Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.
Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.
复制标题
DOI：
10.1039/c7sc03710d
复制
发表时间：
2018-01-14
期刊：
影响因子：
8.4
通讯作者：
Piguet C
中科院分区：
文献类型：
--
作者：
Babel L;Guénée L;Besnard C;Eliseeva SV;Petoud S;Piguet C
金属负载的多三齿受体与[Eu（pbta）3]提供了第一个反合作的因素足够大的编程金属交替在镧系聚合物在室温下。含金属（生物）有机聚合物在能量储存和转换、药物递送、形状记忆物品、负载催化剂、有机导体和智能光子器件中的应用越来越重要。随着聚合物发光器件的不断发展，发光组件的实施例提供了照明和信号的革命。尽管将光学和磁性活性镧系元素引入到有机聚合物中预期具有独特的性质，但目前对金属负载的控制不足将其设计限制在经验和可再现性差的材料上。我们在这里表明，生产可溶性多位点宿主系统Lk所需的合成努力在很大程度上克服了可逆热力学的优点，用于掌握金属负载的帮助下只有两个参数：（1）的亲和力的发光镧系元素容器为一个单一的结合位点和（2）的协同效应，调制连续固定的金属单元到相邻的网站。当不对称的全氟苯-三氟乙酰丙酮共配体（pbta-）被选择用于平衡的三价镧系元素阳离子，Ln 3+，在六坐标[Ln（pbta）3]容器的电荷，探索的反合作络合过程诱导最近邻金属间相互作用的两倍大的热能在室温下（RT = 2.5 kJ mol-1）。当使用标准对称容器时，这些值是没有先例的，它们为编程发光镧系聚合物中的金属交替铺平了道路。
Metal loading of multi-terdentate receptors with [Eu(pbta)3] provides the first anti-cooperative factors large enough for programming metal alternation in lanthanidopolymers at room temperature. 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.
登录
查看更多内容
影响因子：
15
作者：
Beck, JB;Rowan, SJ
通讯作者：
Rowan, SJ
影响因子：
4.3
作者：
Cirera, J;Ruiz, E;Alvarez, S
通讯作者：
Alvarez, S
影响因子：
5.5
作者：
Basak, Supratim;Narayana, Yemineni S. L. V.;Chandrasekar, Rajadurai
通讯作者：
Chandrasekar, Rajadurai
影响因子：
0.6
作者：
Dudar', S. S.;Sveshnikova, E. B.;Ermolaev, V. L.
通讯作者：
Ermolaev, V. L.
影响因子：
3.3
作者：
Bialecka-Florjanczyk, E
通讯作者：
Bialecka-Florjanczyk, E