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Title: Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules

Abstract

On-surface metalation of metal-free phthalocyanine derivatives is a simple and solvent-free way to fabricate MPc compounds. Using phthalocyanine (H 2Pc) molecules on Ag(111) as an example, we investigated the atomic-scale mechanisms of on-surface metalation processes using first-principles calculations based on density functional theory. When the molecules are deposited on a substrate first, we find that transition-metal atoms, except for Zn, drop directly from the vacuum into the molecule’s cavity without an energy barrier and bond with the inner four nitrogen atoms, with the two pyrrolic H atoms still in place. Subsequently, the two H atoms transfer to the substrate by overcoming small energy barriers and diffuse away. The substrate participates in the reaction by hybridization. In the alternative process, when metal atoms are adsorbed first on the surface and the H 2Pc molecules are then added, the metal atoms diffuse into the cavity of the molecule via the molecule–surface interface by overcoming finite energy barriers. Finally, the above results provide insights into the on-surface metalation that can guide the control of the reaction pathway and products at the atomic level.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [2]
  1. Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China); Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy & Dept. of Electrical Engineering and Computer Science
  2. Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China)
  3. Vanderbilt Univ., Nashville, TN (United States). Dept. of Physics and Astronomy & Dept. of Electrical Engineering and Computer Science; Univ. of Chinese Academy of Sciences, Beijing (China). Inst. of Physics; Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1483798
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bao, De-Liang, Zhang, Yu-Yang, Du, Shixuan, Pantelides, Sokrates T., and Gao, Hong-Jun. Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b00086.
Bao, De-Liang, Zhang, Yu-Yang, Du, Shixuan, Pantelides, Sokrates T., & Gao, Hong-Jun. Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules. United States. doi:10.1021/acs.jpcc.8b00086.
Bao, De-Liang, Zhang, Yu-Yang, Du, Shixuan, Pantelides, Sokrates T., and Gao, Hong-Jun. Tue . "Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules". United States. doi:10.1021/acs.jpcc.8b00086. https://www.osti.gov/servlets/purl/1483798.
@article{osti_1483798,
title = {Barrierless On-Surface Metal Incorporation in Phthalocyanine-Based Molecules},
author = {Bao, De-Liang and Zhang, Yu-Yang and Du, Shixuan and Pantelides, Sokrates T. and Gao, Hong-Jun},
abstractNote = {On-surface metalation of metal-free phthalocyanine derivatives is a simple and solvent-free way to fabricate MPc compounds. Using phthalocyanine (H2Pc) molecules on Ag(111) as an example, we investigated the atomic-scale mechanisms of on-surface metalation processes using first-principles calculations based on density functional theory. When the molecules are deposited on a substrate first, we find that transition-metal atoms, except for Zn, drop directly from the vacuum into the molecule’s cavity without an energy barrier and bond with the inner four nitrogen atoms, with the two pyrrolic H atoms still in place. Subsequently, the two H atoms transfer to the substrate by overcoming small energy barriers and diffuse away. The substrate participates in the reaction by hybridization. In the alternative process, when metal atoms are adsorbed first on the surface and the H2Pc molecules are then added, the metal atoms diffuse into the cavity of the molecule via the molecule–surface interface by overcoming finite energy barriers. Finally, the above results provide insights into the on-surface metalation that can guide the control of the reaction pathway and products at the atomic level.},
doi = {10.1021/acs.jpcc.8b00086},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 122,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: The dropping-down reaction pathway for the metalation of an H2Pc molecule on a Ag(111) surface using an Fe atom. (a) The energy profile of the dropping-down process. Each step corresponds to the structures shown in the upper panels in (c). (b) Top view of an H2Pc molecule. (c-f)more » Upper panels: Cross sections of the atomic configurations of the ISdrop, S-I, S-II, and the FSdrop shown in (a), respectively. Lower panels: Cross sections of the electronic densities of the ISdrop, S-I, S-II, and the FSdrop with a zoomed-in scale marked by blue dashed box in the upper panels. The cross sections are crossing the Fe atom and the two inner H atoms. The contour lines in the lower panels in (c-f) indicate the electron density ranges from 0.54 e/Å3 to 3.0 e/Å3, with intervals of 0.4 e/Å3.« less

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