Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission
Zero-dimensional (0D) hybrid organic–inorganic lead halides have been shown to display efficient broadband photoluminescence and are, therefore, of significant interest for artificial lighting applications. However, work that investigates the formability of the materials as a function of templating...
| Main Authors: | , , , , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2020
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/142115 |
| _version_ | 1811690148491952128 |
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| author | Febriansyah, Benny Neo, Daniel Chong Shern Giovanni, David Srivastava, Shivani Lekina, Yulia Koh, Teck Ming Li, Yongxin Shen, Ze Xiang Asta, Mark Sum, Tze Chien Mathews, Nripan England, Jason |
| author2 | School of Materials Science and Engineering |
| author_facet | School of Materials Science and Engineering Febriansyah, Benny Neo, Daniel Chong Shern Giovanni, David Srivastava, Shivani Lekina, Yulia Koh, Teck Ming Li, Yongxin Shen, Ze Xiang Asta, Mark Sum, Tze Chien Mathews, Nripan England, Jason |
| author_sort | Febriansyah, Benny |
| collection | NTU |
| description | Zero-dimensional (0D) hybrid organic–inorganic lead halides have been shown to display efficient broadband photoluminescence and are, therefore, of significant interest for artificial lighting applications. However, work that investigates the formability of the materials as a function of templating organic cation structure is rare. This severely limits our ability to rationally design new materials displaying specific structural and photophysical properties. With the goal of accessing rare 0D trimeric bromoplumbates, we have systematically varied templating N-alkylpyridinium cations and examined their impact upon inorganic lattice structure. Whereas comparatively short and flexible N-alkyl substituents (ethyl, 2-hydroxyethyl, and pentyl) yield one-dimensional (1D) inorganic chains, more rigid substituents (benzyl, acetamidyl, and cyanomethyl) afford hybrids composed of lead bromide face-sharing trimers (i.e., [Pb3Br12]6–). Of the rigid substituents studied, benzyl groups were found to enforce the highest level of distortion of the [PbBr6]4– octahedra that comprise their trimeric structures. Upon exposure to ultraviolet (UV) light, N-benzylpyridinium lead bromide (1)6[Pb3Br12] exhibits a broadband emission, centered at 571 nm, which spans from 400 to 800 nm. More specifically, it displays a large Stokes shift of ca. 1.39 eV and a full width at half-maximum of ca. 146 nm. This broadband emission decays with a comparatively long lifetime of 426 ns at room temperature, which increases to 5.8 μs at 77 K. The reduced size and dimensionality of its inorganic lattice also result in a photoluminescence quantum yield (of at least 10%) that is approximately one order of magnitude higher than that of its 1D congeners. Mechanistically, broadband emission in (1)6[Pb3Br12] is believed to originate from triplet excited state(s) obtained from excited-state structural reorganization of the [Pb3Br12]6– moiety. |
| first_indexed | 2024-10-01T05:59:23Z |
| format | Journal Article |
| id | ntu-10356/142115 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:59:23Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1421152021-11-09T02:21:29Z Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission Febriansyah, Benny Neo, Daniel Chong Shern Giovanni, David Srivastava, Shivani Lekina, Yulia Koh, Teck Ming Li, Yongxin Shen, Ze Xiang Asta, Mark Sum, Tze Chien Mathews, Nripan England, Jason School of Materials Science and Engineering School of Physical and Mathematical Sciences Interdisciplinary Graduate School (IGS) Energy Research Institute @ NTU (ERI@N) Science::Chemistry::Inorganic chemistry Science::Physics Metal Halide Hybrids Trimer Bromoplumbate Zero-dimensional (0D) hybrid organic–inorganic lead halides have been shown to display efficient broadband photoluminescence and are, therefore, of significant interest for artificial lighting applications. However, work that investigates the formability of the materials as a function of templating organic cation structure is rare. This severely limits our ability to rationally design new materials displaying specific structural and photophysical properties. With the goal of accessing rare 0D trimeric bromoplumbates, we have systematically varied templating N-alkylpyridinium cations and examined their impact upon inorganic lattice structure. Whereas comparatively short and flexible N-alkyl substituents (ethyl, 2-hydroxyethyl, and pentyl) yield one-dimensional (1D) inorganic chains, more rigid substituents (benzyl, acetamidyl, and cyanomethyl) afford hybrids composed of lead bromide face-sharing trimers (i.e., [Pb3Br12]6–). Of the rigid substituents studied, benzyl groups were found to enforce the highest level of distortion of the [PbBr6]4– octahedra that comprise their trimeric structures. Upon exposure to ultraviolet (UV) light, N-benzylpyridinium lead bromide (1)6[Pb3Br12] exhibits a broadband emission, centered at 571 nm, which spans from 400 to 800 nm. More specifically, it displays a large Stokes shift of ca. 1.39 eV and a full width at half-maximum of ca. 146 nm. This broadband emission decays with a comparatively long lifetime of 426 ns at room temperature, which increases to 5.8 μs at 77 K. The reduced size and dimensionality of its inorganic lattice also result in a photoluminescence quantum yield (of at least 10%) that is approximately one order of magnitude higher than that of its 1D congeners. Mechanistically, broadband emission in (1)6[Pb3Br12] is believed to originate from triplet excited state(s) obtained from excited-state structural reorganization of the [Pb3Br12]6– moiety. Accepted version 2020-06-16T03:03:22Z 2020-06-16T03:03:22Z 2020 Journal Article Febriansyah, B., Neo, D. C. S., Giovanni, D., Srivastava, S., Lekina, Y., Koh, T. M., . . . England, J. (2020). Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission. Chemistry of Materials, 32(11), 4431-4441. doi:10.1021/acs.chemmater.9b03925 0897-4756 https://hdl.handle.net/10356/142115 10.1021/acs.chemmater.9b03925 11 32 4431 4441 en Chemistry of Materials 10.21979/N9/PZK1H6 This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.9b03925 application/pdf |
| spellingShingle | Science::Chemistry::Inorganic chemistry Science::Physics Metal Halide Hybrids Trimer Bromoplumbate Febriansyah, Benny Neo, Daniel Chong Shern Giovanni, David Srivastava, Shivani Lekina, Yulia Koh, Teck Ming Li, Yongxin Shen, Ze Xiang Asta, Mark Sum, Tze Chien Mathews, Nripan England, Jason Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title | Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title_full | Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title_fullStr | Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title_full_unstemmed | Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title_short | Targeted synthesis of trimeric organic–bromoplumbate hybrids that display intrinsic, highly Stokes-shifted, broadband emission |
| title_sort | targeted synthesis of trimeric organic bromoplumbate hybrids that display intrinsic highly stokes shifted broadband emission |
| topic | Science::Chemistry::Inorganic chemistry Science::Physics Metal Halide Hybrids Trimer Bromoplumbate |
| url | https://hdl.handle.net/10356/142115 |
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