Highly Accurate Synthesis of Quasi Sub Nanoparticles by Dendron Assembled Supramolecular Templates
Highly Accurate Synthesis of Quasi Sub Nanoparticles by Dendron Assembled Supramolecular Templates
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利用树枝状分子组装超分子模板高精度合成准亚纳米颗粒
DOI：
10.1002/anie.202114353
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
K Kimihisa Yamamoto
中科院分区：
文献类型：
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作者：
Takamasa Tsukamoto;Kosuke Tomozawa ;Tatsuya Moriai ;Nozomi Yoshida;Tetsuya Kambe;K Kimihisa Yamamoto
准亚纳米材料（1-3 nm）被预测表现出独特的性质，源于被认为是块状固体和分子的灰色结构，而它们的合成是非常困难的。 本研究描述了一种新的准亚纳米材料的模板合成方法，使用配位化学和聚合物化学的组合。利用客体碱性苯基甲亚胺树枝化单元与具有六个三苯甲基鎓阳离子的主体酸性核心单元的自组装，树枝化组装的超分子容易且定量地构建，而无需昂贵的技术。这种巨大的超分子胶囊在其碱性配体中积累了多种酸性铑盐，使得能够通过形成多核配合物精确合成铑颗粒。所得颗粒（Rh 84，约1.5 nm）的粒径在1-3 nm范围内，大于传统亚纳米颗粒（Rh 14，约0.85 nm），因此成功证明了准亚纳米颗粒的精确模板合成。
Quasi‐sub‐nanomaterials (1–3 nm) have been predicted to exhibit unique properties originating from the gray structures considered both bulk solids and molecules, while their synthesis is extremely difficult. The present study describes a new template synthesis method for quasi‐sub‐nanosized materials using a combination of coordination chemistry and polymer chemistry. Utilizing self‐assembly of guest basic phenylazomethine dendron units onto host acidic core units with six tritylium cations, the dendron‐assembled supramolecules were constructed easily and quantitatively without costly techniques. This huge supramolecular capsule accumulating multiple acidic rhodium salts in its basic ligands enabled a precise synthesis of rhodium particles via formation of multinuclear complexes. The obtained particles (Rh84, ≈1.5 nm) have particle sizes within 1–3 nm range and were larger than conventional sub‐nanoparticles (Rh14, ≈0.85 nm), therefore the precise template synthesis of quasi‐sub‐nanoparticles was successfully demonstrated.