Methylisatin Structural Isomers Have Different Kinetic Pathways to Self-Assembly

Methylisatin Structural Isomers Have Different Kinetic Pathways to Self-Assembly
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甲基靛红结构异构体具有不同的自组装动力学途径

DOI:
10.1021/acs.jpcc.0c05456
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发表时间:
2020
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Kandel, S. Alex
Kandel, S. Alex
中科院分区:
--
文献类型:
--
作者:
Silski-Devlin, Angela M.;Petersen, Jacob P.;Liu, Jonathan;Corcelli, Steven A.;Kandel, S. Alex

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在Au(111)表面制备了甲基靛红结构异构体的单层膜,并在真空中用扫描隧道显微镜成像。通过溶液沉积的单层制备导致这两种异构体的不同单层结构。5-甲基靛红形成紧密堆积的矩形六聚体簇,而6-甲基靛红形成环状五聚体、二聚体和紧密堆积相。通过气相沉积的单层制备导致5-和6-甲基靛红的环状五聚体的形成。将这些结果与靛红单层进行比较,靛红单层也在溶液和气相沉积时形成环状五聚体。DFT结合能计算证实了一个稳定的五聚体,因为靛红,5-甲基靛红,6-甲基靛红的5-分子簇有一个计算的结合能。不寻常的5-甲基靛红六聚体结构的形成可能是由于溶液(脉冲)沉积制备技术中存在的非平衡吸附动力学。
Monolayers of methylisatin structural isomers are prepared on the Au(111) surface and imaged using scanning tunneling microscopy in ultrahigh vacuum. Monolayer preparation via solution deposition results in different monolayer structures for these two isomers. 5-Methylisatin forms rectangular hexamer clusters that are closely packed, while 6-methylisatin forms cyclic pentamers, dimers, and a close-packed phase. Monolayer preparation via vapor deposition results in the formation of cyclic pentamers for both 5- and 6-methylisatin. These results are compared to isatin monolayers, which also form cyclic pentamers upon both solution and vapor deposition. DFT binding energy calculations corroborate a stable pentamer, as there is a calculated binding energy well for 5-molecule clusters for isatin, 5-methylisatin, 6-methylisatin. The formation of the unusual 5-methylisatin hexamer structure is likely due to nonequilibrium adsorption kinetics present in the solution (pulse) deposition preparation technique.
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