On-surface synthesis of doubly-linked porphyrin polymers via cycloaromatization of isopropyl substituents on Au(111)

Shenwei Chen; Haiwei Wang; Lixia Kang; Ran Chen; Zhaokun Wang; Suya Dai; Xiang Zhang; Yongjie Chen; Yucheng Song; Cunfeng Zheng; Zechao Yang; Zengfu Ou; Jin Li; Hongbing Ji

doi:10.1039/D5NR03921E

On-surface synthesis of doubly-linked porphyrin polymers via cycloaromatization of isopropyl substituents on Au(111)

Shenwei Chen,†^a Haiwei Wang,

†^a Lixia Kang,^b Ran Chen,^c Zhaokun Wang,^d Suya Dai,^a Xiang Zhang,^a Yongjie Chen,^a Yucheng Song,^a Cunfeng Zheng,^a Zechao Yang,^b Zengfu Ou,*^e Jin Li

*^a and Hongbing Ji*^a

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* Corresponding authors

^a State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang, China
E-mail: lijin@zjut.edu.cn, jihb@zjut.edu.cn

^b School of Physics, Hangzhou Normal University, Hangzhou, Zhejiang, China

^c Centre of the Protection and Monitoring for Cultural Heritage, Yungang Academy, Datong, Shanxi, China

^d School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi, China

^e College of Physics and Electronic Information Engineering, Guilin University of Technology, Guilin, Guangxi, China
E-mail: ouzengfu@glut.edu.cn

Abstract

We report the surface-mediated synthesis of doubly-linked porphyrin polymers (DPPs) on Au(111) via thermally induced polymerization of 5,10,15,20-tetrakis[4-(1-methylethyl)phenyl]-21H,23H-porphine. The transformation proceeds through a hierarchical process involving (i) [3 + 3] cycloaromatization of isopropyl substituents, (ii) intramolecular cyclodehydrogenation, and (iii) in situ metalation with Au atoms on Au(111). Combining scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations, we systematically elucidate the hierarchical transformation and electronic modulation of DPPs on Au(111). Charge density difference analysis reveals a significant electron transfer (∼1.04 e⁻ per Au) from the Au atoms to the porphyrin π-system, accounting for the n-type doping effect and the transition from semiconducting to semimetallic behavior in the Au-metalated DPPs.

Nanoscale

On-surface synthesis of doubly-linked porphyrin polymers via cycloaromatization of isopropyl substituents on Au(111)

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On-surface synthesis of doubly-linked porphyrin polymers via cycloaromatization of isopropyl substituents on Au(111)

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