Programmable Arrangement of Metal Ions in a Cofacially Stacked Assembly of Porphyrinoids toward Molecular Tags
Programmable Arrangement of Metal Ions in a Cofacially Stacked Assembly of Porphyrinoids toward Molecular Tags
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类卟啉共面堆叠组装中金属离子向分子标签的可编程排列
DOI：
10.1039/c8dt01334a
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发表时间：
2018
影响因子：
4
通讯作者：
Tanaka Kentaro
中科院分区：
文献类型：
--
作者：
Mihara Nozomi;Yamada Yasuyuki;Furukawa Ko;Kato Tatsuhisa;Tanaka Kentaro
金属卟啉的共面组装体代表了一个令人着迷的平台，用于制造基于组分之间的 π-π、d-d 和 d-π 相互作用的新型功能分子组装体。在本文中，我们提出了一种新颖的合成策略，用于在共面堆叠的卟啉三聚体内不同金属离子的可编程排列。为了我们的目的，使用了两种不同组件的组合：具有四个烷基铵链的卟啉和带有四个外围冠醚的酞菁之间的四阳离子四重轮烷异二聚体，以及四重轮烷异二聚体和额外的四阴离子卟啉之间的堆叠组件。三种金属离子，即 Cu(II)、Ag(II) 和 Au(III)，排列在三种卟啉类共面堆叠的组件内。此外，顺磁性 Cu(II) 离子排列在共面堆叠的卟啉异三聚体内，并经过精确编程，提供所需的自旋-自旋通信作为可读信息。这些结果表明，所开发的策略对于在类卟啉共面堆叠组件中排列各种金属离子以创建分子标签或条形码是有效的。
Cofacial assemblies of metalloporphyrinoids represent a fascinating platform for the fabrication of novel functional molecular assemblies based on π–π, d–d, and d–π interactions between components. In this paper, we present a novel synthetic strategy for the programmable arrangement of different metal ions inside a cofacially stacked trimer of porphyrinoids. A combination of two different assemblies was utilized for our purpose: a tetracationic fourfold rotaxane heterodimer between a porphyrin with four alkylammonium chains and a phthalocyanine bearing four peripheral crown ethers, and a stacked assembly between the fourfold rotaxane heterodimer and an additional tetraanionic porphyrin. Three metal ions, namely Cu(II), Ag(II), and Au(III), were arranged inside the cofacially stacked assembly of three porphyrinoids. Moreover, paramagnetic Cu(II) ions were arranged inside a cofacially stacked heterotrimer of porphyrinoids and were precisely programmed, affording the desired spin–spin communications as readable information. These results indicated that the developed strategy is effective for arranging various metal ions in cofacially stacked assemblies of porphyrinoids toward the creation of molecular tags or bar codes.