Journal
ACS NANO
Volume 7, Issue 9, Pages 8190-8198Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nn4035684
Keywords
conjugated polymers; surface polymerization; Ullmann coupling; poly(para-phenylene) (PPP); scanning tunneling microscopy (STM); fast X-ray photoelectron spectroscopy (fast-XPS); near-edge X-ray absorption fine structure spectroscopy (NEXAFS)
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Funding
- NSERC of Canada
- Canada Research Chairs program
- FRQS
- FRQNT
- Alexander von Humboldt Foundation
- Elsevier
- ELETTRA
- Center for Nanophase Materials Sciences (CNMS)
- Oak Ridge National Laboratory by the Division of Scientific User Facilities, U.S. DOE
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We provide insight into surface-catalyzed dehalogenative polymerization, analyzing the organometallic intermediate and its evolution into planar polymeric structures. A combined study using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and first-principles calculations unveils the structural conformation of substrate-bound phenylene intermediates generated from 1,4-dibromobenzene precursors on Cu(110), showing the stabilizing role of the halogen. The appearance of covalently bonded conjugated structures is followed in real time by fast-XPS measurements (with an acquisition time of 2 s per spectrum and heating rate of 2 K/s), showing that the detaching of phenylene units from the copper substrate and subsequent polymerization occur upon annealing above 460 +/- 10 K.
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