A Perylenediimide-Based Zinc-Coordination Polymer for Photosensitized Singlet-Oxygen Generation

Simon N. Deger, Sebastian J. Weishäupl, Alexander Pöthig and Roland A. Fischer
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Simon N. Deger: Chair of Inorganic and Metal-Organic Chemistry, Catalysis Research Center, Ernst-Otto-Fischer-Straße 1, 85748 Garching, Germany
Sebastian J. Weishäupl: Chair of Inorganic and Metal-Organic Chemistry, Catalysis Research Center, Ernst-Otto-Fischer-Straße 1, 85748 Garching, Germany
Alexander Pöthig: Chair of Inorganic and Metal-Organic Chemistry, Catalysis Research Center, Ernst-Otto-Fischer-Straße 1, 85748 Garching, Germany
Roland A. Fischer: Chair of Inorganic and Metal-Organic Chemistry, Catalysis Research Center, Ernst-Otto-Fischer-Straße 1, 85748 Garching, Germany

Energies, 2022, vol. 15, issue 7, 1-12

Abstract: In the face of anthropogenic global warming the design and synthesis of materials, which enable energy transfer processes using sunlight as an energy source, are of high interest. Perylenediimides are a highly absorbing class of chromophores suitable for sunlight absorption and conversion. Therefore, metal–organic frameworks (MOFs) and coordination polymers (CPs) with incorporated organic perylene chromophores are highly interesting materials both for applied, but also fundamental, photophysical research. MOFs/CPs have the advantage of a modular adjustability of interchromophoric distances and angles, and the choice of metal nodes can be used to further tune the material towards the desired photophysical properties. In the present paper, we present a study using a reported organic perylenediimide (PDI) chromophore (H 2 tpdb) as a linker to be incorporated into coordination polymer and test towards applicability within the photochemical 1 O 2 generation. In detail, a novel zinc 2D -coordination polymer Zn(tpdb)(DMF) 3 is reported, which is synthesized using a solvothermal synthesis with Zn(NO 3 ) 2 and a ditopic organic perylene linker. Both the linker and Zn-CP are fully characterized, including SC-XRD, showing a strong aggregation of tightly packed chromophores in the solid state. The photophysical properties are examined and discussed, including the observed shifts within the absorption spectra of the CP are compared to the linker in solution. These shifts are mainly attributed to the for PDIs known H-type aggregation and an additional charge transfer in the framework structure, causing a limited quantum yield of the emission. Finally, the photosensitization of triplet oxygen to singlet oxygen using 1,3-diphenylisobenzofurane (DBPF) as a trapping agent is investigated both for the free linker and the Zn-CP, showing that the perylene chromophore is an efficient photosensitizer and its activity can, in principle, be retained after its incorporation in the coordination polymer.

Keywords: perylene diimide; metal–organic framework; singlet oxygen; photosensitizer; H-type aggregation (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2022
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