Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents

Zhen-Zhen Sun; Yan-Ning Zhang; Hao-Yu Qiu; Xue-Ting Lu; Liang-Xuan Ren; Le-Fei Shen; Wen Li; Afang Zhang

doi:10.1007/s10118-023-2991-6

Your Location：

Home >

Browse articles >

Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents

RESEARCH ARTICLE | Updated：2023-09-21

- Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents
- Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents
- 高分子科学（英文版） 2023年41卷第10期页码：1543-1554
- Affiliations：
  
  International Joint Laboratory of Biomimetic and Smart Polymers, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
- Author bio：
  
  wli@shu.edu.cn (W.L.)
  azhang@shu.edu.cn (A.Z.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 21971160 and 21971161) and Program for Professor of Special Appointment (No. Eastern Scholar TP2019039) at Shanghai Institutions of Higher Learning.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-2991-6.
- DOI：10.1007/s10118-023-2991-6
  中图分类号：
- 收稿：2023-04-01，
  
  修回：2023-4-15，
  
  录用：2023-4-17，
  
  网络首发：2023-06-12，
  
  纸质出版：2023-10-01
- Accepted：
Scan QR Code
Sun, Z. Z.; Zhang, Y. N.; Qiu, H. Y.; Lu, X. T.; Ren, L. X.; Shen, L. F.; Li, W.; Zhang, A. Synthesis of helical poly(phenylacetylene)s carrying dendritic pendants with varied branching densities through polymerization in different solvents. Chinese J. Polym. Sci. 2023, 41, 1543–1554

Zhen-Zhen Sun, Yan-Ning Zhang, Hao-Yu Qiu, et al. Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1543-1554.
Sun, Z. Z.; Zhang, Y. N.; Qiu, H. Y.; Lu, X. T.; Ren, L. X.; Shen, L. F.; Li, W.; Zhang, A. Synthesis of helical poly(phenylacetylene)s carrying dendritic pendants with varied branching densities through polymerization in different solvents. Chinese J. Polym. Sci. 2023, 41, 1543–1554 DOI： 10.1007/s10118-023-2991-6.

Zhen-Zhen Sun, Yan-Ning Zhang, Hao-Yu Qiu, et al. Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1543-1554. DOI： 10.1007/s10118-023-2991-6.

摘要

A homologous series of dendronized helical poly(phenylacetylene)s (PPAs) carrying dendritic oligoethylene glycols (OEGs) with different branching density were synthesized. These dendronized PPAs exhibit different thermoresponsiveness according to branching density of the OEGs

and their helicities are relevant to polymerization solvents due to varied shielding effect from the dendritic OEGs.

Abstract

Helical poly(phenylacetylene)s (PPAs) have received extensive attention because of their features in dynamic chirality and promising applications. Therefore

understanding relationship among the polymer molecular structures

polymerization conditions and tunability of their chirality is of key scientific value. Recently

we developed a novel class of dendronized PPAs carrying 3-fold dendritic oligo(ethylene glycols) (OEGs)

via

alanine linkage

and found that these bulky polymers exhibited tunable helical conformations through thermally-mediated dehydration and aggregation. Herein

we report on synthesis of a homologous series of dendronized PPAs that carry 2-fold

3-fold or 6-fold dendritic OEG pendants

and focus on effects of molecular topological structures

peripheral units and polymerization solvents on the thermoresponsiveness and their conformation switching behaviors. Effects of branching density and peripheral units (ethoxyl or methoxyl) of the dendritic OEG pendants were examined

and found to play a decisive role on the helical conformation and thermoresponsiveness of these dendronized PPAs due to their different bulkiness and overall hydrophilicity. In addition

different polymerization solvents were checked for their possible influence on the polymerization

thermoresponsive behavior and the chirality of the resulting polymers. For polymerization in selective solvents like water or methanol

the obtained dendronized PPAs exhibited weak thermal transitions

while polymerization in non-selective solvent like THF furnished PPAs with characteristic thermoresponsive behavior

indicating that solvents were involved in the process of polymerization of the dendronized macromonomers. More interestingly

different chiralities of the PPAs through polymerization in various solvents were retained

irrelevant to the purification process and solvents treatments. This work suggests that the topological structures together with polymerization solvents can modulate the thermoresponsive behavior and helical conformation of the dendronized PPAs.

关键词

Keywords

references

Okamoto,Y.Helicalpolymersforefficientenantiomerseparation. Adv. Polym. Sci. 2013 , 261 ,391−414..

Leigh,T.;Fernandez-Trillo,P.Helicalpolymersforbiologicalandmedicalapplications. Nat. Rev. Chem. 2020 , 4 ,291−310..

