Abstract

Efficient electron transport and minimizing recombination losses are crucial for optimizing DSSC performance, necessitating strategies to improve electron diffusion and reduce charge recombination. Two new eco-friendly polyimides based on χ-type polyoxometalates namely Tris@ZnPOM, and Tris@NiPOM, one with the Zn-containing Anderson-type POM(ADP), and the other with the Ni-containing Anderson-type POM, respectively have been synthesized and characterized by FT-IR, UV–vis. spectral analysis, TGA,1H NMR, fluorescence and cyclic voltametric analysis. The fluorescence quenching in Tris@ZnPOM, and Tris@NiPOM was observed as98% and 99.7% as compared to Tris@anhydride, referring the photo-induced transfer of electrons between POM and Tris@anhydrides. The dielectric loss is found to be higher in Tris@anhydride as compared to the Tris@NiPOM, and Tris@ZnPOM. From the MEP analysis it has been seen that POM act as an electron with drawing subunit when conjugated with the anhydride. Different global reactivity parameters (μ, η and ω) were estimated from the frontier molecular orbitals (FMO) analysis, and the order of reactivity for Tris@anhydride, Tris@NiPOM, and Tris@ZnPOM is determined to be in accordance with their increasing band gap i.e., Tris@anhydride > Tris@NiPOM > Tris@ZnPOM. The increase in efficiency (η) of photovoltaics response for Tris@ZnPOM (2.35) is found to be higher as compared to Tris@NiPOM (1.25) and Tris@anhydride(0.62). The presence of Zn in ADP is responsible for increasing the efficiency of Tris@ZnPOM due to its low band gap that causes the easiest transfer of electron.

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