title: Single-molecule imaging of activated nitrogen adsorption on individual manganese phthalocyanine.
abstract: An atomic-scale understanding of gas adsorption mechanisms on metal-porphyrins or metal-phthalocyanines is essential for their practical application in biological processes, gas sensing, and catalysis. Intensive research efforts have been devoted to the study of coordinative bonding with relatively active small molecules such as CO, NO, NH3, O2, and H2. However, the binding of single nitrogen atoms has never been addressed, which is both of fundamental interest and indeed essential for revealing the elementary chemical binding mechanism in nitrogen reduction processes. Here, we present a simple model system to investigate, at the single-molecule level, the binding of activated nitrogen species on the single Mn atom contained within the manganese phthalocyanine (MnPc) molecule supported on an inert graphite surface. Through the combination of in situ low-temperature scanning tunneling microscopy, scanning tunneling spectroscopy, ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations, the active site and the binding configuration between the activated nitrogen species (neutral nitrogen atom) and the Mn center of MnPc are investigated at the atomic scale.
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.|‡Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore.
authors.forename: Jia Lin
authors.initials: JL
authors.lastname: Zhang
authors.affiliation: §Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China.|⊥Guizhou Provincial Key Laboratory of Computational Nanomaterial Science, Guizhou Normal College, Guiyang 550018, China.
authors.forename: Zhunzhun
authors.initials: Z
authors.lastname: Wang
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.|‡Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore.
authors.forename: Jian Qiang
authors.initials: JQ
authors.lastname: Zhong
authors.affiliation: ‡Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore.
authors.forename: Kai Di
authors.initials: KD
authors.lastname: Yuan
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
authors.forename: Qian
authors.initials: Q
authors.lastname: Shen
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
authors.forename: Lei Lei
authors.initials: LL
authors.lastname: Xu
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
authors.forename: Tian Chao
authors.initials: TC
authors.lastname: Niu
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
authors.forename: Cheng Ding
authors.initials: CD
authors.lastname: Gu
authors.affiliation: ¶Department of Chemistry and Physics, La Trobe University, Melbourne, Victoria 3086, Australia.
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Wright
authors.affiliation: ¶Department of Chemistry and Physics, La Trobe University, Melbourne, Victoria 3086, Australia.|#Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168, Australia.
authors.forename: Anton
authors.initials: A
authors.lastname: Tadich
authors.affiliation: ¶Department of Chemistry and Physics, La Trobe University, Melbourne, Victoria 3086, Australia.
authors.forename: Dongchen
authors.initials: D
authors.lastname: Qi
authors.affiliation: ∥Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University, Shanghai 200234, China.
authors.forename: He Xing
authors.initials: HX
authors.lastname: Li
authors.affiliation: ∇Singapore-Peking University Research Center for a Sustainable Low-Carbon Future, 1 CREATE Way, #15-01, CREATE Tower, Singapore 138602, Singapore.|○College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
authors.forename: Kai
authors.initials: K
authors.lastname: Wu
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.|∇Singapore-Peking University Research Center for a Sustainable Low-Carbon Future, 1 CREATE Way, #15-01, CREATE Tower, Singapore 138602, Singapore.
authors.forename: Guo Qin
authors.initials: GQ
authors.lastname: Xu
authors.affiliation: §Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Zhenyu
authors.initials: Z
authors.lastname: Li
authors.affiliation: †Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.|‡Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore.|∇Singapore-Peking University Research Center for a Sustainable Low-Carbon Future, 1 CREATE Way, #15-01, CREATE Tower, Singapore 138602, Singapore.|◆NUS (Suzhou) Research Institute, National University of Singapore, 377 Lin Quan Street, Suzhou Industrial Park, Jiang Su 215123, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Chen
keywords: Single molecule; activated nitrogen; axial coordination; manganese phthalocyanine