{"title":"Fluorine-Induced Anomalous Optical Stability and Pressure-Enhanced Emission Property of 0D Lead Perovskite Derivatives","authors":"Congcong Chen, Yifan Zhang, Huan Liu, Xuanyu Zhang, Zhongshiqi Luo, Jiawei Lin, Yuhong Mao, Rui Chen, Songhao Guo*, Xujie Lü and Lingling Mao*, ","doi":"10.1021/acs.chemmater.5c0011210.1021/acs.chemmater.5c00112","DOIUrl":null,"url":null,"abstract":"<p >Low-dimensional metal halides, especially zero-dimensional (0D) compounds, are important derivative members of the halide perovskite family primarily due to their highly emissive properties. Here, we report two highly luminescent 0D lead bromides, (BPP)<sub>2</sub>PbBr<sub>4</sub> and (BPPF)<sub>2</sub>PbBr<sub>4</sub>·2H<sub>2</sub>O, abbreviated as BPP-0D and BPPF-0D (BPP = benzyltriphenylphosphonium, BPPF = (4-fluorobenzyl)triphenylphosphonium). Both compounds share mutual seesaw inorganic units [PbBr<sub>4</sub>]<sup>2–</sup> separated by bulky organic cations. BPP-0D and BPPF-0D emit yellow and green lights, respectively, with photoluminescence (PL) quantum yields (PLQYs) of ∼15 and ∼55% at ambient conditions. Both compounds show excellent environmental stability and practical applications in light-emitting diodes. Upon compression, BPP-0D experiences a rapid decrease in PL intensity, accompanied by an obvious change in its emissive color from yellow to blue. In contrast, BPPF-0D demonstrates excellent optical stability, retaining its green emission, while the PL increases by ∼1.7 times at 0.8 GPa and the PLQY increases to 93%. For BPPF-0D, the presence of an extra highly electronegative fluoride group adds many more noncovalent interactions, such as C–H···F hydrogen bond and F···F interactions. These interactions strengthen the structural and optical stabilities of BPPF-0D, maintaining its emission peak position with elevated pressure. The straightforward comparison between two similar compounds and their optical properties under pressure modulation underscores the importance of engineering organic cations to control and optimize their properties.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2314–2324 2314–2324"},"PeriodicalIF":7.2000,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.5c00112","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Low-dimensional metal halides, especially zero-dimensional (0D) compounds, are important derivative members of the halide perovskite family primarily due to their highly emissive properties. Here, we report two highly luminescent 0D lead bromides, (BPP)2PbBr4 and (BPPF)2PbBr4·2H2O, abbreviated as BPP-0D and BPPF-0D (BPP = benzyltriphenylphosphonium, BPPF = (4-fluorobenzyl)triphenylphosphonium). Both compounds share mutual seesaw inorganic units [PbBr4]2– separated by bulky organic cations. BPP-0D and BPPF-0D emit yellow and green lights, respectively, with photoluminescence (PL) quantum yields (PLQYs) of ∼15 and ∼55% at ambient conditions. Both compounds show excellent environmental stability and practical applications in light-emitting diodes. Upon compression, BPP-0D experiences a rapid decrease in PL intensity, accompanied by an obvious change in its emissive color from yellow to blue. In contrast, BPPF-0D demonstrates excellent optical stability, retaining its green emission, while the PL increases by ∼1.7 times at 0.8 GPa and the PLQY increases to 93%. For BPPF-0D, the presence of an extra highly electronegative fluoride group adds many more noncovalent interactions, such as C–H···F hydrogen bond and F···F interactions. These interactions strengthen the structural and optical stabilities of BPPF-0D, maintaining its emission peak position with elevated pressure. The straightforward comparison between two similar compounds and their optical properties under pressure modulation underscores the importance of engineering organic cations to control and optimize their properties.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.