{"title":"有机钛聚合物元素后转化平行合成供受体π共轭聚合物。","authors":"Yoshimasa Matsumura, Alvin Tanudjaja, Mizuki Fukushima, Makoto Higuchi, Shin Ogino, Makoto Ishidoshiro, Yasuyuki Irie, Hiroaki Imoto, Kensuke Naka, Ryoyu Hifumi, Shinsuke Inagi, Ikuyoshi Tomita","doi":"10.1080/15685551.2023.2233228","DOIUrl":null,"url":null,"abstract":"<p><p>The donor-acceptor type π-conjugated polymers having heterole units were prepared by the reaction of a regioregular organometallic polymer having both reactive titanacyclopentadiene and electron-donor thiophene-2,5-diyl units in the main chain with electrophiles such as diphenyltin dichloride, dichlorophenylphosphine, and diiodophenylarsine. For example, a polymer having electron-accepting phosphole unit was obtained in 54% yield whose number-average molecular weight (<i>M</i><sub>n</sub>) and molecular weight distribution (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>) were estimated as 3,000 and 1.9, respectively. The obtained polymer exhibits a high highest occupied molecular orbital (HOMO) and low lowest unoccupied molecular orbital (LUMO) energy levels (-5.13 eV and -3.25 eV, respectively) due to the electron-donating thiophene and electron-accepting phosphole units. Reflecting upon the alternating structure of thiophene and phosphole, the polymer exhibits a band gap energy level (<i>E</i><sub>g</sub>) of 1.78 eV which is narrower than that of a derivative of poly(thiophene) (<i>E</i><sub>g</sub> = 2.25 eV).</p>","PeriodicalId":11170,"journal":{"name":"Designed Monomers and Polymers","volume":"26 1","pages":"190-197"},"PeriodicalIF":1.8000,"publicationDate":"2023-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10327520/pdf/","citationCount":"0","resultStr":"{\"title\":\"Parallel synthesis of donor-acceptor π-conjugated polymers by post-element transformation of organotitanium polymer.\",\"authors\":\"Yoshimasa Matsumura, Alvin Tanudjaja, Mizuki Fukushima, Makoto Higuchi, Shin Ogino, Makoto Ishidoshiro, Yasuyuki Irie, Hiroaki Imoto, Kensuke Naka, Ryoyu Hifumi, Shinsuke Inagi, Ikuyoshi Tomita\",\"doi\":\"10.1080/15685551.2023.2233228\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The donor-acceptor type π-conjugated polymers having heterole units were prepared by the reaction of a regioregular organometallic polymer having both reactive titanacyclopentadiene and electron-donor thiophene-2,5-diyl units in the main chain with electrophiles such as diphenyltin dichloride, dichlorophenylphosphine, and diiodophenylarsine. For example, a polymer having electron-accepting phosphole unit was obtained in 54% yield whose number-average molecular weight (<i>M</i><sub>n</sub>) and molecular weight distribution (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>) were estimated as 3,000 and 1.9, respectively. The obtained polymer exhibits a high highest occupied molecular orbital (HOMO) and low lowest unoccupied molecular orbital (LUMO) energy levels (-5.13 eV and -3.25 eV, respectively) due to the electron-donating thiophene and electron-accepting phosphole units. Reflecting upon the alternating structure of thiophene and phosphole, the polymer exhibits a band gap energy level (<i>E</i><sub>g</sub>) of 1.78 eV which is narrower than that of a derivative of poly(thiophene) (<i>E</i><sub>g</sub> = 2.25 eV).</p>\",\"PeriodicalId\":11170,\"journal\":{\"name\":\"Designed Monomers and Polymers\",\"volume\":\"26 1\",\"pages\":\"190-197\"},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2023-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10327520/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Designed Monomers and Polymers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1080/15685551.2023.2233228\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Designed Monomers and Polymers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1080/15685551.2023.2233228","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Parallel synthesis of donor-acceptor π-conjugated polymers by post-element transformation of organotitanium polymer.
The donor-acceptor type π-conjugated polymers having heterole units were prepared by the reaction of a regioregular organometallic polymer having both reactive titanacyclopentadiene and electron-donor thiophene-2,5-diyl units in the main chain with electrophiles such as diphenyltin dichloride, dichlorophenylphosphine, and diiodophenylarsine. For example, a polymer having electron-accepting phosphole unit was obtained in 54% yield whose number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were estimated as 3,000 and 1.9, respectively. The obtained polymer exhibits a high highest occupied molecular orbital (HOMO) and low lowest unoccupied molecular orbital (LUMO) energy levels (-5.13 eV and -3.25 eV, respectively) due to the electron-donating thiophene and electron-accepting phosphole units. Reflecting upon the alternating structure of thiophene and phosphole, the polymer exhibits a band gap energy level (Eg) of 1.78 eV which is narrower than that of a derivative of poly(thiophene) (Eg = 2.25 eV).
期刊介绍：
Designed Monomers and Polymers ( DMP) publishes prompt peer-reviewed papers and short topical reviews on all areas of macromolecular design and applications. Emphasis is placed on the preparations of new monomers, including characterization and applications. Experiments should be presented in sufficient detail (including specific observations, precautionary notes, use of new materials, techniques, and their possible problems) that they could be reproduced by any researcher wishing to repeat the work.
The journal also includes macromolecular design of polymeric materials (such as polymeric biomaterials, biomedical polymers, etc.) with medical applications.
DMP provides an interface between organic and polymer chemistries and aims to bridge the gap between monomer synthesis and the design of new polymers. Submssions are invited in the areas including, but not limited to:
-macromolecular science, initiators, macroinitiators for macromolecular design
-kinetics, mechanism and modelling aspects of polymerization
-new methods of synthesis of known monomers
-new monomers (must show evidence for polymerization, e.g. polycondensation, sequential combination, oxidative coupling, radiation, plasma polymerization)
-functional prepolymers of various architectures such as hyperbranched polymers, telechelic polymers, macromonomers, or dendrimers
-new polymeric materials with biomedical applications
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