Green hydrothermal synthesis yields perylenebisimide–SiO<sub>2</sub> hybrid materials with solution-like fluorescence and photoredox activity

Moura, Hipassia M.; Peterlik, Herwig; Unterlass, Miriam M.

doi:10.1039/d1ta03214c

Cited by 4 publications

(3 citation statements)

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“…[33] Moreover, PDIs in homogeneous or heterogeneous systems can accumulate enough energy via consecutive visible light excitations to reduce stable aryl halides to aryl radicals. [34][35][36][37][38][39][40] However, the difficult stabilization of PDI radical anions formed by photoinduced electron transfer limits further research on the photocatalytic properties of PDIs. Zhu's group reported a PDI/TiO 2 composite photocatalyst showing impressive visible light-driven photocatalytic activity toward phenol degradation.…”

Section: Introductionmentioning

confidence: 99%

“…PDIs have recently been shown to produce radical anions by photoinduced electron transfer and therefore photochromism [33] . Moreover, PDIs in homogeneous or heterogeneous systems can accumulate enough energy via consecutive visible light excitations to reduce stable aryl halides to aryl radicals [34–40] . However, the difficult stabilization of PDI radical anions formed by photoinduced electron transfer limits further research on the photocatalytic properties of PDIs.…”

Section: Introductionmentioning

confidence: 99%

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Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Dai,

Li,

et al. 2024

Chemistry A European J

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Four radical‐doped PDI‐based crystalline hybrid materials, Cl4‐PDI·SiW12O40 (1), Cl4‐PDI·SiMo12O40 (2), Cl4‐PDI·PW12O40 (3), and Cl4‐PDI·PMo12O40 (4), were attainedby slow diffusion of polyoxometalates (POMs) into acidified Cl4‐PDI solutions. The obtained PDI‐based crystalline hybrid materials not only exhibited prominent photochromism, but also possessed reactive organic radicals under ambient conditions. Furthermore, all hybrid materials could be easily photoreduced to their radical anions (Cl4‐PDI•‒), and then underwent a second photoexcitation to form energetic excited state radical anions (Cl4‐PDI•‒*). However, experiments and theoretical calculations demonstrated that the formed energetic Cl4‐PDI•‒* showed unusual POM‐dependent photocatalytic efficiencies toward the oxidative coupling of amines and the iodoperfluoroalkylation of alkenes; higher photocatalytic efficiencies were found for hybrid materials 1 and 2 compared to 3 and 4. The photocatalytic efficiencies of these hybrid materials are mainly controlled by the energy differences between the SOMO‐2 level of Cl4‐PDI•‒* and the LUMO level of the POMs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Dai,

Li,

et al. 2024

Chemistry A European J

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“…Perylenediimides (PDIs) are a prominent class of electron-deficient organic compounds with an expanded π-electron-deficient plane; they have attracted considerable attention due to their outstanding electronic, optical, and light-fastness properties in combination with their high thermal and photostabilities and chemical robustness. − Compared to traditional electron-deficient organic compounds, PDIs, with a highly redox active and intense visible-light absorption ability, can go through a photoinduced single-electron-transfer process to generate colored PDI radical anions. − The resulting PDI radical anions, even under near-infrared or visible light, can further produce the double excited-state PDI radical anion (PDI •–* ), which is a strong reductant and can reduce inert organic substrates. A consecutive photoinduced electron transfer yields highly reactive PDI radical anions that can overcome the energy limitations of visible or near-infrared light photoredox catalysis, thereby enabling the photocatalytic transformation of inert chemical bonds in organic synthesis. − König and co-workers first reported the use of photoexcited PDI radical anions as photosensitizers to induce reductive dehalogenation of inert aryl halides …”

Section: Introductionmentioning

confidence: 99%

Perylenediimide-Based Hybrid Materials for the Iodoperfluoroalkylation of Alkenes and Oxidative Coupling of Amines: Bay-Substituent-Mediated Photocatalytic Activity

