A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe
Abstract Solvent-free, nonvolatile, room-temperature alkylated-π functional molecular liquids (FMLs) are rapidly emerging as a new generation of fluid matter. However, precision design to tune their physicochemical properties remains a serious challenge because the properties are governed by subtle...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2017-06-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-017-03584-1 |
| _version_ | 1818420205592772608 |
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| author | Fengniu Lu Tomohisa Takaya Koichi Iwata Izuru Kawamura Akinori Saeki Masashi Ishii Kazuhiko Nagura Takashi Nakanishi |
| author_facet | Fengniu Lu Tomohisa Takaya Koichi Iwata Izuru Kawamura Akinori Saeki Masashi Ishii Kazuhiko Nagura Takashi Nakanishi |
| author_sort | Fengniu Lu |
| collection | DOAJ |
| description | Abstract Solvent-free, nonvolatile, room-temperature alkylated-π functional molecular liquids (FMLs) are rapidly emerging as a new generation of fluid matter. However, precision design to tune their physicochemical properties remains a serious challenge because the properties are governed by subtle π-π interactions among functional π-units, which are very hard to control and characterize. Herein, we address the issue by probing π-π interactions with highly sensitive pyrene-fluorescence. A series of alkylated pyrene FMLs were synthesized. The photophysical properties were artfully engineered with rational modulation of the number, length, and substituent motif of alkyl chains attached to the pyrene unit. The different emission from the excimer to uncommon intermediate to the monomer scaled the pyrene-pyrene interactions in a clear trend, from stronger to weaker to negligible. Synchronously, the physical nature of these FMLs was regulated from inhomogeneous to isotropic. The inhomogeneity, unexplored before, was thoroughly investigated by ultrafast time-resolved spectroscopy techniques. The result provides a clearer image of liquid matter. Our methodology demonstrates a potential to unambiguously determine local molecular organizations of amorphous materials, which cannot be achieved by conventional structural analysis. Therefore this study provides a guide to design alkylated-π FMLs with tailorable physicochemical properties. |
| first_indexed | 2024-12-14T12:50:46Z |
| format | Article |
| id | doaj.art-352ad2599baf456693931eef6fb1d44c |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-12-14T12:50:46Z |
| publishDate | 2017-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-352ad2599baf456693931eef6fb1d44c2022-12-21T23:00:41ZengNature PortfolioScientific Reports2045-23222017-06-017111210.1038/s41598-017-03584-1A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a ProbeFengniu Lu0Tomohisa Takaya1Koichi Iwata2Izuru Kawamura3Akinori Saeki4Masashi Ishii5Kazuhiko Nagura6Takashi Nakanishi7Frontier Molecules Group, International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)Department of Chemistry, Faculty of Science, Gakushuin UniversityDepartment of Chemistry, Faculty of Science, Gakushuin UniversityGraduate School of Engineering, Yokohama National UniversityDepartment of Applied Chemistry, Graduate School of Engineering, Osaka UniversitySurface Physics and Characterization Group, Research Center for Advanced Measurement and CharacterizationInternational Center for Young Scientists, NIMSFrontier Molecules Group, International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)Abstract Solvent-free, nonvolatile, room-temperature alkylated-π functional molecular liquids (FMLs) are rapidly emerging as a new generation of fluid matter. However, precision design to tune their physicochemical properties remains a serious challenge because the properties are governed by subtle π-π interactions among functional π-units, which are very hard to control and characterize. Herein, we address the issue by probing π-π interactions with highly sensitive pyrene-fluorescence. A series of alkylated pyrene FMLs were synthesized. The photophysical properties were artfully engineered with rational modulation of the number, length, and substituent motif of alkyl chains attached to the pyrene unit. The different emission from the excimer to uncommon intermediate to the monomer scaled the pyrene-pyrene interactions in a clear trend, from stronger to weaker to negligible. Synchronously, the physical nature of these FMLs was regulated from inhomogeneous to isotropic. The inhomogeneity, unexplored before, was thoroughly investigated by ultrafast time-resolved spectroscopy techniques. The result provides a clearer image of liquid matter. Our methodology demonstrates a potential to unambiguously determine local molecular organizations of amorphous materials, which cannot be achieved by conventional structural analysis. Therefore this study provides a guide to design alkylated-π FMLs with tailorable physicochemical properties.https://doi.org/10.1038/s41598-017-03584-1 |
| spellingShingle | Fengniu Lu Tomohisa Takaya Koichi Iwata Izuru Kawamura Akinori Saeki Masashi Ishii Kazuhiko Nagura Takashi Nakanishi A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe Scientific Reports |
| title | A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe |
| title_full | A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe |
| title_fullStr | A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe |
| title_full_unstemmed | A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe |
| title_short | A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe |
| title_sort | guide to design functional molecular liquids with tailorable properties using pyrene fluorescence as a probe |
| url | https://doi.org/10.1038/s41598-017-03584-1 |
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