Navigating the chalcogens: Sulfur substitution for n-type organic materials

Pahlavanlu, Paniz; Seferos, Dwight S.

doi:10.1080/10426507.2019.1602625

Cited by 12 publications

(21 citation statements)

References 19 publications

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“…The introduction of the main group elements into the organic conjugated molecules can efficiently modulate the electronic structure and energy levels of the conjugated systems. − Especially, the replacement of oxygen atoms with sulfur can greatly modify the electron mobility since sulfur has a larger atomic radius relative to oxygen and thereby improve the performance of organic batteries and optoelectronic devices . Meanwhile, the solubility issue of the electrode materials − can also be mitigated by introducing the sulfur atoms into the rigid backbone structure and appropriately choosing the functional groups. − For instance, the specific capacity of organic sodium battery is increased to 567 mAh g –1 at a current density of 50 mA g –1 when all of the O atoms of sodium terephthalate were replaced by S atoms .…”

Section: Introductionmentioning

confidence: 99%

Isometric Thionated Naphthalene Diimides As Organic Cathodes for High Capacity Lithium Batteries

Zhang

Yang

et al. 2020

Chem. Mater.

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Although naphthalene diimide (NDI) and its derivatives have been widely used for organic Li-ion batteries (OLIBs), they are limited by a low lithium uptake capacity and ambiguous lithiation mechanism. Herein, we report two isometric thionated-NDI cathodes (cis-2S and trans-2S) obtained by replacing O with S in the imide groups which improves the battery performance compared with parent NDI (P-NDI). Remarkably, the position of S atoms plays an important role as the potential plateau of cis-2S was 100 mV higher than trans-2S, 256 mV higher than P-NDI, and the capacity of cis-2S was twice than that of trans-2S, four times as P-NDI after 400 cycles. The in situ Raman, X-ray photoelectron spectroscopy (XPS), and DFT calculations revealed that the lithiation process occurs on the less electronegative S atoms. For cis-2S, the electron density on the lithiation sites is lower than trans-2S because of a stronger electron inductive effect. This in turn enhances the redox potential and cycling stability of cis-2S. This contribution provides an additional molecular engineering strategy to develop novel organic cathode materials for high performance OLIBs.

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Section: Introductionmentioning

confidence: 99%

Isometric Thionated Naphthalene Diimides As Organic Cathodes for High Capacity Lithium Batteries

Zhang

Yang

et al. 2020

Chem. Mater.

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“…[28][29][30][31] This approach has only recently been utilised for both PDI and related naphthalene diimide (NDI) systems. 32 Oxygen-to-sulphur exchange has a number of reported effects on the optoelectronic properties of these chromophores. Firstly, absorbance is bathochromically shifted significantly, resulting in a distinctive colour change.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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“…Subtle changes in chemical structure, imparted by single atom substitution, afford a range of monomers with varying optoelectronic and chemical properties. Specifically, sulfur substitution of naphthalene diimide (NDI) acceptor units corresponds to an increase in electron affinity, while selenium substitution produces larger and less aromatic donor units. − Through this systematic study, we aimed to investigate the role of monomer design in anion-radical polymerization while expanding its scope to include selenophene-flanked NDI-based polymers ,− and thionated NDI-based polymers , with targeted properties.…”

Section: Introductionmentioning

confidence: 99%

Anion-Radical Polymerization of Sulfur- and Selenium-Substituted N-Type Conjugated Polymers

Pahlavanlu

Panchuk

et al. 2021

Macromolecules

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While controlled chain-growth polymerizations have been developed for a handful of p-type conjugated polymers, most n-type conjugated polymers are still synthesized through step-growth methods that offer little to no control over the polymerization. The anion-radical polymerization of thiophene-flanked naphthalene diimides has been shown to exhibit non-living chain-growth behavior; however, anion-radical polymerizations are limited to a few examples that exhibit varying degrees of control. Strategies to improve and expand the scope of this promising methodology have not been developed. In this study, we investigate the anion-radical polymerization of a series of oxygenated and thionated, thiophene-and selenophene-flanked naphthalene diimides. We show, through optical and spectroelectrochemical studies, that anion-radical monomers likely consist of a complex mixture of organic radicals with varying oxidation states. Surprisingly, subtle changes in monomer structure afforded by sulfur and selenium substitution result in significant changes in polymer synthesis. Notably, selenophene-flanked naphthalene diimides polymerize more rapidly to reach higher degrees of polymerization when compared to thiophene-flanked analogues. While thionated naphthalene diimides form anion-radical complexes and exhibit signs of catalyst insertion, they do not undergo polymerization. These results provide insights into the further development of anion-radical polymerization as a promising route to well-defined n-type conjugated polymers.

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Navigating the chalcogens: Sulfur substitution for n-type organic materials

Cited by 12 publications

References 19 publications

Isometric Thionated Naphthalene Diimides As Organic Cathodes for High Capacity Lithium Batteries

Isometric Thionated Naphthalene Diimides As Organic Cathodes for High Capacity Lithium Batteries

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

Anion-Radical Polymerization of Sulfur- and Selenium-Substituted N-Type Conjugated Polymers

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