End-Group Telechelic Oligo- and Polythiophenes by “Click” Reactions: Synthesis and Analysis via LC-ESI-TOF MS
End-Group Telechelic Oligo- and Polythiophenes by “Click” Reactions: Synthesis and Analysis via LC-ESI-TOF MS
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通过“Click”反应进行端基遥爪寡聚物和聚噻吩：通过 LC-ESI-TOF MS 进行合成和分析
DOI：
10.1021/ma1016727
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发表时间：
2010
期刊：
影响因子：
5.5
通讯作者：
Wolfgang H. Binder
中科院分区：
文献类型：
--
作者：
Claudia Enders;Susanne Tanner;Wolfgang H. Binder
以聚3-己基噻吩（P3 HT）为原料，通过铜催化的叠氮化物/炔“点击”反应，制备了具有复杂氢键结构的端基改性P3 HT。最终的聚合物预计安排成假嵌段共聚物组成的交替供体/受体聚合物在太阳能电池材料中的应用。从经由McCullough方法制备的溴-遥爪P3 HT（Mn= 2000 g/mol;Mw/Mn= 1.2）开始，接着进行另外的溴化反应，产生具有（80%Br/Br; 20%H/Br）端基的遥爪P3 HT，经由Sonogashira偶联反应制备相应的α，ω-（三甲基甲硅烷基）乙炔基-P3 HT。首次采用LC-ESI-TOF方法对炔基-遥爪P3 HT的端基进行了分析，证明在α，ω-（三甲基硅烷基）乙炔基-P3 HT中形成了约59%（乙炔基/乙炔基）和约40%（乙炔基/H）的端基，只有少量（约1%）的相应（H/H）-修饰的端基。此外，MALDI方法用于定性评估。在CuI、CuBr（PPh 3）3或CuI·P（OEt）3催化下，与1-（6-叠氮己基）胸腺嘧啶或5-（（4-叠氮苯甲酰基）氨基）-N，N′-（6-（辛酰氨基）吡啶-2-基）N，N ′-二甲酰胺发生叠氮/炔“点击”反应，生成了最终产物，通过LC-ESI-TOF方法判断，这些产物具有连接的氢键。所描述的方法打开了通向具有氢键部分的超分子P3 HT聚合物的途径。
End-group-modified poly(3-hexylthiophenes) (P3HT) with complex hydrogen-bonding moieties have been prepared starting from telechelic alkyne-functionalized P3HT via a copper(I) catalyzed azide/alkyne “click” reaction. The final polymers are projected to arrange into pseudoblock copolymers consisting of alternating donor/acceptor polymers for application in solar cell materials. Starting from a bromine-telechelic P3HT (Mn= 2000 g/mol;Mw/Mn= 1.2) prepared via the McCullough method followed by additional bromination reaction yielding telechelic P3HTs with (80% Br/Br; 20% H/Br) end groups, the respective α,ω-(trimethylsilyl)ethynyl-P3HTs were prepared via Sonogashira coupling reactions. Analysis of the end groups of the alkynyl-telechelic P3HT species was achieved by use of LC-ESI-TOF methods for the first time, proving the formation of ∼59% (ethynyl/ethynyl) and ∼40% (ethynyl/H) species within the α,ω-(trimethylsilyl)ethynyl-P3HTs, with only minor amounts (∼1%) of the respective (H/H)-modified species. Additionally, MALDI methods were used for a qualitative assessment. Subsequent azide/alkyne “click” reaction with either 1-(6-azidohexyl)thymine or 5-((4-azidobenzoyl)amino)-N,N′-(6-(octanoylamino)pyridin-2-yl)isophthalamide using CuI, CuBr(PPh3)3, or CuI·P(OEt)3as catalyst yielded the final products with attached hydrogen bonds as judged by LC-ESI-TOF methods. The described method opens an access toward supramolecular P3HT polymers with hydrogen-bonding moieties.