Zhang,Y.;Deng,J.Chiralhelicalpolymermaterialsderivedfromachiralmonomersandtheirchiralapplications. Polym. Chem. 2020 , 11 ,5407−5423..

Zheng,Z.G.;Lu,Y.Q.;Li,Q.Photoprogrammablemesogenicsofthelicalarchitectures:apromisingavenuetowardfuturechiro-optics. Adv. Mater. 2020 , 32 ,1905318..

Li,S.Y.;Gao,R.T.;Chen,Z.;Liu,N.;Wu,Z.Q.Advancesincircularlypolarizedluminescencematerialsbasedonhelicalpolymers. J. Mater. Chem. C 2023 , 11 ,1242−1250..

Nakano,T.;Okamoto,Y.Synthetichelicalpolymers: conformationandfunction. Chem. Rev. 2001 , 101 ,4013−4038..

Liu,J.Z.;Lam,J.W.Y.;Tang,B.Z.Acetylenicpolymers:syntheses,structures,andfunctions. Chem. Rev. 2009 , 109 ,5799−5867..

Scanga,R.A.;Reuther,J.F.Helicalpolymerself-assemblyandchiralnanostructureformation. Polym. Chem. 2021 , 12 ,1857−1897..

Wen,T.;Wang,H.F.;Li,M.C.;Ho,R.M.Homochiralevolutioninself-assembledchiralpolymersandblockcopolymers. Acc. Chem. Res. 2017 , 50 ,1011−1021..

Zhang,L.;Wang,T.;Shen,Z.;Liu,M.Chiralnanoarchitectonics:towardsthedesign,self-assembly,andfunctionofnanoscalechiraltwistsandhelices. Adv. Mater. 2016 , 28 ,1044−1059..

Bisoyi,H.K.;Li,Q.Light-directeddynamicchiralityinversioninfunctionalself-organizedhelicalsuperstructures. Angew. Chem. Int. Ed. 2016 , 55 ,2994−3010..

Leiras,S.;Freire,F.;Quiñoá,E.;Riguera,R.Reversibleassemblyofenantiomerichelicalpolymers:fromfiberstogels. Chem. Sci. 2015 , 6 ,246−253..

Yashima,E.;Maeda,K.;Iida,H.;Furusho,Y.;Nagai,K.Helicalpolymers:synthesis,structuresandfunctions. Chem. Rev. 2009 , 109 ,6102−6211..

Freire,F.;Quiñoá,E.;Riguera,R.Supramolecularassembliesfrompoly(phenylacetylene)s. Chem. Rev. 2016 , 116 ,1242−1271..

Rey-Tarrio,F.;Guisan-Ceinos,S.;Cuerva,J.M.;Miguel,D.;Ribagorda,M.;Quinoa,E.;Freire,F.Photostabilityanddynamichelicalbehaviorinchiralpoly(phenylacetylene)swithapreferredscrew-sense. Angew. Chem. Int. Ed. 2022 , 61 ,202207623..

Yashima,E.;Maeda,K.Chirality-responsivehelicalpolymers. Macromolecules 2008 , 41 ,3−12..

Okamoto,Y.;Nakano,T.Asymmetricpolymerization. Chem. Rev. 1994 , 94 ,349−372..

Zhang,A.;Ropero,F.R.;Zanuy,D.,Alemán,C.;Meijer,E.;Schlüter,A.Arigid,chiral,dendronizedpolymerwithathermallystable,right-handedhelicalconformation. Chem. Eur. J. 2008 , 14 ,6924−6934..

Liu,K.;Zhang,X.;Tao,X.;Yan,J.;Kuang,G.,Li,W.,Zhang,A.Lysine-baseddendronizedpolymerswithpreferredchirality. Polym. Chem. 2012 , 3 ,2708−2711..

Aoki,T.;Kaneko,T.;Maruyama,N.;Sumi,A.;Takahashi,M.;Sato,T.;Teraguchi,M.Helix-sense-selectivepolymerizationofphenylacetylenehavingtwohydroxygroupsusingachiralcatalyticsystem. J. Am. Chem. Soc. 2003 , 125 ,6346−6347..

Percec,V.;Aqad,E.;Peterca,M.;Rudick,J.G.;Lemon,L.;Ronda,J.C.;De,B.B.;Heiney,P.A.;Meijer,E.W.Stericcommunicationofchiralinformationobservedindendronizedpolyacetylenes. J. Am. Chem. Soc. 2006 , 128 ,16365−16372..

Maeda,K.;Mochizuki,H.;Osato,K.;Yashima,E.Stimuli-responsivehelicalpoly(phenylacetylene)sbearingcyclodextrinpendantsthatexhibitenantioselectivegelationinresponsetochiralityofachiralamineandhierarchicalsuper-structuredhelixformation. Macromolecules 2011 , 44 ,3217−3226..

