Reinvestigation of thermal isomerization of cis-stereoregulated poly(phenylacetylene) by spectroscopic study and DFT calculation
Cis-stereoregulated poly(phenylacetylene) [poly(PA)] was synthesized by polymerization of PA using Rh catalysts, and the thermal isomerization behavior was analyzed by DSC, 1H NMR, IR and Raman spectroscopies. Cis-poly(PA) exhibited DSC exothermic peaks around 170 °C corresponding to isomerization o...
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| Veröffentlicht in: | Polymer (Guilford) 2021-08, Vol.229, p.124013, Article 124013 |
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| creator | Goto, Masahide Minami, Masaki Sogawa, Hiromitsu Sanda, Fumio |
| description | Cis-stereoregulated poly(phenylacetylene) [poly(PA)] was synthesized by polymerization of PA using Rh catalysts, and the thermal isomerization behavior was analyzed by DSC, 1H NMR, IR and Raman spectroscopies. Cis-poly(PA) exhibited DSC exothermic peaks around 170 °C corresponding to isomerization of main chain from cis to trans. The cis content decreased to 12% after heating at 170 °C, and became almost zero after heating at 180 °C, which was determined by 1H NMR spectroscopy. Vibration frequencies of 8-mer models of cis- and trans-poly(PA) were calculated by DFT method to simulate IR and Raman spectra. DFT calculations indicated that an IR absorption peak at 737 cm−1 of poly(PA) originates from out-of-plane bending vibrations of C–H and C–Ph bonded to cis-main chain, and a peak at 692 cm−1 originates from out-of-plane deformation vibrations of C–H in phenyl moieties substituted with trans-main chain. These two IR absorption peaks were used to determine the geometrical structures of poly(PA) main chain. The present study confirmed that DFT calculations provide useful evidences for characterizing geometrical structures of poly(PA).
[Display omitted]
•Thermal isomerization of cis-stereoregulated poly(phenylacetylene) [poly(PA)] into trans-poly(PA).•Monitoring the isomerization utilizing IR absorption spectroscopy.•Providing evidence for assignment of IR absorption peaks based on DFT calculations. |
| doi_str_mv | 10.1016/j.polymer.2021.124013 |
| format | Article |
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[Display omitted]
•Thermal isomerization of cis-stereoregulated poly(phenylacetylene) [poly(PA)] into trans-poly(PA).•Monitoring the isomerization utilizing IR absorption spectroscopy.•Providing evidence for assignment of IR absorption peaks based on DFT calculations.</description><identifier>ISSN: 0032-3861</identifier><identifier>EISSN: 1873-2291</identifier><identifier>DOI: 10.1016/j.polymer.2021.124013</identifier><language>eng</language><publisher>OXFORD: Elsevier Ltd</publisher><subject>Absorption ; Catalysts ; Density functional theory calculation ; Heating ; Isomerization ; Magnetic resonance spectroscopy ; NMR ; NMR spectroscopy ; Nuclear magnetic resonance ; Out of plane bending ; Phenylacetylene ; Physical Sciences ; Polyacetylene ; Polymer Science ; Polyphenylacetylene ; Raman spectra ; Raman spectroscopy ; Science & Technology ; Spectrum analysis ; Vibration ; Vibrations</subject><ispartof>Polymer (Guilford), 2021-08, Vol.229, p.124013, Article 124013</ispartof><rights>2021 Elsevier Ltd</rights><rights>Copyright Elsevier BV Aug 16, 2021</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>true</woscitedreferencessubscribed><woscitedreferencescount>7</woscitedreferencescount><woscitedreferencesoriginalsourcerecordid>wos000715760400007</woscitedreferencesoriginalsourcerecordid><citedby>FETCH-LOGICAL-c450t-11d36fa66269995d0d8cb8b6c79528f3a7801e878db813380d959f39fbebfe813</citedby><cites>FETCH-LOGICAL-c450t-11d36fa66269995d0d8cb8b6c79528f3a7801e878db813380d959f39fbebfe813</cites><orcidid>0000-0002-1113-4771</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.polymer.2021.124013$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>315,781,785,3551,27929,27930,39263,46000</link.rule.ids></links><search><creatorcontrib>Goto, Masahide</creatorcontrib><creatorcontrib>Minami, Masaki</creatorcontrib><creatorcontrib>Sogawa, Hiromitsu</creatorcontrib><creatorcontrib>Sanda, Fumio</creatorcontrib><title>Reinvestigation of thermal isomerization of cis-stereoregulated poly(phenylacetylene) by spectroscopic study and DFT calculation</title><title>Polymer (Guilford)</title><addtitle>POLYMER</addtitle><description>Cis-stereoregulated poly(phenylacetylene) [poly(PA)] was synthesized by polymerization of PA using Rh catalysts, and the thermal isomerization behavior was analyzed by DSC, 1H NMR, IR and Raman spectroscopies. Cis-poly(PA) exhibited DSC exothermic peaks around 170 °C corresponding to isomerization of main chain from cis to trans. The cis content decreased to 12% after heating at 170 °C, and became almost zero after heating at 180 °C, which was determined by 1H NMR spectroscopy. Vibration frequencies of 8-mer models of cis- and trans-poly(PA) were calculated by DFT method to simulate IR and Raman spectra. DFT calculations indicated that an IR absorption peak at 737 cm−1 of poly(PA) originates from out-of-plane bending vibrations of C–H and C–Ph bonded to cis-main chain, and a peak at 692 cm−1 originates from out-of-plane deformation vibrations of C–H in phenyl moieties substituted with trans-main chain. These two IR absorption peaks were used to determine the geometrical structures of poly(PA) main chain. The present study confirmed that DFT calculations provide useful evidences for characterizing geometrical structures of poly(PA).
