在半金屬Bi(111)表面上四聯苯分子的手性自組裝
首發時間:2023-08-24
摘要:本文利用低溫掃描隧道顯微鏡(STM)研究了四聯苯分子在半金屬Bi(111)表面上的超分子手性和自組裝結構。實驗發現,在低覆蓋度下形成的納米團簇中,四聯苯分子有平躺和側躺兩種不同的吸附取向。在亞單層的覆蓋度下,四聯苯分子形成多疇的自組裝單層結構。自組裝單層的基本單元是由兩個平躺分子和一個側躺分子構成的三聚體。高分辯的STM圖表明,平躺的四聯苯分子具有平面化的非手性結構,而側躺的四聯苯分子具有扭曲的非平面手性結構,從而導致三聚體團簇具有超分子手性。有趣的是,在疇區內部相鄰三聚體的手性總是相反;而在疇界兩側三聚體的手性保持相同,表明同手性的三聚體之間存在空間位阻作用。當覆蓋度增加到一個滿層時疇界不復存在,整個分子單層形成長程有序的消旋結構。此外,由于四聯苯分子與半金屬Bi(111)襯底之間較弱的相互作用,無論是側躺的分子還是平躺的分子,都容易受到針尖電場的影響發生平移或轉動。上述研究結果為理解四聯苯分子和半金屬之間的相互作用,超分子手性和分子自組裝結構之間的關聯,實現分子-襯底界面結構的長程有序提供了重要信息。
關鍵詞: 超分子手性 四聯苯 自組裝;掃描隧道顯微鏡 疇界
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Chiral self-assembly of p-quaterphenyl on semimetallic Bi(111) surface
Abstract:The supramolecular chirality and self-assembly of p-quaterphneyl on the semimetallic Bi(111) surface have been investgated with a low temperature scanning tunneling microscopy (STM). It is found that there are flat-lying and edge-on molecules in the nanoclusters of p-quaterphneyl. In the submonolayer regime,p-quaterphneyl molecules form the self-assembled structure with multiple domains. The building bolcks of self-assemblies are molecular trimer with two flat-lying and one edge-on molecules. High-resolution STM images demonstrate that the flat-lying molecules have a planar achiral structure, while the edge-on molecules have a twisted chiral structure, which result in the supramolecular chirality of p-quaterphneyl strimers. Interestingly, theneighboring trimers inside the domains reveal opposite chirality, while the same chirality appears for the trimers at the domain boundaries, indicating the steric hindrance between the trimers with same handedness. When the voerage is increased to full monolayer, the domain boundaries disappear from the self-assembled structure, which have the long-range ordering with racemates. Moreover, due to the weak molecule-substrate interaction, both the flat-lying and the edge-on molecules can be moved or rotated under the electrical filed of STM tip. These results provide important information for the understadning of interaction between p-quaterphneyl and Bi(111) surface, the correlation between the supramolecular chirality and self-assembly, and realization of the organic-metal interface with long-range order.
Keywords: Supramolecular chirality p-quaterphenyl self-assembly STM domain boundary
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在半金屬Bi(111)表面上四聯苯分子的手性自組裝
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