according to the previous reported literature.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Evaluation of the Oxygen Reduction Reaction Electrocatalytic Activity of Postsynthetically Modified Covalent Organic Frameworks

Martínez-Fernández

Martínez‐Periñán

Martínez

et al. 2023

ACS Sustainable Chem. Eng.

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The pyrolysis of organic precursors to produce heteroatomic-doped carbonaceous materials has emerged as a powerful tool to construct metal-free heterogeneous electrocatalysts due to their low cost and their environmental friendliness. However, the lack of control in the atomic positions or the location of the chemical functionalities makes it difficult to establish structure–property relationships. Herein, we report an easy strategy to compare the electrocatalytic oxygen reduction reaction (ORR) performance of metal-free and nonpyrolyzed materials by postsynthetic modification of covalent organic frameworks (COFs) via click-chemistry. This method facilitates the evaluation of different active centers using materials with the same morphology and prevents active site agglomeration by covalently anchoring these moieties inside of a porous and crystalline framework. In this study we developed a series of diimide-based materials (XDI0.17-COFs) with a loading of 7.65 × 10–4 mol of active site/mg of host COF. The bulk COFs have been delaminated to perform electrode modification by drop-casting. The electrocatalytic response toward the ORR has been studied in alkaline media obtaining the best results for the NDI0.17-COF with an onset potential of 0.77 V (vs reversible hydrogen electrode, RHE) and a limiting current of 4.2 mA/cm2 by a preferred pathway toward water electroreduction. Finally, an adequate combination of density functional theory with the thermochemical Gibbs free energy formalism has been used to theoretically rationalize the ORR mechanism in these metal-free and nonpyrolyzed materials. We have obtained theoretical ORR overpotentials for each COF system agreeing with the experimental observation, which correlate with the ability of the NDI, BzDI, and PDI molecular blocks to accommodate electrons. Our work provides a guideline on how to study the electrocatalytic performance of different organic moieties in metal-free and non-pyrolyzed COFs avoiding their de novo synthesis by using the click postsynthetic methodology.

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Comparing the microstructure and photovoltaic performance of 3 perylene imide acceptors with similar energy levels but different packing tendencies

Abstract: While it is widely recognized that microstructure plays an important role in the performance of organic photovoltaics (OPV), systematic studies are often challenging, as varying the molecular packing through typical...

Cited by 8 publications

References 66 publications

Linker-Derived Contortion Controls Performance in Organic Polymer Pseudocapacitors

Linker-Derived Contortion Controls Performance in Organic Polymer Pseudocapacitors

Tailoring the Electron‐Deficient Central Core on Fused‐Ring Nonfullerene Acceptors: Deciphering the Relationships Between Structure, Property, and Photovoltaic Performance

Evaluation of the Oxygen Reduction Reaction Electrocatalytic Activity of Postsynthetically Modified Covalent Organic Frameworks

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