Recent advances in the asymmetrical templation effect of polyoxometalate in silver clusters

Jia-Yang Shi, Rakesh Kumar Gupta, Yong-Kai Deng, Di Sun, and Zhi Wang^*

This review summarizes the state-of-the-art synthesis, design, properties, applications, and critical challenges of asymmetrically wrapped polyoxometalate (POM)–silver clusters.

山东大学孙頔教授课题组总结了银簇中多酸发挥不对称模板效应的最新进展，包括它们的合成、结构与性质，并详细地分析和解释了这类不对称团簇的形成，以及具有独特的氧化还原和电催化性质的原因，并讨论了该领域内存在的挑战以及对未来前景的展望。

Polyoxometalates, 2022, 1, 9140010

https://doi.org/10.26599/POM.2022.9140010

Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials

Huaiying Zhang, Wan-Lei Zhao, Hongqiang Li, Qinghe Zhuang, Zeqian Sun, Dongyuan Cui, Xuejie Chen, Ao Guo, Xiang Ji, Sai An^*, Wei Chen, and Yu-Fei Song^*

This review summarized the latest progress (2017‒2022) of covalently modified polyoxometalates (POMs) from functional perspective, which can be classified as assembly chemistry, photochemistry, electrochemistry, homogeneous/heterogeneous catalysis and biological application.

北京化工大学宋宇飞教授课题组总结了近五年（2017-2022）共价修饰的POMs在组装化学、光化学、电化学、均相催化和非均相催化以及生命科学领域的研究进展。利用共价键将功能性基团（如光敏分子、表面活性剂、生物分子等）修饰POMs，调控了其光响应性、氧化还原性、酸性、亲疏水性和生物相容性等。与非共价修饰的POMs相比，共价修饰的POMs具有更高的稳定性、更快的多电子转移、更好的分散性和可及性、以及更加优异的可回收性。在文中，作者结合代表性示例对于POMs以及共价修饰物种发挥的作用进行了深入分析，并详细讨论了针对特定的功能应用的共价修饰POMs的合理设计。最后特别强调了设计和开发以功能为导向的共价修饰POMs的重要性，并对未来的挑战和机遇进行了展望。

Polyoxometalates, 2022, 1, 9140011

https://doi.org/10.26599/POM.2022.9140011

Catalytic application of polyoxovanadates in the selective oxidation of organic molecules

Jie Li, Di Zhang, Yingnan Chi^*, and Changwen Hu^*

The review summarized the selective oxidation of organic molecules (e.g. alkanes, alkenes, alcohols, sulfur mustard simulants, sulfides and dyes) catalyzed by all-inorganic polyoxovanadates (POVs), organic-functionalized POVs and inorganic-organic hybrid POVs.

北京理工大学胡长文教授和迟瑛楠教授课题组总结了近十年来POVs在催化有机小分子氧化转化方面的进展。主要集中在无机POVs、有机官能化POVs以及无机-有机杂化POVs对烷烃、烯烃、醇、硫化物、芥子气模拟物和有机染料分子的选择性催化氧化。对于多数氧化反应而言，POVs在过氧化氢或叔丁基过氧化氢存在下产生活性V-peroxo物种，进而实现有机底物分子的快速转化。此外，本文还讨论了该领域发展中面临的机遇和挑战，为其持续发展提供了参考。

Polyoxometalates, 2022, 1, 9140012

https://doi.org/10.26599/POM.2022.9140012

Syntheses, crystal structures, and properties of four polyoxometalate-based metal–organic frameworks based on Ag(I) and 4,4’-dipyridine-N,N’-dioxide

Haiyan Li, Hui Pan, Yanhua Fan, Yan Bai^*, and Dongbin Dang^*

Four new Ag(I) inorganic–organic hybrid coordination polymers (1–4) based on polyoxometalate (POM) and 4,4'-bipyridine-N,N'-dioxide have been synthesized. Polymers 1 and 4 exhibit a three-dimensional (3D) POM-pillared metal–organic framework and polymer 2 and 3 show a two-dimensional (2D) grid-like network.

河南大学柏䶮教授课题组以Keggin型多酸阴离子为构筑块，通过引入Ag(I)及氮氧化4,4'-联吡啶（dpdo）配体合成了4例Ag(I)-氮氧化4,4'-联吡啶修饰的多酸基金属有机框架材料，并将它们作为催化剂应用于亚硝酸盐的电化学还原。

Polyoxometalates, 2022, 1, 9140007

https://doi.org/10.26599/POM.2022.9140007

Old molybdenum blue for new application: {Mo₇₂X₃₀}/PANI/MWCNTs (X = Fe, V) ternary coaxial cable-like fibers for superior electromagnetic wave absorption

Peng He, Ling Ran, Rui Huang, Ruiting Hu, Runze Ma, Yani Li, Youcai Liang, and Jun Yan*

The rational design of molybdenum blue/polyaniline/multiwalled carbon nanotubes ({Mo₇₂X₃₀}/PANI/MWCNTs, X = Fe, V) ternary coaxial cable-like structure with rich heterointerfaces has explored the direction for excellent electromagnetic absorbing materials.

中南大学颜军教授课题组通过一种层层自组装的方法设计合成了{Mo₇₂X₃₀}/PANI/MWCNTs (X = Fe, V)三元同轴电缆状纤维，并首次将其用作电磁波吸收材料。该材料层与层间的异质界面具有促进偶极极化、界面极化和调节传导损耗等优点。此外，钼蓝的加入提高了以涡流损耗为主的磁损耗，改善了阻抗匹配。基于此，三元同轴电缆状纤维展示出优异的电磁波吸收性能。本研究不仅有助于对电磁波吸收材料中异质界面的功能作用的理解，也为今后在电磁波吸收领域中对钼蓝功能分子的研究奠定了基础。

Polyoxometalates, 2022, 1, 9140008

https://doi.org/10.26599/POM.2022.9140008

Multistimuli-responsive circularly polarized luminescent material of achiral Eu-containing polyoxometalates and cellulose nanocrystals

Rong Wang, Peiyao Yu, Junyan Tan, Yue Zhou, and Jie Zhang^*

We constructed stimuli-responsive circularly polarized luminescence (CPL) material based on cellulose nanocrystals (CNC), polyethylene glycol (PEG), and polyoxometalates Na₉EuW₁₀O₃₆·32H₂O (EuW₁₀). CNC photonic films act as a chiral template and induce the CPL of EuW₁₀. With the increase in PEG content, the photonic bandgaps of composite films were redshifted. The dissymmetric factor g_lum became the maximum when PBG matched the fluorescence emission peak of EuW₁₀. The CPL materials also demonstrated outstanding humidity responsiveness.

北京大学张洁研究员课题组成功地构建了基于纤维素纳米晶体（CNC）手性模板的非手性钨铕多酸（EuW₁₀）强圆偏振发光（CPL）杂化材料。高浓度的纤维素纳米晶体可以自发形成手性向列相液晶，选择性反射左旋圆偏振光和透射右旋圆偏振光，是制备圆偏振发光材料理想的基质。EuW₁₀与CNC之间可形成分子间氢键、静电相互作用，相容性好，通过简单共混即可以制备得到均匀稳定的薄膜。

Polyoxometalates, 2022, 1, 9140009

https://doi.org/10.26599/POM.2022.9140009