Isomeric fluorescence sensors for wide range detection of ionizing radiations

Abstract

In order to achieve a wider range of ionizing radiations detection, novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer (PET) effect. Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized, and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry (HRMS), nuclear magnetic resonance hydrogen and carbon spectroscopy (1H and 13C NMR). The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration. The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process. Despite the similarities in chemical structures, the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine. In the direct irradiation experiments of ionizing radiation, the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4, respectively. Furthermore, density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 eV and 1.13 eV, respectively. A wider energy range has a stronger driving force on electrons, which is conducive to fluorescence quenching. Both femtosecond transient absorption spectroscopy (fs-TAS) and transient fluorescence spectroscopy (TFS) tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant. Although both isomers can significantly reduce LOD during PET process, PDI-B with aromatic amine has a wider detection range of 0.118–240 Gy due to its larger emission enhancement, which is a leap of three orders of magnitude. It breaks through the detection range of gamma radiation reported in existing studies, and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.