Naphthalenediimide-BasedHybrid Material with Eu-SubstitutedPolyoxometalate: Photochromism, Near-Infrared Photothermal Conversion,and C‑3 Functionalization of Indoles

Designing and developing novel photochromic materials with additional functions such as photothermal conversion and photocatalysis are challenging but meaningful objectives. Crystalline naphthalenediimide (NDI)-based hybrids are an attractive class of multifunctional materials with fast-response photoinduced electron transfer and charge separation properties. They are promising photothermal conversion materials and photocatalysts. Herein, a novel hybrid material, EuPMo<sub>11</sub>O<sub>39</sub>(L)<sub>1.5</sub>(H<sub>2</sub>O)<sub>2</sub>]·DMA (<b>EuMo-NDI</b>) (L = <i>N,N</i>′-di(1-oxido-4-pyridyl)-1,4,5,8-naphthalenediimide), was prepared with a solvothermal method, integrating a photoactive NDI derivative and an Eu-substituted polyoxometalate. <b>EuMo-NDI</b> exhibits 0D structure with sensitive photochromic behavior under UV–vis light irradiation due to fast-response photoinduced electron transfer between its components. The colored <b>EuMo-NDI</b> sample demonstrated efficient near-infrared photothermal conversion due to the strong absorption of the photogenerated radical anion NDI<sup>•–</sup> and mixed valence heteropoly blue in the near-infrared region. Meanwhile, <b>EuMo-NDI</b> is easily excited in the presence of electron donors to form the radical species, which can activate inert O<sub>2</sub> to superoxide radical O<sub>2</sub><sup>•–</sup>. <b>EuMo-NDI</b> exhibited high photocatalytic activity for C-3 thiocyanation of indoles under mild conditions using white light as a driving force. This work provides an effective avenue to design novel photothermal conversion materials and photocatalysts using photochromic materials as platforms.

Publication Details

Journal
Figshare
Published
2025-02-07
DOI
https://doi.org/10.1021/acs.inorgchem.4c05331.s001
Primary Topic
Agriculture and Biological Studies
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article
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Naphthalenediimide-BasedHybrid Material with Eu-SubstitutedPolyoxometalate: Photochromism, Near-Infrared Photothermal Conversion,and C‑3 Functionalization of Indoles

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Agriculture and Biological Studies
article

Naphthalenediimide-BasedHybrid Material with Eu-SubstitutedPolyoxometalate: Photochromism, Near-Infrared Photothermal Conversion,and C‑3 Functionalization of Indoles

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Abstract

Designing and developing novel photochromic materials with additional functions such as photothermal conversion and photocatalysis are challenging but meaningful objectives. Crystalline naphthalenediimide (NDI)-based hybrids are an attractive class of multifunctional materials with fast-response photoinduced electron transfer and charge separation properties. They are promising photothermal conversion materials and photocatalysts. Herein, a novel hybrid material, EuPMo<sub>11</sub>O<sub>39</sub>(L)<sub>1.5</sub>(H<sub>2</sub>O)<sub>2</sub>]·DMA (<b>EuMo-NDI</b>) (L = <i>N,N</i>′-di(1-oxido-4-pyridyl)-1,4,5,8-naphthalenediimide), was prepared with a solvothermal method, integrating a photoactive NDI derivative and an Eu-substituted polyoxometalate. <b>EuMo-NDI</b> exhibits 0D structure with sensitive photochromic behavior under UV–vis light irradiation due to fast-response photoinduced electron transfer between its components. The colored <b>EuMo-NDI</b> sample demonstrated efficient near-infrared photothermal conversion due to the strong absorption of the photogenerated radical anion NDI<sup>•–</sup> and mixed valence heteropoly blue in the near-infrared region. Meanwhile, <b>EuMo-NDI</b> is easily excited in the presence of electron donors to form the radical species, which can activate inert O<sub>2</sub> to superoxide radical O<sub>2</sub><sup>•–</sup>. <b>EuMo-NDI</b> exhibited high photocatalytic activity for C-3 thiocyanation of indoles under mild conditions using white light as a driving force. This work provides an effective avenue to design novel photothermal conversion materials and photocatalysts using photochromic materials as platforms.

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