Solvent-Dependent Core-Modified Rubyrin Self-Assembly at Liquid/Solid Interfaces

Chen Chen; Siqi Zhang; Bin Tu; Ting Meng; Jianqiao Li; Yuxin Qian; Pengfei Li; Bo Liu; Wubiao Duan; Haijun Xu; Fengying Zhao; Yang Peng; Jing Li; Qingdao Zeng

doi:10.1021/acs.langmuir.9b03867

Solvent-Dependent Core-Modified Rubyrin Self-Assembly at Liquid/Solid Interfaces

Langmuir. 2020 Apr 14;36(14):3879-3886. doi: 10.1021/acs.langmuir.9b03867. Epub 2020 Apr 6.

Authors

Chen Chen^{1

2}, Siqi Zhang^{1

2}, Bin Tu², Ting Meng^{2

3}, Jianqiao Li^{1

2}, Yuxin Qian^{1

2}, Pengfei Li³, Bo Liu¹, Wubiao Duan¹, Haijun Xu³, Fengying Zhao^{4

5}, Yang Peng^{4

5}, Jing Li^{4

5}, Qingdao Zeng^{2

6}

Affiliations

¹ Department of Chemistry, School of Science, Beijing Jiaotong University, Beijing 100044, China.
² CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology (NCNST), Beijing 100190, China.
³ College of Chemical Engineering Jiangsu Key Lab of Biomass-based Green Fuels and Chemicals, Nanjing Forestry University, Nanjing 210037, China.
⁴ Jiangxi College of Applied Technology, Ganzhou 341000, China.
⁵ Engineering Research Center of Nano-Geo Materials of Ministry of Education, China University of Geosciences, Wuhan 430074, China.
⁶ Center of Materials Science and Optoelectonics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.

PMID: 32212611
DOI: 10.1021/acs.langmuir.9b03867

Abstract

Scanning tunneling microscopy (STM) was utilized to disclose four novel core-modified rubyrin self-assembly behaviors on the highly-oriented pyrolytic graphite (HOPG) surface, of which N₂S₄-OR(1)/N₂Se₄-OR(2) had no phenanthrene pyrrole ring and N₂S₄-OR(3)/N₂Se₄-OR(4) had phenanthrene-fused pyrrole rings and meso-aryl substituents. It was discovered that the core-modified rubyrin could self-assemble into either face-on or edge-on monolayer structures selectively at the liquid/HOPG interface in different solvents. There was an obvious solvent-dependent self-assembly for N₂S₄-OR(3)/N₂Se₄-OR(4), which adopted an edge-on and face-on structure in 1-phenyloctane and 1-heptanoic acid solvents, respectively, whereas N₂S₄-OR(1)/N₂Se₄-OR(2) showed no obvious difference in the assembly structure, which both adopted a face-on structure in the two solvents. Density functional theory (DFT) calculations were also utilized to reveal the relevant self-assembly mechanisms. This study shows a typical solvent effect regulating core-modified rubyrin self-assembly, which is essential for porphyrin-based functional devices' design and manufacture.