Amarjith V Dev, Manasa G. Basavarajappa, Swapnil S. Deshpande, Poulomi Mukherjee, Avija Ajayakumar, Chinnadurai Muthu, Takuya Okamoto, Sudip Chakraborty*, D. D. Sarma, Vasudevanpillai Biju and Chakkooth Vijayakumar*,
{"title":"二维杂化铜(I)-卤化物单晶中的自阱激子发射热诱导可逆荧光","authors":"Amarjith V Dev, Manasa G. Basavarajappa, Swapnil S. Deshpande, Poulomi Mukherjee, Avija Ajayakumar, Chinnadurai Muthu, Takuya Okamoto, Sudip Chakraborty*, D. D. Sarma, Vasudevanpillai Biju and Chakkooth Vijayakumar*, ","doi":"10.1021/acs.chemmater.4c00045","DOIUrl":null,"url":null,"abstract":"<p >Organic–inorganic metal halides (OIMHs) have gained significant attention as promising materials for various applications, including lighting, imaging, and energy conversion. The development of Pb-free alternatives to traditional Pb-based materials has become increasingly important for environmental and health reasons. In this study, we report on the thermally induced fluorochromism of a two-dimensional OIMH based on Cu(I), namely, (Bz)<sub>2</sub>Cu<sub>2</sub>I<sub>4</sub>·H<sub>2</sub>O (abbreviated as BzCuI). Density functional theory calculations revealed that BzCuI has a direct bandgap of 2.11 eV. Sequential fluorescence spectral shifts were observed in the temperature range of 80 to 300 K, indicating a reduction in the bandgap due to increased electron–phonon interactions at higher temperatures. The Huang–Rhys factor further confirmed the strong coupling between electrons and phonons in BzCuI. Additionally, BzCuI exhibited a unique fluorescence-switching behavior, transitioning from blue to red, which was triggered by a structural phase change involving the trapping and release of water molecules. This finding was supported by the temperature-dependent X-ray diffraction (XRD) pattern, which showed evidence of crystal lattice contraction upon heating. Furthermore, when mixed with silicon oil, BzCuI demonstrated the potential for applications such as anticounterfeiting ink and moisture-sensitivity assays. Compared to other OIMHs, BzCuI exhibited the most significant fluorescence shift within the visual spectrum, making it highly promising for various optical sensing applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermally Induced Reversible Fluorochromism by Self-Trapped Excitonic Emission in a Two-Dimensional Hybrid Copper(I)-Halide Single Crystal\",\"authors\":\"Amarjith V Dev, Manasa G. Basavarajappa, Swapnil S. Deshpande, Poulomi Mukherjee, Avija Ajayakumar, Chinnadurai Muthu, Takuya Okamoto, Sudip Chakraborty*, D. D. Sarma, Vasudevanpillai Biju and Chakkooth Vijayakumar*, \",\"doi\":\"10.1021/acs.chemmater.4c00045\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Organic–inorganic metal halides (OIMHs) have gained significant attention as promising materials for various applications, including lighting, imaging, and energy conversion. The development of Pb-free alternatives to traditional Pb-based materials has become increasingly important for environmental and health reasons. In this study, we report on the thermally induced fluorochromism of a two-dimensional OIMH based on Cu(I), namely, (Bz)<sub>2</sub>Cu<sub>2</sub>I<sub>4</sub>·H<sub>2</sub>O (abbreviated as BzCuI). Density functional theory calculations revealed that BzCuI has a direct bandgap of 2.11 eV. Sequential fluorescence spectral shifts were observed in the temperature range of 80 to 300 K, indicating a reduction in the bandgap due to increased electron–phonon interactions at higher temperatures. The Huang–Rhys factor further confirmed the strong coupling between electrons and phonons in BzCuI. Additionally, BzCuI exhibited a unique fluorescence-switching behavior, transitioning from blue to red, which was triggered by a structural phase change involving the trapping and release of water molecules. This finding was supported by the temperature-dependent X-ray diffraction (XRD) pattern, which showed evidence of crystal lattice contraction upon heating. Furthermore, when mixed with silicon oil, BzCuI demonstrated the potential for applications such as anticounterfeiting ink and moisture-sensitivity assays. Compared to other OIMHs, BzCuI exhibited the most significant fluorescence shift within the visual spectrum, making it highly promising for various optical sensing applications.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-06-06\",\"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.4c00045\",\"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}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00045","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}
Thermally Induced Reversible Fluorochromism by Self-Trapped Excitonic Emission in a Two-Dimensional Hybrid Copper(I)-Halide Single Crystal
Organic–inorganic metal halides (OIMHs) have gained significant attention as promising materials for various applications, including lighting, imaging, and energy conversion. The development of Pb-free alternatives to traditional Pb-based materials has become increasingly important for environmental and health reasons. In this study, we report on the thermally induced fluorochromism of a two-dimensional OIMH based on Cu(I), namely, (Bz)2Cu2I4·H2O (abbreviated as BzCuI). Density functional theory calculations revealed that BzCuI has a direct bandgap of 2.11 eV. Sequential fluorescence spectral shifts were observed in the temperature range of 80 to 300 K, indicating a reduction in the bandgap due to increased electron–phonon interactions at higher temperatures. The Huang–Rhys factor further confirmed the strong coupling between electrons and phonons in BzCuI. Additionally, BzCuI exhibited a unique fluorescence-switching behavior, transitioning from blue to red, which was triggered by a structural phase change involving the trapping and release of water molecules. This finding was supported by the temperature-dependent X-ray diffraction (XRD) pattern, which showed evidence of crystal lattice contraction upon heating. Furthermore, when mixed with silicon oil, BzCuI demonstrated the potential for applications such as anticounterfeiting ink and moisture-sensitivity assays. Compared to other OIMHs, BzCuI exhibited the most significant fluorescence shift within the visual spectrum, making it highly promising for various optical sensing applications.
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.