Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole
Three new amino-<i>s</i>-triazine-based dendrons, <b>1a</b>, <b>1b</b>, and <b>1c</b>, containing an aryl-CN moiety in the dendritic skeleton were prepared in 72–81% yields (<b>1a</b>: R<sup>1</sup> = − N(<i>n</i>-C&...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-01-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/12/2/185 |
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| author | Yao-Chih Lu Yu-Tsz Hsu Tsung-Yen Yang I-Chun Liou Sheng-Wei Wang Po-Chia Huang Jey-Jau Lee Long-Li Lai Hsiu-Fu Hsu |
| author_facet | Yao-Chih Lu Yu-Tsz Hsu Tsung-Yen Yang I-Chun Liou Sheng-Wei Wang Po-Chia Huang Jey-Jau Lee Long-Li Lai Hsiu-Fu Hsu |
| author_sort | Yao-Chih Lu |
| collection | DOAJ |
| description | Three new amino-<i>s</i>-triazine-based dendrons, <b>1a</b>, <b>1b</b>, and <b>1c</b>, containing an aryl-CN moiety in the dendritic skeleton were prepared in 72–81% yields (<b>1a</b>: R<sup>1</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, R<sup>2</sup> = <i>n</i>-OC<sub>8</sub>H<sub>17</sub>, <b>1b</b>: R<sup>1</sup> = R<sup>2</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, <b>1c</b>: R<sup>1</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, R<sup>2</sup> = − N(<i>n</i>-C<sub>4</sub>H<sub>9</sub>)<sub>2</sub>). Dendrons <b>1a</b> with N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub> and <i>n</i>-OC<sub>8</sub>H<sub>17</sub> peripheral substituents, surprisingly, did not show any mesogenic phase during the thermal process. However, non-mesogenic <b>1a</b> can be converted to mesogenic <b>1b</b> or <b>1c</b> by eliminating the peripheral dipole arising from the alkoxy substituent; dendron <b>1b</b> only comprising the same N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub> peripheral groups showed a ~25 °C mesogenic range on heating and ~108 °C mesogenic range on cooling. In contrast, dendron <b>1c</b> possessing different N(<i>n</i>-C<sub>m</sub>H<sub>2m+1</sub>)<sub>2</sub> (m = 8 versus m = 4) peripheral units, having similar stacking as <b>1b</b>, exhibited a columnar phase on thermal treatment, but its mesogenic range (~9 and ~66 °C on heating and cooling, respectively) was much narrower than that of <b>1b,</b> attributed to <b>1c</b>’s less flexible alkyl chains in the peripheral part of dendron. Dendron <b>1a</b> with the alkoxy substituent in the peripheral skeleton, creating additional dipole correspondingly, thus, leads to the dendritic molecules having a non-mesogenic stacking. Without the peripheral dipole for intermolecular side-by-side interaction, dendrons <b>1b</b> and <b>1c</b> exhibit a columnar phase on thermal treatment because of the vibration from the peripheral alkyl chain. |
| first_indexed | 2024-03-10T00:49:21Z |
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| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-10T00:49:21Z |
| publishDate | 2022-01-01 |
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| series | Nanomaterials |
| spelling | doaj.art-c9f59b55fcbb475a82d95f60bc873fb32023-11-23T14:54:18ZengMDPI AGNanomaterials2079-49912022-01-0112218510.3390/nano12020185Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral DipoleYao-Chih Lu0Yu-Tsz Hsu1Tsung-Yen Yang2I-Chun Liou3Sheng-Wei Wang4Po-Chia Huang5Jey-Jau Lee6Long-Li Lai7Hsiu-Fu Hsu8Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, TaiwanDepartment of Chemistry, Tamkang University, No. 151, Yingzhuan Rd., New Taipei City 251, TaiwanDepartment of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, TaiwanDepartment of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, TaiwanDepartment of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, TaiwanNational Synchrotron Radiation Research Center, No. 101, Hsin-Ann Rd., Hsinchu 300, TaiwanNational Synchrotron Radiation Research Center, No. 101, Hsin-Ann Rd., Hsinchu 300, TaiwanDepartment of Applied Chemistry, National Chi Nan University, No. 1 University Rd., Puli, Nantou 545, TaiwanDepartment of Chemistry, Tamkang University, No. 151, Yingzhuan Rd., New Taipei City 251, TaiwanThree new amino-<i>s</i>-triazine-based dendrons, <b>1a</b>, <b>1b</b>, and <b>1c</b>, containing an aryl-CN moiety in the dendritic skeleton were prepared in 72–81% yields (<b>1a</b>: R<sup>1</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, R<sup>2</sup> = <i>n</i>-OC<sub>8</sub>H<sub>17</sub>, <b>1b</b>: R<sup>1</sup> = R<sup>2</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, <b>1c</b>: R<sup>1</sup> = − N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, R<sup>2</sup> = − N(<i>n</i>-C<sub>4</sub>H<sub>9</sub>)<sub>2</sub>). Dendrons <b>1a</b> with N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub> and <i>n</i>-OC<sub>8</sub>H<sub>17</sub> peripheral substituents, surprisingly, did not show any mesogenic phase during the thermal process. However, non-mesogenic <b>1a</b> can be converted to mesogenic <b>1b</b> or <b>1c</b> by eliminating the peripheral dipole arising from the alkoxy substituent; dendron <b>1b</b> only comprising the same N(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>2</sub> peripheral groups showed a ~25 °C mesogenic range on heating and ~108 °C mesogenic range on cooling. In contrast, dendron <b>1c</b> possessing different N(<i>n</i>-C<sub>m</sub>H<sub>2m+1</sub>)<sub>2</sub> (m = 8 versus m = 4) peripheral units, having similar stacking as <b>1b</b>, exhibited a columnar phase on thermal treatment, but its mesogenic range (~9 and ~66 °C on heating and cooling, respectively) was much narrower than that of <b>1b,</b> attributed to <b>1c</b>’s less flexible alkyl chains in the peripheral part of dendron. Dendron <b>1a</b> with the alkoxy substituent in the peripheral skeleton, creating additional dipole correspondingly, thus, leads to the dendritic molecules having a non-mesogenic stacking. Without the peripheral dipole for intermolecular side-by-side interaction, dendrons <b>1b</b> and <b>1c</b> exhibit a columnar phase on thermal treatment because of the vibration from the peripheral alkyl chain.https://www.mdpi.com/2079-4991/12/2/185triazineliquid crystaldendron |
| spellingShingle | Yao-Chih Lu Yu-Tsz Hsu Tsung-Yen Yang I-Chun Liou Sheng-Wei Wang Po-Chia Huang Jey-Jau Lee Long-Li Lai Hsiu-Fu Hsu Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole Nanomaterials triazine liquid crystal dendron |
| title | Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole |
| title_full | Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole |
| title_fullStr | Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole |
| title_full_unstemmed | Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole |
| title_short | Converting non-Mesogenic to Mesogenic Stacking of Amino-<i>s</i>-Triazine-Based Dendrons with <i>p</i>-CN Phenyl Unit by Eliminating Peripheral Dipole |
| title_sort | converting non mesogenic to mesogenic stacking of amino i s i triazine based dendrons with i p i cn phenyl unit by eliminating peripheral dipole |
| topic | triazine liquid crystal dendron |
| url | https://www.mdpi.com/2079-4991/12/2/185 |
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