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

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 (H2tpdb) as a linker to be incorporated into coordination polymer and test towards applicability within the photochemical 1O2 generation. In detail, a novel zinc 2D -coordination polymer Zn(tpdb)(DMF)3 is reported, which is synthesized using a solvothermal synthesis with Zn(NO3)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.