具有不對稱配體金屬超分子的自組裝及掃描隧道顯微鏡表徵
作者:
小柯機器人發布時間:2021/1/7 11:44:14
深圳大學李霄鵬團隊揭示了具有不對稱配體金屬超分子的自組裝並使用掃描隧道顯微鏡進行表徵。相關論文發表在2021年1月4日出版的《美國化學會志》。
不對稱和不對稱結構廣泛存在,在自然界和生命系統中起著至關重要的作用。在金屬超分子組裝領域,利用非對稱模塊構建人工結構尚處於起步階段。
該文中,研究人員報導了基於兩個不對稱雙層配體的超分子體系的自組裝。藉助超高真空低溫掃描隧道顯微鏡(UHV-LT-STM),研究人員研究了對應四種類型結合模式的具有兩個主要的構象配合物A的配體LA的四種異構結構。研究人員研究了配體LA與兩種主要構象配合物A的四種結合模式對應的四種異構體結構。通過STM測量的異構體分布和密度泛函理論(DFT)計算得到的每個異構體的總結合能表明,最豐富的異構體可能是總結合能最高的最穩定的異構體。
最後,通過縮短內外層之間的連接體和臂長,可以將不對稱配體LB的排列控制在與B的單一構象相對應的一種結合模式內。
附:英文原文
Title: Self-Assembly of Metallo-Supramolecules with Dissymmetrical Ligands and Characterization by Scanning Tunneling Microscopy
Author: Junjuan Shi, Yiming Li, Xin Jiang, Hao Yu, Jiaqi Li, Houyu Zhang, Daniel J. Trainer, Saw Wai Hla, Heng Wang, Ming Wang, Xiaopeng Li
Issue&Volume: January 4, 2021
Abstract: Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Finally, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.
DOI: 10.1021/jacs.0c12508
Source: https://pubs.acs.org/doi/10.1021/jacs.0c12508