Metal-containing (bio)organic polymers are materials of continuously increasing importance for applications in energy storage and conversion, drug delivery, shape-memory items, supported catalysts, organic conductors and smart photonic devices. The embodiment of luminescent components provides a revolution in lighting and signaling with the ever-increasing development of polymeric light-emitting devices. Despite the unique properties expected from the introduction of optically and magnetically active lanthanides into organic polymers, the deficient control of the metal loading currently limits their design to empirical and poorly reproducible materials. We show here that the synthetic efforts required for producing soluble multi-site host systems Lk are largely overcome by the virtue of reversible thermodynamics for mastering the metal loading with the help of only two parameters: (1) the affinity of the luminescent lanthanide container for a single binding site and (2) the cooperative effect which modulates the successive fixation of metallic units to adjacent sites. When unsymmetrical perfluorobenzene-trifluoroacetylacetonate co-ligands (pbta⁻) are selected for balancing the charge of the trivalent lanthanide cations, Ln³⁺, in six-coordinate [Ln(pbta)₃] containers, the explored anti-cooperative complexation processes induce nearest-neighbor intermetallic interactions twice as large as thermal energy at room temperature (RT = 2.5 kJ mol⁻¹). These values have no precedent when using standard symmetrical containers and they pave the way for programming metal alternation in luminescent lanthanidopolymers.

中文翻译：

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多点受体与镧系元素的协同​​加载：一种有组织的发光金属聚合物的方法†

含金属的（生物）有机聚合物对于在能量存储和转换，药物输送，形状记忆物品，负载型催化剂，有机导体和智能光子设备中的应用而言，具有越来越重要的意义。随着聚合物发光器件的不断发展，发光组件的实施方式在照明和信号传输方面掀起了一场革命。尽管将光学和磁性活性镧系元素引入有机聚合物中有望获得独特的性能，但对金属负载的控制不足目前将其设计限于经验性和可复制性差的材料。我们在这里表明，生产可溶性多站点宿主系统L k所需的综合努力借助可逆的热力学，仅借助两个参数即可掌握金属负载，从而在很大程度上克服了上述问题：（1）发光镧系元素容器对单个结合位点的亲和力；（2）调节连续固定的协同作用金属单元到相邻位置。当不对称全氟苯-三氟乙酰共配体（PBTA ^- ）被选择用于平衡电荷的三价镧系元素阳离子，LN ³⁺，在六配位[LN（PBTA）₃ ]的容器中，探索了反合作络合过程诱导最接近的邻金属间的相互作用是室温下热能的两倍（RT = 2.5 kJ mol ^-1）。这些值在使用标准对称容器时没有先例，它们为在发光镧系元素聚合物中编程金属交替铺平了道路。