Leiras,S.;Freire,F.;Seco,J.;Quinoa,E.;Ricardo,R.Controlledmodulationofthehelicalsenseandtheelongationofpoly(phenylacetylene)sbypolaranddonoreffects. Chem. Sci. 2013 , 4 ,2735−2743..

Guan,X.;Wang,S.;Shi,G.;Zhang,J.;Wan,X.Thermoswitchingofhelicalinversionofdynamicpolyphenylacetylenesthrough cis-trans isomerizationofamidependants. Macromolecules 2021 , 54 ,4592−4600..

Xu,A.;Masuda,T.;Zhang,A.Stimuli-responsivepolyacetylenesanddendronizedpoly(phenylacetylene)s. Polym. Rev. 2017 , 57 ,138−158..

Wamura,H.;Takeyama,Y.;Yamamoto,M.;Kurihara,H.;Morino,K.;Yashima,E.Chiralityresponsivehelicalpoly(phenylacetylene)bearingL-prolinependants. Chirality 2011 , 23 ,35−42..

Sanda,F.;Shiotsuki,M.;Masuda,T.Controlledpolymerizationofphenylacetylenesusingwell-definedRhodiumcatalysts. Macromol. Symp. 2015 , 350 ,67−75..

Motoshige,R.;Mawatari,Y.;Motoshige,A.;Yoshida,Y.;Sasaki,T.;Yoshimizu,H.;Suzuki,T.;Tsujita,Y.;Tabata,M.Mutualconversionbetweenstretchedandcontractedhelicesaccompaniedbyadrasticchangeincolorandspatialstructureofpoly(phenylacetylene)preparedwitha[Rh(nbd)Cl] 2 -aminecatalyst. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 ,752−759..

Miyagawa,T.;Furuko,A.;Maeda,K.;Katagiri,H.;Furusho,Y.;Yashima,E.Dualmemoryofenantiomerichelicesinapolyacetyleneinducedbyasingleenantiomer. J. Am. Chem. Soc. 2005 , 127 ,5018−5019..

Maeda,K.;Mochizuki,H.;Watanabe,M.;Yashima,E.Switchingofmacromolecularhelicityofopticallyactivepoly(phenylacetylene)sbearingcyclodextrinpendantsinducedbyvariousexternalstimuli. J. Am. Chem. Soc. 2006 , 128 ,7639−7650..

Li,S.;Liu,K.;Kuang,G.;Masuda,T.;Zhang,A.Thermoresponsivehelicalpoly(phenylacetylene)s. Macromolecules 2014 , 47 ,3288−3296..

Suarez-Picado,E.;Quinoa,E.;Riguera,R.;Freire,F.Poly(phenylacetylene)amines:ageneralroutetowater-solublehelicalpolyamines. Chem. Mater. 2018 , 30 ,6908−6914..

Cheuk,K.;Lam,J.;Lai,L.;Tang,B.Syntheses,hydrogen-bondinginteractions,tunablechainhelicities,andcooperativesupramolecularassociationsanddissociationsofpoly(phenylacetylene)sbearingL-valinependants: towardthedevelopmentofproteomimeticpolyenes. Macromolecules 2003 , 36 ,9752−9762..

Okoshi,K.;Sakurai,S.I.;Ohsawa,S.;Kumaki,J.;Yashima,E.Controlofmain-chainstiffnessofahelicalpoly(phenylacetylene)byswitchingonandofftheintramolecularhydrogenbondingthroughmacromolecularhelicityinversion. Angew. Chem. Int. Ed. 2006 , 45 ,8173−8176..

Sakurai,S.I.;Okoshi,K.;Kumaki,J.;Yashima,E.Two-dimensionalsurfacechiralitycontrolbysolvent-inducedhelicityinversionofahelicalpolyacetyleneongraphite. J. Am. Chem. Soc. 2006 , 128 ,5650–5651..

Rodriguez,R.;Quinoa,E.;Riguera,R.;FreireF.Architectureofchiralpoly(phenylacetylene)s:fromcompressed/highlydynamictostretched/quasi-statichelices. J. Am. Chem. Soc. 2016 , 138 ,9620–9628..

Sakai,R.;Satoh,T.;Kakuchi,T.Polyacetylenesascolorimetricandfluorescentchemosensorforanions. Polym. Rev. 2017 , 57 ,159−174..

Bergueiro,J.;Freire,F.;Wendler,E.;Seco,J.M.;Quinoa,E.;Riguera,R.TheON/OFFswitchingbymetalionsofthe“sergeantsandsoldiers”chiralamplificationeffectonhelicalpoly(phenylacetylene)s. Chem. Sci. 2014 , 5 ,2170−2176..

