Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds |
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| Authors: | Dr. Lara Ferrighi Dr. Igor Píš Dr. Thanh Hai Nguyen Mattia Cattelan Silvia Nappini Andrea Basagni Dr. Matteo Parravicini Prof. Antonio Papagni Dr. Francesco Sedona Elena Magnano Dr. Federica Bondino Prof. Cristiana Di Valentin Dr. Stefano Agnoli |
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| Affiliation: | 1. Department of Materials Science, Università di Milano‐Bicocca, Via Cozzi 55, 20125 Milano (Italy);2. IOM CNR, Laboratorio TASC, S.S. 14 Km. 163.5, 34149 Basovizza (TS) (Italy);3. Elettra‐Sincrotrone Trieste S.C.p.A. S.S. 14 Km 163.5, 34149 Basovizza (TS) (Italy);4. Department of Chemical Sciences, University of Padua, Via Marzolo 1, 35131 Padova (Italy) |
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| Abstract: | Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature‐programmed desorption (TPD) to high‐resolution X‐ray spectroscopy (XPS) and near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS). State‐of‐the‐art density‐functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon‐radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper‐bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close‐packed rows as a consequence of radical‐site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions. |
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| Keywords: | C H activation density functional calculations organic electronics surfaces and interfaces Ullmann reaction |
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