Long-lived NIR emission in sulfur-doped zeolites due to the presence of [S3]2- clusters

Abstract

Funding Information: The authors want to acknowledge the Portuguese Foundation for Science and Technology for funding through the grants SFRH/BD/145009/2019 and SFRH/BPD/120599/2016 , the individual contract 2020.00252. CEECIND and several projects PTDC/QUI-QFI/32007/2017, UIDB/04565/2020, UIDP/04565/2020, LA/P/0140/2020, LAQV-REQUIMTE (LA/P/0008/2020, UIDB/50006/2020 and UIDP/50006/2020), VICARTE (UIDP/00729/2020, UIDB/00729/2020) and C2TN (UIDB/04349/2020). MOSTMICRO-ITQB R&D Unit (UIDB/04612/2020, UIDP/04612/2020) and LS4FUTURE Associated Laboratory (LA/P/0087/2020) and by European Union's Horizon 2020 research and innovation program under grant agreement No. 810856. Funding Information: The authors want to acknowledge the Portuguese Foundation for Science and Technology for funding through the grants SFRH/BD/145009/2019 and SFRH/BPD/120599/2016, the individual contract 2020.00252. CEECIND and several projects PTDC/QUI-QFI/32007/2017, UIDB/04565/2020, UIDP/04565/2020, LA/P/0140/2020, LAQV-REQUIMTE (LA/P/0008/2020, UIDB/50006/2020 and UIDP/50006/2020), VICARTE (UIDP/00729/2020, UIDB/00729/2020) and C2TN (UIDB/04349/2020). MOSTMICRO-ITQB R&D Unit (UIDB/04612/2020, UIDP/04612/2020) and LS4FUTURE Associated Laboratory (LA/P/0087/2020) and by European Union's Horizon 2020 research and innovation program under grant agreement No. 810856. Publisher Copyright: © 2023 The Author(s)The exploration of novel long-lived near-infrared (NIR) luminescent materials has attracted significant attention due to their applications in optical communications, anticounterfeiting, and bioimaging. However, these materials usually present low photoluminescence quantum yields and low photo- and chemical stability. Novel emitters that overcome these limitations are in demand. In this study, NIR emission was achieved using widely available, sustainable, and non-toxic materials through the synthesis of sulfur-doped zeolites, with different S/Cl ratios. With a combination of computational calculations (TD-DFT) and spectroscopic data, this emission was assigned to the radiative decay of excited triplet states of [S3]2- clusters, which resulted in a remarkably high Stokes shift (1.97 eV, 440 nm) and an average decay time of 0.54 ms. These new materials present high stability, external quantum efficiency of up to 17%, and a long-lived NIR emission, placing these compounds in a unique position to be used in applications demanding NIR emitters.publishersversionpublishe