Cao,Y.;Ren,L.;Zhang,Y.;Lu,X.;Zhang,X.;Yan,J.;Li,W.;Masuda,T.;Zhang,A.Remarkableeffectsofanionsonthechiralityofthermoresponsivehelicaldendronizedpoly(phenylacetylene)s. Macromolecules 2021 , 54 ,7621−7631..

Tabata,M.;Mawatari,Y.Emerging π -conjugatedstretchedandcontractedhelicesandtheirmutualconversionsofsubstitutedpolyacetylenespreparedusinganorgano-rhodiumcatalyst. Polym. Rev. 2017 , 57 ,65−88..

Fukushima,T.;Kimura,H.;Tsuchihara,K.Colorandchiropticalcontrolofpoly(phenylacetylene)filmswithchiralhydroxylgroup. Macromolecules 2009 , 42 ,8619−8626..

Yoshida,Y.;Mawatari,Y.;Motoshige,A.;Motoshige,R.;Hiraoki,T.;Wagner,M.;Müllen,K.;Tabata,M.Accordion-likeoscillationofcontractedandstretchedhelicesofpolyacetylenessynchronizedwiththerestrictedrotationofsidechains. J. Am. Chem. Soc. 2013 , 135 ,4110−4116..

Motoshige,R.;Mawatari,Y.;Motoshige,A.;Yoshida,Y.;Sasaki,T.;Yoshimizu,H.;Suzuki,T.;Tsujita,Y.;Tabata,M.“Mutualconversionbetweenstretchedandcontractedhelicesaccompaniedbyadrasticchangeincolorandspatialstructureofpoly(phenylacetylene)preparedwitha[Rh(nbd)Cl] 2 -aminecatalyst”. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 ,752–759..

Wang,F.;Zhou,C.;Liu,K.;Yan,J.;Li,W.;Masuda,T.;Zhang,A.Thermoresponsivedendronizedpoly(phenylacetylene)sshowingtunablehelicity. Macromolecules 2019 , 52 ,8631−8642..

Kim,Y.;Shin,S.;Lee,M.Developmentoftoroidalnanostructuresbyself-assembly:rationaldesignsandapplications. Acc. Chem. Res. 2013 , 46 ,2888−2897..

Kouwer,P.H.J.;Koepf,M.;LeSage,V.A.A.;Jaspers,M.;vanBuul,A.M.;Eksteen-Akeroyd,Z.H.;Woltinge,T.;Schwartz,E.;Kitto,H.J.;Hoogenboom1,R.;Picken,S.J.;Nolte,R.J.M.;Mendes,E.;Rowan,A.E.Responsivebiomimeticnetworksfrompolyisocyanopeptidehydrogels. Nature 2013 , 493 ,651−655..

Hu,G.X.;Li,W.;Hu,Y.L.;Xu,A.Q.;Yan,J.T.;Liu,L.X.;Zhang,X.C.;Liu,K.;Zhang,A.Water-solublechiralpolyisocyanidesshowingthermoresponsivebehavior. Macromolecules 2013 , 46 ,1124−1132..

Xu,G.;Zhang,J.;Jia,R.;Li,W.;Zhang,A.Topologicaleffectsofdendronizedpolymersontheirthermoresponsivenessandmicroconfinement. Macromolecules 2022 , 55 ,630−642..

Li,W.;Zhang,A.;Chen,Y.;Feldman,K.;Wu,H.;Schluter,A.D.Lowtoxic,thermoresponsivedendrimersbasedonoligoethyleneglycolswithsharpandfullyreversiblephasetransitions. Chem. Commun. 2008 ,5948−5950..

Xu,G.;Zhang,J.;Qi,M.;Zhang,X.;Li,W.;Zhang,A.Thermoresponsivedendriticoligoethyleneglycols. Phys. Chem. Chem. Phys. 2022 , 24 ,11848−11855..

Zhang,A.;Zhang,B.;Wachtersbach,E.;Schmidt,M.;Schluter,A.D.Efficientsynthesisofhighmolarmass,first-tofourth-generationdistributeddendronizedpolymersbythemacromonomerapproach. Chem. Eur. J. 2003 , 9 ,6083−6092..

浏览量

202

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Advances in Polymer-based Circularly Polarized Luminescent Materials

Chiral Recognition and Resolution Based on Helical Polymers

Thermoresponsive Nanogels from Dendronized Copolymers for Complexation, Protection and Release of Nucleic Acids

Two-way Shape Memory Effect of Polycaprolactone-based Polyurethane via Synergistic Role of Hydrogen Bonding and Crystallization Tuned by Malic Acid

Highly Regio- and trans-Selective Ring-opening Metathesis Polymerization of Chiral Aza-norbornene with a Simple Phenylimido-Tungsten Catalyst