Molecularly Designed Cluster?Surface Interaction for Halogen-like and Alkali-like Metal-Encapsulating Silicon Cage Superatoms on n- and p-Type Organic Substrates
Molecularly Designed Cluster?Surface Interaction for Halogen-like and Alkali-like Metal-Encapsulating Silicon Cage Superatoms on n- and p-Type Organic Substrates
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分子设计簇？n型和p型有机基底上类卤和类碱金属封装硅笼超原子的表面相互作用
DOI：
10.1021/acs.jpcc.2c02196
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Nakajima Atsushi
中科院分区：
文献类型：
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作者：
Kamoshida Toshiaki;Shibuta Masahiro;Ohta Tsutomu;Eguchi Toyoaki;Nakajima Atsushi
金属包覆的Si 16笼状团簇（M @ Si 16）是一种很有前途的超原子（SA），可以通过改变中心金属原子来设计其组装材料的可调性质：第3、4和5族中心金属原子分别具有卤素、稀有气体和碱金属性质。为了制造SA组件，金属封装的M@Si16SA（M = Lu、Hf和Ta）必须可控地固定在衬底上。用有机分子修饰的衬底可以促进簇-表面相互作用的优化，因为SA和预沉积的有机分子之间的分子局部相互作用通过分子络合来控制电子性质。在本研究中，M @ Si 16 SA被尺寸选择性地软着陆在沉积有n型富勒烯（C60）和p型六-叔丁基-六-围-六苯并冠烯（HB-HBC，C66 H66）的有机衬底上，并且M @ Si 16在有机衬底上的电子状态被X射线和紫外光电子能谱表征。在C60衬底上，所有的M@Si16都被固定为阳离子，通过电荷转移相互作用形成M@Si16+C60-，而在HB-HBC衬底上，M@Si16-HB-HBC+（M = Lu和Hf）与阴离子M@Si16-形成。结合密度泛函理论计算，基于其对O2气体暴露的化学稳定性检查了M@Si16 SA的电荷偏好; HB-HBC上的Lu@Si16比C60上的对O2更稳健，而HB-HBC上的Ta@Si16比C60上的稳健性差。根据SA的性质，适当选择用于沉积的有机分子提供了通过簇-表面相互作用形成SA组装的纳米材料的分子设计师概念。
Metal-encapsulating Si16cage clusters (M@Si16) are promising superatoms (SAs) for designing tunable properties for their assembled materials by changing the central metal atom: halogen-like, rare-gas-like, and alkali-like characteristics appear for the central metal atom of groups 3, 4, and 5, respectively. To fabricate SA assemblies, metal-encapsulating M@Si16SAs (M = Lu, Hf, and Ta) must be controllably immobilized on a substrate. Substrates decorated with organic molecules can facilitate optimization of a cluster–surface interaction because the molecular local interactions between SAs and predeposited organic molecules govern the electronic properties through molecular complexation. In this study, M@Si16SAs are size-selectively soft-landed on organic substrates deposited with n-type fullerene (C60) and p-type hexa-tert-butyl-hexa-peri-hexabenzocoronene (HB-HBC, C66H66), and the electronic states of M@Si16on the organic substrates are characterized by X-ray and ultraviolet photoelectron spectroscopy. On the C60substrate, all M@Si16are fixed to be cationic, forming M@Si16+C60–via a charge transfer interaction, while on an HB-HBC substrate, M@Si16–HB-HBC+(M = Lu and Hf) is formed with anionic M@Si16–. Together with density functional theory calculations, the charge preference of the M@Si16SA is examined based on its chemical stability against O2gas exposure; Lu@Si16on HB-HBC is more robust toward O2than that on C60, while Ta@Si16on HB-HBC is less robust than that on C60. Depending on the SA properties, an appropriate selection of organic molecules for deposition provides a molecular designer concept for forming SA-assembled nanomaterials through the cluster–surface interaction.