Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties
Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties
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DOI：
10.1021/acs.macromol.8b00977
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发表时间：
2018-07-24
期刊：
影响因子：
5.5
通讯作者：
Pammer, Frank
中科院分区：
文献类型：
--
作者：
Schraff, Sandra;Sun, Yu;Pammer, Frank
我们描述了由9-苄基- 9h -芴（Flu）、5-苄基-1,2,3,4-四苯基环戊二烯（TPCp）和5-苄基- 5hdibenzo [a，d]环庚烯（Dbs）衍生的共轭氟烯基芳基异氰化物单体的制备。表征了单体及其前驱体的电化学和光学性质，并一致显示了相应的官能团（-NO2, -NH2， -NHCHO和-N相当于C）与氟乙烯基部分的共轭效应。异氰化物随后聚合成相应的多异氰化物（PICs），其数平均分子量为124-136 kDa (PDI = 2.0-2.7)，在The与聚苯乙烯标准中通过凝胶渗透色谱测定。详细研究了聚合物的热学、光学和电化学性能。具有氧化还原活性的五富尔烯基团的聚合物的光谱电化学分析显示可逆电致变色，这允许通过化学或电化学还原将光学间隙从2.38 eV降低到1.20 eV (Flu)，从2.27 eV降低到1.55 eV （TPCp）。
We describe the preparation of arylisocyanide monomers bearing conjugated fulvenyl groups derived from 9-benzylidene-9H-fluorene (Flu), 5-benzylidene-1,2,3,4-tetraphenylcyclopentadiene (TPCp), and 5-benzylidene-5Hdibenzo[a,d]cycloheptene (Dbs). The electrochemical and optical properties of the monomers and their precursors have been characterized and consistently showed the effect of the conjugation of the respective functional group (-NO2, -NH2, -NHCHO, and -N equivalent to C with the fulvenyl moiety. The isocyanides have been subsequently polymerized to the corresponding polyisocyanides (PICs), which exhibited number-average molecular weights of 124-136 kDa (PDI = 2.0-2.7), as determined by gel permeation chromatography in THE vs polystyrene standards. The thermal, optical, and electrochemical properties of the polymers have been studied in detail. Spectroelectrochemical analyses of polymers equipped with redox-active pentafulvene groups show reversible electrochromism, which allows to lower the optical gap from 2.38 to 1.20 eV (Flu) and from 2.27 to 1.55 eV (TPCp) via chemical or electrochemical reduction.