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Title: Influence of Dissolved O 2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite

Abstract

The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H 2OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H 2OEP, indicating that the metal center of CuOEP plays a critical role. Finally, when the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes.

Authors:
 [1];  [1];  [1];  [2];  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1608257
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 32; Journal Issue: 22; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Liquid-STM; supramolecular self-assembly; enzyme; O2

Citation Formats

Hao, Yibo, Weatherup, Robert S., Eren, Baran, Somorjai, Gabor A., and Salmeron, Miquel. Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite. United States: N. p., 2016. Web. doi:10.1021/acs.langmuir.6b01580.
Hao, Yibo, Weatherup, Robert S., Eren, Baran, Somorjai, Gabor A., & Salmeron, Miquel. Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite. United States. doi:10.1021/acs.langmuir.6b01580.
Hao, Yibo, Weatherup, Robert S., Eren, Baran, Somorjai, Gabor A., and Salmeron, Miquel. Mon . "Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite". United States. doi:10.1021/acs.langmuir.6b01580. https://www.osti.gov/servlets/purl/1608257.
@article{osti_1608257,
title = {Influence of Dissolved O2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite},
author = {Hao, Yibo and Weatherup, Robert S. and Eren, Baran and Somorjai, Gabor A. and Salmeron, Miquel},
abstractNote = {The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H2OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H2OEP, indicating that the metal center of CuOEP plays a critical role. Finally, when the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes.},
doi = {10.1021/acs.langmuir.6b01580},
journal = {Langmuir},
issn = {0743-7463},
number = 22,
volume = 32,
place = {United States},
year = {2016},
month = {5}
}

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