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Endohedrally Doped Cage Clusters.
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-08-31 , DOI: 10.1021/acs.chemrev.9b00651 Jijun Zhao 1 , Qiuying Du 1 , Si Zhou 1 , Vijay Kumar 2, 3
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-08-31 , DOI: 10.1021/acs.chemrev.9b00651 Jijun Zhao 1 , Qiuying Du 1 , Si Zhou 1 , Vijay Kumar 2, 3
Affiliation
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The discovery of carbon fullerene cages and their solids opened a new avenue to build materials from stable cage clusters as “artificial atoms” or “superatoms” instead of atoms. However, cage clusters of other elements are generally not stable. In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to highly stable Zr@Si16 fullerene and Ti@Si16 Frank–Kasper polyhedral clusters with large HOMO–LUMO gaps. In 2002, Zr@Ge16 was shown to form a Frank–Kasper polyhedron, suggesting the possibility of designing novel clusters by tuning endohedral and cage atoms. These results were subsequently confirmed from experiments. In the past nearly two decades, many experimental and theoretical studies have been carried out on different clusters, and many very stable cage clusters with possibly high abundance have been found by endohedral doping. Indeed in 2017, Ta@Si16 and Ti@Si16 cage clusters have been synthesized in bulk quantity of about 100 mg using a dry-chemistry method, giving rise to a new hope of developing cluster-based materials in macroscopic quantity besides the well-known C60 fullerene solid. Also, wet-chemistry methods have been used to synthesize endohedrally doped clusters as well as ligated clusters and their solids, which auger well for the development of novel nanostructured materials using atomically precise clusters with unique properties. In this comprehensive review, we present results of many such developments in this fast-growing field including (i) endohedrally doped Al, Ga, and In clusters, (ii) small endohedral carbon fullerene cages with ≤ 28 carbon atoms, (iii) metal doped boron cages, (iv) endohedrally doped cages of group 14 elements (Si, Ge, Sn, and Pb), (v) coinage metal (Cu, Ag, Au) cages doped with a transition metal atom as well as their ligated clusters and crystals, (vi) endohedrally doped cages of compound semiconductors, and (vii) multilayer Matryoshka cages and core–shell structures. In a large number of cases, we have performed ab initio calculations to present updated results of the most stable atomic structures and fundamental electronic properties of the endohedrally doped cage clusters. We discuss electronic, magnetic, optical, and catalytic properties in order to shed light on their potential applications. The stability of the doped cage clusters has been correlated to the concept of filling the electronic shells for superatoms such as within a spherical potential model and also using various electron counting rules including Wade–Mingos rules, systems with 18 and 32 electrons, and the spherical aromaticity rule. We also discuss cluster–cluster interaction in cluster dimers and assemblies of some of the promising doped cage clusters in different dimensions. Finally, we give a perspective of this field with a bright future.
