Discrete Covalent Organic-Inorganic Hybrids: Terpyridine Functionalized Polyoxometalates Obtained by a Modular Strategy and Their Metal Complexation
Discrete Covalent Organic-Inorganic Hybrids: Terpyridine Functionalized Polyoxometalates Obtained by a Modular Strategy and Their Metal Complexation
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DOI：
10.1021/ic200752v
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发表时间：
2011-07-18
影响因子：
4.6
通讯作者：
Hasenknopf, Bernold
中科院分区：
文献类型：
--
作者：
Santoni, Marie-Pierre;Pal, Amlan K.;Hasenknopf, Bernold
有机-无机杂化材料作为功能分子材料的合理设计和合成依赖于构建模块的仔细构思及其组装策略。合成了三个系列的三烷氧基聚氧乙烯醚（Lindqvist 2，安德森3，道森4）接枝远程三联吡啶配位位点，以扩展可用的积木。这些新的单元可以与金属络合物结合，所述金属络合物起到以下作用：（i）发色团朝向捕光装置中的电荷分离系统，以及（ii）用于朝向多功能分子杂化材料的金属定向组装的配位基序。聚氧乙烯酸-三联吡啶杂化物的X射线晶体结构表明2和3中两个三联吡啶配位点之间的距离分别为21和19，配位矢量之间的角度分别为180度和177.4度。Lindqvist 2在-0.52 V vs. SCE处显示还原，而安德森3在-1.28 V vs. SCE处显示一个归因于Mn（III）/Mn（IV）（+0.75 V vs. SCE）的可逆氧化和归因于Mn（III）/Mn（II）还原的宽波。Dawson 4在很宽的电位范围（+0.5至-2.0 V vs SCE）内显示了几个过程，这些过程以V（V）、W（VI）和有机配体为中心，电位依次降低。安德森3和道森4中的三联吡啶配体分别成功地与{PdCl}（+）和{RuCl 3}配位。聚氧乙烯酸盐和过渡金属络合物在最终组装体中保持其固有性质。
The rational design and synthesis of organic-inorganic hybrids as functional molecular materials relies on both the careful conception of building-blocks and the strategy for their assembly. Three families of trialkoxo polyoxometalates (Lindqvist 2, Anderson 3, Dawson 4) grafted with remote terpyridine coordination sites have been synthesized to extend the available building-blocks. These new units can be combined with metal complexes that play a role as (i) chromophores toward charge-separated systems in light-harvesting devices and (ii) coordination motifs for metal-directed assembly toward toward multifunctional molecular hybrid materials. The X-ray crystal structures of polyoxometalate-terpyridine hybrids indicate distances of 21 A and 19 A between the two terpyridyl coordination sites in 2 and 3, respectively, with angles between the coordination vectors of 180 degrees and 177.4 degrees, respectively. Lindqvist 2 displays a reduction at -0.52 V vs SCE while Anderson 3 exhibits one reversible oxidation attributed to Mn(III)/Mn(IV) (+0.75 V vs SCE) and a broad wave at -1.28 V vs SCE assigned to the Mn(III)/Mn(II) reduction. Dawson 4 displays several processes on a wide range of potentials (+0.5 to -2.0 V vs SCE) centered on V(V), W(VI) and the organic ligand in order of decreasing potentials. The grafted terpyridine ligands in Anderson 3 and Dawson 4 were successfully coordinated to {PdCl}(+) and {RuCl3} moieties, respectively. The polyoxometalates and transition metal complexes retain their intrinsic properties in the final assemblies.