Metal-chloride-Anion Containing Polymers with Expanded pi-Conjugation Systems Derived from Through-Space Interactions in the Piperazinium Ring
Metal-chloride-Anion Containing Polymers with Expanded pi-Conjugation Systems Derived from Through-Space Interactions in the Piperazinium Ring
复制标题
含有金属氯化物阴离子的聚合物，其具有源自哌嗪鎓环中的空间相互作用的扩展π共轭系统
DOI：
10.1002/pi.5778
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
A. Wang
中科院分区：
文献类型：
--
作者：
I. Yamaguchi;Y. Hamada;K. Miyoshi;A. Wang
n‐（2,4‐二硝基苯）氯化吡啶（盐（Cl））与H+MCl4−1（M≡Fe和Bi）的反应导致Cl−和MCl4−之间的阴离子交换，生成具有金属氯离子的锌盐，分别是盐（Fe）和盐（Bi）。锌盐与哌嗪反应导致吡啶环开环，生成具有5 -哌嗪- 2,4 -二乙烯基金属氯铵单元的离子聚合物，即聚合物（Fe）和聚合物（Bi）。以盐（Bi）或盐（Cl）为原料，通过反应合成相应的模型化合物。聚合物的紫外可见光谱比模型化合物在更长的波长处具有吸收最大值。这表明π共轭体系是沿聚合物主链展开的。超导量子干涉装置测量表明，聚合物（Fe）具有顺磁性。循环伏安分析表明聚合物发生了电化学氧化。©2019化学工业协会
Reactions ofN‐(2,4‐dinitrophenyl)pyridinium chloride (salt(Cl)) with H+MCl4−1(M ≡ Fe and Bi) resulted in an anion exchange between Cl−and MCl4−to yield Zincke salts with metal chloride anions, namely salt(Fe) and salt(Bi), respectively. Reactions of the Zincke salts with piperazine resulted in ring‐opening of the pyridinium ring, yielding ionic polymers with 5‐piperazinium‐2,4‐dienylideneammonium metal chloride units, namely polymer(Fe) and polymer(Bi). The corresponding model compounds were synthesized via reactions using salt(Bi) or salt(Cl) as starting materials. The UV–visible spectra of the polymers had absorption maxima at longer wavelengths than those of the model compounds. This indicated that the π‐conjugation system is expanded along the polymer main chain. Superconducting quantum interference device measurements indicated that polymer(Fe) was paramagnetic. Cyclic voltammetry analysis suggested that the polymers underwent electrochemical oxidation. © 2019 Society of Chemical Industry