Tuning the Magnetic Coupling of a Porphyrin with the Substrate through the Intramolecular Cyclization Reaction  

作　　者：Yixuan Gao Lei Tao Dongfei Wang Hui Guo Hui Chen 高艺璇;陶蕾;王东飞;郭辉;陈辉(State Key Laboratory for Advanced Metals and Materials,University of Science and Technology Beijing,Beijing 100083,China;Beijing National Center for Condensed Matter Physics and Institute of Physics,Chinese Academy of Sciences,Beijing 100190,China;School of Physical Sciences,University of Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]State Key Laboratory for Advanced Metals and Materials,University of Science and Technology Beijing,Beijing 100083,China [2]Beijing National Center for Condensed Matter Physics and Institute of Physics,Chinese Academy of Sciences,Beijing 100190,China [3]School of Physical Sciences,University of Chinese Academy of Sciences,Beijing 100190,China

出　　处：《Chinese Physics Letters》2025年第3期186-196,共11页中国物理快报(英文版)

基　　金：supported by the National Natural Science Foundation of China(Grant Nos.52350322,52201231,and 62488201);the National Key Research and Development Projects of China(Grant No.2022YFA1204100);the CAS Project for Young Scientists in Basic Research(Grant Nos.YSBR-003 and YSBR053);the Fundamental Research Funds for the Central Universities(Grant No.FRF-TP-24-055A)。

摘　　要：One of the primary objectives in molecular nano-spintronics is to manipulate the electronic configurations of organic molecules with a d-electron center by suitable external means.Here,we demonstrate the tuning of the electronic configuration of tetrakis(pentafluorophenyl)porphyrin(FeF20TPP)molecules on the Au(111)surface through a thermally induced intramolecular quadrauplicate cyclization reaction.During the reaction,the electronic configuration of a FeF20TPP molecule on the Au(111)surface changes from(d_(z)^(1)2d_(π)^(2))to(d_(z)^(2)2d_(π)^(2)).We attribute this change to significant difference in the adsorption height and variations in coupling between the orbitals of central metal atoms and the Au(111)surface.To further validate this mechanism,we substituted the central Fe ion with a Mn ion,predicting that an electronic configuration transition would not occur in MnF_(20)TPP and its product.Low-temperature scanning tunneling microscopy(STM)revealed that the FeF20TPP on Au(111)exhibits no Kondo resonance,while its cyclization product exhibits Kondo dip near the Fermi level(E_(F)).In contrast,both the MnF_(20)TPP and its product show pronounced Kondo dip at E_(F).Our work marks a significant step forward in controlling molecular electronic configuration through on-surface chemical reactions,paving the way for advanced molecular spintronics.

关 键 词：reaction. surface. KONDO 

分 类 号：O62[理学—有机化学]