[Display omitted]
•Thermal isomerization of cis-stereoregulated poly(phenylacetylene) [poly(PA)] into trans-poly(PA).•Monitoring the isomerization utilizing IR absorption spectroscopy.•Providing evidence for assignment of IR absorption peaks based on DFT calculations.</description><subject>Absorption</subject><subject>Catalysts</subject><subject>Density functional theory calculation</subject><subject>Heating</subject><subject>Isomerization</subject><subject>Magnetic resonance spectroscopy</subject><subject>NMR</subject><subject>NMR spectroscopy</subject><subject>Nuclear magnetic resonance</subject><subject>Out of plane bending</subject><subject>Phenylacetylene</subject><subject>Physical Sciences</subject><subject>Polyacetylene</subject><subject>Polymer Science</subject><subject>Polyphenylacetylene</subject><subject>Raman spectra</subject><subject>Raman spectroscopy</subject><subject>Science & Technology</subject><subject>Spectrum analysis</subject><subject>Vibration</subject><subject>Vibrations</subject><issn>0032-3861</issn><issn>1873-2291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><sourceid>HGBXW</sourceid><recordid>eNqNkE2L1TAUhoMoeB39CULAjSK95qNN05XIHUeFAUHGdUiTk5lcepuapCN15U83tZfZ6ioh533OOXkQeknJnhIq3h33UxiWE8Q9I4zuKasJ5Y_QjsqWV4x19DHaEcJZxaWgT9GzlI6EENaweod-fwM_3kPK_lZnH0YcHM53EE96wD6F0tT_eigYn6qUIUKIcDsPOoPF6-jX0x2My6AN5GWAEd7gfsFpApNjSCZM3uCUZ7tgPVp8eXWDjR7Mype-z9ETp4cEL87nBfp-9fHm8Lm6_vrpy-HDdWXqhuSKUsuF00Iw0XVdY4mVppe9MG3XMOm4biWhIFtpe0k5l8R2Ted453roHZSnC_Rq6zvF8GMuH1bHMMexjFSsEbLo4aQuqWZLmbJ5iuDUFP1Jx0VRolbZ6qjOstUqW22yC_d2435CH1wyHkYDD2yx3dKmFaQm67Wk5f-nDz7_FXUI85gL-n5Dobi692WNM259LL6VDf4fq_4BnnGujQ</recordid><startdate>20210816</startdate><enddate>20210816</enddate><creator>Goto, Masahide</creator><creator>Minami, Masaki</creator><creator>Sogawa, Hiromitsu</creator><creator>Sanda, Fumio</creator><general>Elsevier Ltd</general><general>Elsevier</general><general>Elsevier BV</general><scope>BLEPL</scope><scope>DTL</scope><scope>HGBXW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QO</scope><scope>7QQ</scope><scope>7SC</scope><scope>7SE</scope><scope>7SP</scope><scope>7SR</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>JG9</scope><scope>JQ2</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>P64</scope><orcidid>https://orcid.org/0000-0002-1113-4771</orcidid></search><sort><creationdate>20210816</creationdate><title>Reinvestigation of thermal isomerization of cis-stereoregulated poly(phenylacetylene) by spectroscopic study and DFT calculation</title><author>Goto, Masahide ; Minami, Masaki ; Sogawa, Hiromitsu ; Sanda, Fumio</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c450t-11d36fa66269995d0d8cb8b6c79528f3a7801e878db813380d959f39fbebfe813</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Absorption</topic><topic>Catalysts</topic><topic>Density functional theory calculation</topic><topic>Heating</topic><topic>Isomerization</topic><topic>Magnetic resonance spectroscopy</topic><topic>NMR</topic><topic>NMR spectroscopy</topic><topic>Nuclear magnetic resonance</topic><topic>Out of plane bending</topic><topic>Phenylacetylene</topic><topic>Physical Sciences</topic><topic>Polyacetylene</topic><topic>Polymer Science</topic><topic>Polyphenylacetylene</topic><topic>Raman spectra</topic><topic>Raman spectroscopy</topic><topic>Science & Technology</topic><topic>Spectrum analysis</topic><topic>Vibration</topic><topic>Vibrations</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Goto, Masahide</creatorcontrib><creatorcontrib>Minami, Masaki</creatorcontrib><creatorcontrib>Sogawa, Hiromitsu</creatorcontrib><creatorcontrib>Sanda, Fumio</creatorcontrib><collection>Web