Liu

Yin

et al. 2022

ACS Appl. Mater. Interfaces

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Inorganic−organic donor−acceptor hybrid compounds are an emerging class of multifunctional crystalline materials with well-defined structures built from semiconductive inorganic and organic components. Perylenediimides (PDIs) are a prominent class of electron-deficient organic dyes, which can undergo consecutive photoinduced electron transfers to generate doublet excitedstate radical anions for photoredox-inert chemical bonds. Thus, this is an excellent organic component for building hybrid materials to study the structure−property relationships in organic synthesis. In this context, three molecular structure modified PDI-based hybrid materials, (Me 4 -PDI) 2 •SiW 12 O 40 (1), (Me 4 -Cl 4 -PDI) 2 • SiW 12 O 40 (2), and (Me 4 -Br 2 -PDI) 1.5 •HSiW 12 O 40 (3), were studied. By the introduction of different substituent groups at the bay positions, these three hybrid materials were successfully fabricated to investigate the impact of substituent groups on the photocatalytic activity. As expected, all PDI-based hybrid materials easily underwent consecutive photoexcitation to obtain their excited-state radical anions. However, experimental and theoretical analyses showed that these obtained excited-state radical anions displayed unusual bay-substituent-group-dependent photocatalytic conversion activities for the iodoperfluoroalkylation of alkenes and oxidative coupling of amines. Higher conversion yields were obtained for complexes 1 and 3 (bay-unsubstituted and Br-substituted PDI hybrid materials, respectively), and lower conversion was observed for complex 2 (Cl-substituted PDI hybrid material), which is attributed to the excited-state SOMO-1 energies of the PDI radical anions. The structure−property relationship established in this work provides insights for the further exploration of baysubstituted PDI hybrid materials in other small-molecule photocatalytic transformations.

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Covalently Linked Pigment@TiO₂ Hybrid Materials by One‐Pot Solvothermal Synthesis

Sailer,

Moura,

Purkait

et al. 2024

Small Structures

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Hybrid materials (HMs) combine the high diversity of functionalities of organic compounds with properties typical for inorganic materials, such as high mechanical strength or high thermal stability. Herein, HMs combining organic pigment molecules and TiO2 as inorganic component, with covalently linked components, i.e., so‐called class II HMs, are reported. The synthesis of such HMs is intrinsically challenging, as the apolar organic pigment component and the inorganic polar TiO2 component require different conditions for their respective formation. Herein, we circumvent this issue by employing solvothermal synthesis in superheated isopropanol, which through temperature tunability of the solvent properties allows for both generating and linking both components in one‐pot. First, it is shown that an organic benzimidazole‐based pigment molecule designed for readily binding to Ti can be synthesized solvothermally. Second, new class II titanium‐based HMs are generated from Ti(OiPr)4 and pigment precursors in a solvothermal reaction. The pigment@TiO2 HMs feature significant porosity and are structurally identified as layered structures of lepidocrocite‐like TiO2 linked via pigment molecules. These layered HMs assemble into hierarchical nanoflowers, and depending on the pigment segments, different interlayer spacings in between inorganic layers are observed. Third, the pigment@TiO2 materials are shown to be usable as electrode materials in lithium‐ion batteries.

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Green hydrothermal synthesis yields perylenebisimide–SiO₂ hybrid materials with solution-like fluorescence and photoredox activity

Abstract: PBI dyes@SiO2 hybrid materials are generated by hydrothermal synthesis. They exhibit solution-like fluorescence and photocatalytic activity. An in-depth materials formation study reveals a network of PBI-linked POSS-type cages.

Cited by 4 publications

References 51 publications

Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Perylenediimide-Based Hybrid Materials for the Iodoperfluoroalkylation of Alkenes and Oxidative Coupling of Amines: Bay-Substituent-Mediated Photocatalytic Activity

Covalently Linked Pigment@TiO₂ Hybrid Materials by One‐Pot Solvothermal Synthesis

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Green hydrothermal synthesis yields perylenebisimide–SiO2 hybrid materials with solution-like fluorescence and photoredox activity

Abstract: PBI dyes@SiO2 hybrid materials are generated by hydrothermal synthesis. They exhibit solution-like fluorescence and photocatalytic activity. An in-depth materials formation study reveals a network of PBI-linked POSS-type cages.

Cited by 4 publications

References 51 publications

Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Perylenediimide-Based Hybrid Materials for the Iodoperfluoroalkylation of Alkenes and Oxidative Coupling of Amines: Bay-Substituent-Mediated Photocatalytic Activity

Covalently Linked Pigment@TiO2 Hybrid Materials by One‐Pot Solvothermal Synthesis

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Green hydrothermal synthesis yields perylenebisimide–SiO₂ hybrid materials with solution-like fluorescence and photoredox activity

Covalently Linked Pigment@TiO₂ Hybrid Materials by One‐Pot Solvothermal Synthesis