The polyacidic character of polyoxometalate (POM) clusters endows high ionic conductivity, making these clusters good candidates for solar and fuel cells. Covalent bonding of clusters to polymer chains creates poly(POM)s that are polyelectrolytes with both cluster functions and polymer performance. Thus, solution-processable poly(POM)s are expected to be used as key materials in advanced devices. Further understanding of poly(POM)s will optimize the preparation process and improve device performance. Herein, we report a study of the first linear poly(POM)s by directly visualizing the chains using scanning transmission electron microscopy. Compared with traditional polymers, individual clusters of poly(POM)s can be directly visualized because of the resistance to electron-beam damage and the high contrast of the tungsten POM pendants. Thus, cluster aggregates with diverse shapes were observed. Counting the number of clusters in the aggregates allowed the degree of polymerization and molecular weight distribution to be determined, and studying the aggregate shapes revealed the presence of a curved semirigid chain in solution. Further study of shape diversity revealed that strong interactions between clusters determine the diverse chain shapes formed during solution processing. Fundamental insight is critical to understanding the formation of poly(POM) films from solutions as key functional materials, especially for fuel and solar cells.

多金属氧酸盐（POM）团簇的多酸特性赋予其高离子电导率，使其成为太阳能电池和燃料电池的理想候选者。团簇与聚合物链的共价键结合产生的聚（POM）是具有团簇功能和聚合物性能的聚电解质。因此，可溶液加工的聚（POM）有望用作先进设备中的关键材料。对聚（POM）的进一步了解将优化制备过程并提高器件性能。在这里，我们通过使用扫描透射电子显微镜直接可视化链报告了第一个线性poly（POM）的研究。与传统聚合物相比，聚（POM）的单个簇可以直接可视化，因为它具有抗电子束损伤的能力以及钨POM悬垂物的高对比度。从而，观察到具有不同形状的团簇聚集体。计算聚集体中簇的数目可以确定聚合度和分子量分布，并且研究聚集体形状揭示了溶液中存在弯曲的半刚性链。对形状多样性的进一步研究表明，簇之间的强相互作用决定了溶液加工过程中形成的各种链形状。对于理解由溶液作为关键功能材料的聚（POM）膜的形成至关重要，基本见识至关重要，尤其是对于燃料和太阳能电池而言。研究骨料形状揭示了溶液中存在弯曲的半刚性链。对形状多样性的进一步研究表明，簇之间的强相互作用决定了溶液加工过程中形成的各种链形状。对于理解由溶液作为关键功能材料的聚（POM）膜的形成至关重要，基本见识至关重要，尤其是对于燃料和太阳能电池而言。研究骨料形状揭示了溶液中存在弯曲的半刚性链。对形状多样性的进一步研究表明，簇之间的强相互作用决定了溶液加工过程中形成的各种链形状。对于理解由溶液作为关键功能材料的聚（POM）膜的形成至关重要，基本见识至关重要，尤其是对于燃料和太阳能电池而言。