of Science Core Collection</collection><collection>Science Citation Index Expanded</collection><collection>Web of Science - Science Citation Index Expanded - 2021</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Biotechnology Research Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Biotechnology and BioEngineering Abstracts</collection><jtitle>Polymer (Guilford)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Goto, Masahide</au><au>Minami, Masaki</au><au>Sogawa, Hiromitsu</au><au>Sanda, Fumio</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reinvestigation of thermal isomerization of cis-stereoregulated poly(phenylacetylene) by spectroscopic study and DFT calculation</atitle><jtitle>Polymer (Guilford)</jtitle><stitle>POLYMER</stitle><date>2021-08-16</date><risdate>2021</risdate><volume>229</volume><spage>124013</spage><pages>124013-</pages><artnum>124013</artnum><issn>0032-3861</issn><eissn>1873-2291</eissn><abstract>Cis-stereoregulated poly(phenylacetylene) [poly(PA)] was synthesized by polymerization of PA using Rh catalysts, and the thermal isomerization behavior was analyzed by DSC, 1H NMR, IR and Raman spectroscopies. Cis-poly(PA) exhibited DSC exothermic peaks around 170 °C corresponding to isomerization of main chain from cis to trans. The cis content decreased to 12% after heating at 170 °C, and became almost zero after heating at 180 °C, which was determined by 1H NMR spectroscopy. Vibration frequencies of 8-mer models of cis- and trans-poly(PA) were calculated by DFT method to simulate IR and Raman spectra. DFT calculations indicated that an IR absorption peak at 737 cm−1 of poly(PA) originates from out-of-plane bending vibrations of C–H and C–Ph bonded to cis-main chain, and a peak at 692 cm−1 originates from out-of-plane deformation vibrations of C–H in phenyl moieties substituted with trans-main chain. These two IR absorption peaks were used to determine the geometrical structures of poly(PA) main chain. The present study confirmed that DFT calculations provide useful evidences for characterizing geometrical structures of poly(PA).
[Display omitted]
•Thermal isomerization of cis-stereoregulated poly(phenylacetylene) [poly(PA)] into trans-poly(PA).•Monitoring the isomerization utilizing IR absorption spectroscopy.•Providing evidence for assignment of IR absorption peaks based on DFT calculations.</abstract><cop>OXFORD</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.polymer.2021.124013</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-1113-4771</orcidid><oa>free_for_read</oa></addata></record> |
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| source | ScienceDirect Journals (5 years ago - present); Web of Science - Science Citation Index Expanded - 2021<img src="https://exlibris-pub.s3.amazonaws.com/fromwos-v2.jpg" /> |
| subjects | Absorption Catalysts Density functional theory calculation Heating Isomerization Magnetic resonance spectroscopy NMR NMR spectroscopy Nuclear magnetic resonance Out of plane bending Phenylacetylene Physical Sciences Polyacetylene Polymer Science Polyphenylacetylene Raman spectra Raman spectroscopy Science & Technology Spectrum analysis Vibration Vibrations |
| title | Reinvestigation of thermal isomerization of cis-stereoregulated poly(phenylacetylene) by spectroscopic study and DFT calculation |
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