Supramolecular assembly of conjugated polymers containing polyoxometalate terminal side chains in polar and nonpolar solvents.
Supramolecular assembly of conjugated polymers containing polyoxometalate terminal side chains in polar and nonpolar solvents.
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DOI：
10.1002/chem.201103782
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发表时间：
2012-05
期刊：
影响因子：
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通讯作者：
Panchao Yin;Lu Jin;Dong Li;Peng Cheng;D. Vezenov;Emily Bitterlich;Xia Wu;Zhonghua Peng;Tianbo Liu
中科院分区：
文献类型：
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作者：
Panchao Yin;Lu Jin;Dong Li;Peng Cheng;D. Vezenov;Emily Bitterlich;Xia Wu;Zhonghua Peng;Tianbo Liu
共轭聚合物是具有独特电学和光电特性的重要材料，并已在各种分子电子器件中得到应用，包括发光二极管、太阳能电池、场效应晶体管、光电探测器、传感器和非线性光学。多金属氧酸盐（POM）是一大类由早期过渡金属阳离子和氧配体组成的金属氧化物簇，也被认为是电活性材料，并且由于其在催化、医学和光电响应方面的出色性能，近年来引起了越来越多的关注。将 POM 簇与共轭聚合物共价结合可能会产生不仅具有增值特性而且具有协同效应的杂化材料。例如，含 POM 的杂化聚合物已被发现是光伏电池、光催化材料和催化纳米粒子的良好候选者。虽然众所周知，杂化材料的器件性能很大程度上取决于其聚集的微米或纳米结构，但对溶液和固态中含 POM 共轭聚合物聚集的研究却很少。如果要实现基于 POM 的可控有序结构，此类研究至关重要。另一方面，了解聚电解质溶液的聚集行为一直是高分子和生物科学的一个重要目标，因为它可能有助于解释活细胞中DNA、RNA和蛋白质的行为，并指导基于聚电解质的功能材料的设计。然而，由于复杂的链间和链内静电相互作用的共存，聚电解质溶液仍然知之甚少。在此，我们报道了含有 POM 末端侧链的共轭聚合物在极性和非极性溶剂中的自组装行为。如图 1 所示，此类聚合物由于亚苯基-亚乙炔基主链而具有刚性棒状结构。 POM 簇是一种大小约为 1 nm 的有机酰亚胺衍生的六钼酸盐，带有两个负电荷，并以两个四丁基铵 (TBA) 作为抗衡离子，作为侧链末端与聚合物主链共价连接。
Conjugated polymers are important materials with unique electrical and optoelectronic properties, and have found applications in a variety of molecular electronic devices including light-emitting diodes, solar cells, field effect transistors, photodetectors, sensors, and nonlinear optics. Polyoxometalates (POMs), a large group of metal oxide clusters consisting of early-transition-metal cations and oxo ligands, are also considered electrically active materials and have attracted increasing interest in recent years due to their outstanding properties in catalysis, medicine, and photoelectronic responses. Incorporating POM clusters covalently with conjugated polymers may lead to hybrid materials with not only value-adding properties, but also synergistic effects. For example, POM-containing hybrid polymers have been found to be good candidates for photovoltaic cells, photocatalytic materials, and catalytic nanoparticles. While it is known that the device performance of hybrid materials depends strongly on their aggregated microor nanostructures, there has been very little research on the aggregation of POM-containing conjugated polymers in both solution and solid states. Such studies are essential if POM-based controllable ordered structures are to be realized. On the other hand, understanding the aggregation behavior of polyelectrolyte solutions has always been an important goal in polymer and biological sciences, since it may help explain the behaviors of DNA , RNA, and proteins in living cells and guide the design of polyelectrolyte-based functional materials. However, due to the coexistence of complex interand intrachain electrostatic interactions, polyelectrolyte solutions are still poorly understood. Herein, we report the self-assembly behavior of conjugated polymers containing POM terminal side chains in polar and nonpolar solvents. As shown in Figure 1, such polymers have rigid rodlike structures due to the phenylene–ethynylene backbone. The POM cluster, an organoimido-derivatized hexamolybdate approximately 1 nm in size and carrying two negative charges with two tetrabutyl ammonium (TBA) as the counterions, is covalently linked to the polymer backbone as the terminal of their side chains.