Intramolecular hydrogen-bond-assisted planarization of asymmetrically functionalized alternating phenylene-pyridinylene copolymers.
Intramolecular hydrogen-bond-assisted planarization of asymmetrically functionalized alternating phenylene-pyridinylene copolymers.
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DOI：
10.1002/chem.200500078
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发表时间：
2005-10
期刊：
影响因子：
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通讯作者：
Muthalagu Vetrichelvan;S. Valiyaveettil
中科院分区：
文献类型：
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作者：
Muthalagu Vetrichelvan;S. Valiyaveettil
我们报道了一系列具有交替π-供体单元的不对称官能化两亲聚合物的合成和表征（例如，取代的苯）和π-受体单元（例如，吡啶）沿着聚合物骨架。我们目前的工作的目的涉及纳入官能团沿着主链形成链内氢键，这促进了聚合物主链的平面化，并微调的光学性能。通过FTIR、1H和13 C NMR、UV/维斯光谱、荧光光谱、凝胶渗透色谱、热重分析、循环伏安和X射线粉末衍射等分析方法研究了聚合物P1-P6的结构与性能的关系。所有聚合物均可溶于普通有机溶剂中，并且聚合物的光学和荧光光谱根据沿聚合物主链的分子内氢键沿着形成（P4，P5）或不存在（P6）而显示出显著的变化。此外，P5和P6中吡啶环的2，6-或3，5-键分别降低了沿聚合物主链的共轭沿着，这反映在它们的光学性质中。聚合物的光学性质受酸（P1-P6）、碱（P4-P6）和金属离子（例如，Cu 2+、Fe 3+、Ag+、Ni 2+、Pd 2+、Mn 2+、Zn 2+、Mg 2+和Pr 3+）。这种聚合物可用于各种应用，包括传感器和刺激响应显示器。
We report on the synthesis and characterization of a series of asymmetrically functionalized amphiphilic polymers with alternating pi-donor units (e.g., substituted benzene) and pi-acceptor units (e.g., pyridine) along the polymer backbone. The purpose of our present work involves incorporation of functional groups along the main chain to form intrachain hydrogen bonds, which promote planarization of the polymer backbone, and to fine-tune the optical properties. The structure-property relationship of polymers P1-P6 was investigated by means of analytical methods, such as FTIR spectroscopy, 1H and 13C NMR spectroscopy, UV/Vis spectroscopy, fluorescence spectroscopy, gel permeation chromatography, thermogravimetric analysis, cyclic voltammetry, and X-ray powder diffraction. All polymers were soluble in common organic solvents, and the optical and fluorescence spectra of the polymers showed significant changes according to the formation (P4, P5) or absence (P6) of intramolecular hydrogen bonding along the polymer backbone. Moreover, the 2,6- or 3,5-linkage of the pyridine rings in P5 and P6, respectively, reduced the conjugation along the polymer backbone and this is reflected in their optical properties. The optical properties of the polymers were influenced by the addition of acid (P1-P6), base (P4-P6), and metal ions (e.g., Cu2+, Fe3+, Ag+, Ni2+, Pd2+, Mn2+, Zn2+, Mg2+, and Pr3+). Such polymers could be used in various applications, including sensors and stimuli-responsive displays.