中文翻译：
内掺杂的笼型簇。
碳富勒烯笼子及其固体的发现开辟了一条新的途径，可以从稳定的笼子簇中以“人造原子”或“超原子”代替原子来制造材料。但是，其他元素的笼状簇通常不稳定。从2001年开始，从头算计算表明Zr和Ti原子的内面掺杂会导致具有高HOMO-LUMO间隙的高度稳定的Zr @ Si 16富勒烯和Ti @ Si 16 Frank-Kasper多面体簇。2002年，Zr @ Ge 16结果表明它形成了Frank–Kasper多面体，这表明可以通过调节内面和笼形原子设计新颖的簇。这些结果随后被实验证实。在过去的近二十年中，对不同的簇进行了许多实验和理论研究，通过内面掺杂发现了许多非常稳定的笼形簇，可能具有很高的丰度。确实在2017年，使用干化学方法以大约100 mg的体积合成了Ta @ Si 16和Ti @ Si 16笼形簇，这为开发除井眼之外的宏观数量的簇状材料带来了新希望已知的C 60富勒烯固体。而且，湿化学方法已被用于合成内掺有杂质的团簇以及连接的团簇及其固体，这预示着使用具有独特性质的原子精确团簇的新型纳米结构材料的发展。在这份全面的综述中，我们介绍了在这个快速增长的领域中许多此类进展的结果，其中包括：（i）内杂掺杂的Al，Ga和In团簇；（ii）碳原子数≤28的小型内嵌碳富勒烯笼，（iii）金属掺杂硼的笼子，（iv）掺入第14组元素（硅，锗，锡和铅）的内掺铁的笼子，（v）掺杂过渡金属原子及其连接簇的钱币金属（铜，银，金）笼子和晶体，（vi）化合物半导体内掺杂的笼子，以及（vii）多层Matryoshka笼子和核-壳结构。从头算起以显示内掺有杂质的笼形团簇的最稳定原子结构和基本电子性质的更新结果。我们讨论电子，磁性，光学和催化性质，以阐明它们的潜在应用。掺杂的笼状簇的稳定性与填充超原子的电子壳的概念（例如球形势模型）以及使用各种电子计数规则（包括Wade–Mingos规则，具有18和32个电子的系统以及球形）相关联芳香性规则。我们还将讨论簇二聚体中的簇与簇之间的相互作用以及一些不同尺寸的有希望的掺杂笼簇的组装。最后，我们给出了这个领域的光明前景。
更新日期：2020-08-31
中文翻译：
内掺杂的笼型簇。
碳富勒烯笼子及其固体的发现开辟了一条新的途径，可以从稳定的笼子簇中以“人造原子”或“超原子”代替原子来制造材料。但是，其他元素的笼状簇通常不稳定。从2001年开始，从头算计算表明Zr和Ti原子的内面掺杂会导致具有高HOMO-LUMO间隙的高度稳定的Zr @ Si 16富勒烯和Ti @ Si 16 Frank-Kasper多面体簇。2002年，Zr @ Ge 16结果表明它形成了Frank–Kasper多面体，这表明可以通过调节内面和笼形原子设计新颖的簇。这些结果随后被实验证实。在过去的近二十年中，对不同的簇进行了许多实验和理论研究，通过内面掺杂发现了许多非常稳定的笼形簇，可能具有很高的丰度。确实在2017年，使用干化学方法以大约100 mg的体积合成了Ta @ Si 16和Ti @ Si 16笼形簇，这为开发除井眼之外的宏观数量的簇状材料带来了新希望已知的C 60富勒烯固体。而且，湿化学方法已被用于合成内掺有杂质的团簇以及连接的团簇及其固体，这预示着使用具有独特性质的原子精确团簇的新型纳米结构材料的发展。在这份全面的综述中，我们介绍了在这个快速增长的领域中许多此类进展的结果，其中包括：（i）内杂掺杂的Al，Ga和In团簇；（ii）碳原子数≤28的小型内嵌碳富勒烯笼，（iii）金属掺杂硼的笼子，（iv）掺入第14组元素（硅，锗，锡和铅）的内掺铁的笼子，（v）掺杂过渡金属原子及其连接簇的钱币金属（铜，银，金）笼子和晶体，（vi）化合物半导体内掺杂的笼子，以及（vii）多层Matryoshka笼子和核-壳结构。从头算起以显示内掺有杂质的笼形团簇的最稳定原子结构和基本电子性质的更新结果。我们讨论电子，磁性，光学和催化性质，以阐明它们的潜在应用。掺杂的笼状簇的稳定性与填充超原子的电子壳的概念（例如球形势模型）以及使用各种电子计数规则（包括Wade–Mingos规则，具有18和32个电子的系统以及球形）相关联芳香性规则。我们还将讨论簇二聚体中的簇与簇之间的相互作用以及一些不同尺寸的有希望的掺杂笼簇的组装。最后，我们给出了这个领域的光明前景。
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