二维亚稳态自组装网格主客体识别中的催组装

doi:10.3866/PKU.WHXB202309011

物理化学学报 >> 2024, Vol. 40 >> Issue (9): 2309011.doi: 10.3866/PKU.WHXB202309011

论文上一篇

二维亚稳态自组装网格主客体识别中的催组装

薛仁杰¹^,†, 马超¹^,†, 何晶¹, 李雪超¹, 唐雁宁¹, 迟力峰¹^,²^,*(), 张海明¹^,*()

¹ 苏州大学功能纳米与软物质研究院(FUNSOM), 江苏省碳基功能材料与器件高技术研究重点实验室, 江苏苏州 215123
² 澳门科技大学材料科学与工程学院, 澳苏先进功能材料联合研究中心, 澳门 999078

收稿日期:2023-09-08 修回日期:2023-09-30 录用日期:2023-10-09 发布日期:2023-10-16
通讯作者: Email: hmzhang@suda.edu.cn, Tel.: +86-512-65885085 (张海明)chilf@suda.edu.cn (迟力峰)
作者简介:
^†These authors contributed equally to this work.
基金资助:
国家自然科学基金(22072103); 国家自然科学基金(51821002); 国家自然科学基金(22161132026); 苏州市纳米科技协同创新中心, 江苏省高校重点学科发展项目(PAPD); 苏州市表面与界面智能物质重点实验室(SZS2022011); 高等学校学科创新引智计划(“111”计划)

Catassembly in the Host-Guest Recognition of 2D Metastable Self-Assembled Networks

Renjie Xue¹, Chao Ma¹, Jing He¹, Xuechao Li¹, Yanning Tang¹, Lifeng Chi¹^,²^,*(), Haiming Zhang¹^,*()

¹ Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, Jiangsu Province, China
² Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa 999078, Macao, China

Received:2023-09-08 Revised:2023-09-30 Accepted:2023-10-09 Published:2023-10-16
Contact: Email: hmzhang@suda.edu.cn, Tel.: +86-512-65885085 (Haiming Zhang)chilf@suda.edu.cn (Lifeng Chi)
Supported by:
the National Natural Science Foundation of China(22072103); the National Natural Science Foundation of China(51821002); the National Natural Science Foundation of China(22161132026); the Collaborative Innovation Center of Suzhou Nano Science & Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD); the Suzhou Key Laboratory of Surface and Interface Intelligent Matter(SZS2022011); "111" Project(“111”计划)

1. WHXB202309011-SI-5p.pdf(6102KB)

摘要/Abstract

摘要：

催组装是用于描述催组剂帮助下的分子组装的新概念，目前还未报道过催组装过程的分子水平表征。本文中，我们利用扫描隧道显微镜(STM)，在辛酸和高序热解石墨之间的液固界面，观察到了1, 3, 5-三(4-羧基苯基)-苯(BTB)亚稳态自组装网格在主客体识别过程中的催组装过程。实验中采用的是低浓度的客体分子酞菁铜(CuPc)，以及晕苯(COR)分子。我们对比了单客体(COR/BTB或CuPc/BTB)体系和多客体(COR & CuPc/BTB)体系中客体分子在主客体组装过程中的不同吸附特征。在多客体分子(COR & CuPc/BTB)体系中，晕苯分子优先填入主体六边形网络中，随着组装的进行逐渐被酞菁铜分子取代。晕苯分子在组装过程中发挥了催组装剂的作用，帮助低浓度酞菁铜完成了其本身无法形成的、大面积的CuPc/BTB共组装。这是首次在分子尺度观察到的完整的催组装过程，有助于指导构建更高复杂度的二维分子组装单层膜。

关键词: 催组装, 自组装网格, 主客体现象, 扫描隧道显微镜, 选择性识别

Abstract:

Catassembly is a newly developed concept concerning the process of molecular assembly improved by a catalyst-assembler (catassembler). However, it has not been visualized in detail at the molecular level. To achieve the formation of highly complex structures with high efficiency and selectivity, a deeper understanding of catassembly is essential. In this study, we present the scanning tunneling microscopy (STM) characterization of a catassembly process within host-guest assembly. We utilize a metastable self-assembled network of 1, 3, 5-tris(4-carboxyphenyl)-benzene (BTB) at the liquid-solid interface between 1-octanoic acid and highly oriented pyrolytic graphite (HOPG). Different adsorption behaviors of low-concentration guest molecules (copper phthalocyanine (CuPc), and coronene (COR)) are contrastively analyzed during the host-guest assembly in both single-guest (COR/BTB or CuPc/BTB) and multi-guest molecule (COR & CuPc/BTB) systems. The spontaneous phase transition from a hexagonal to an oblique structure of BTB monolayers (high concentration, approximately 500 μmol∙L⁻¹ in octanoic acid) provides an ideal metastable phase for studying the dynamic assembly process. In the host-guest assembly, the metastable BTB hexagonal phase serves as a host network and can be stabilized by co-assembling guest molecules under a negative bias voltage. However, the stability of the metastable phase varies with different guest molecules. We observe that the BTB metastable phase is more robust with COR guest molecules than with CuPc. In the CuPc/BTB system, we find that low-concentration CuPc (approximately 1.5 μmol∙L⁻¹ in octanoic acid) can hardly co-assemble with BTB, leading to the gradual collapse of the metastable BTB networks into the oblique phase. The different stability of BTB metastable phase in the host-guest assembly is attributed to differences in the kinetics of trapping guest molecules. Guest COR molecules exhibit kinetic advantages over CuPc when assembling with host BTB networks under a negative sample bias. The lower trapping rate of CuPc hinders the formation of co-assembled BTB/CuPc networks. These differences in the dynamic behavior of the guest molecules are further explored in the research of catassembly. In a multi-guest molecule system (COR & CuPc/BTB), COR molecules are preferentially trapped by BTB hexagonal networks and can gradually be replaced by CuPc during continuous scanning. The more energetically stable structure of CuPc/BTB compared to COR/BTB rationalizes the exchange of the guest molecule and the evolution of the assembly phase. The involvement of COR significantly increases both the efficiency and quality of the CuPc/BTB assembly, serving as a catassembler. This observation provides insights into a complete catassembly process at the molecular level, enabling further investigations into the selectivity and efficiency of host-guest phenomena for potential applications in analysis and separation. Additionally, this work serves as a prototype for constructing highly complex 2D assembled monolayers.

Key words: Catassembly, Self-assembled networks, Host-guest phenomena, Scanning tunneling microscopy, Selective recognition

薛仁杰, 马超, 何晶, 李雪超, 唐雁宁, 迟力峰, 张海明. 二维亚稳态自组装网格主客体识别中的催组装[J]. 物理化学学报, 2024, 40(9), 2309011. doi: 10.3866/PKU.WHXB202309011

Renjie Xue, Chao Ma, Jing He, Xuechao Li, Yanning Tang, Lifeng Chi, Haiming Zhang. Catassembly in the Host-Guest Recognition of 2D Metastable Self-Assembled Networks[J]. Acta Phys. -Chim. Sin. 2024, 40(9), 2309011. doi: 10.3866/PKU.WHXB202309011

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202309011

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I9/2309011

图/表 5

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二维亚稳态自组装网格主客体识别中的催组装

Catassembly in the Host-Guest Recognition of 2D Metastable Self-Assembled Networks

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