Anchoring of a Carboxyl-Functionlized Norbornadiene Derivative to an Atomically-Defined Cobalt Oxide Surface

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Details zur Publikation

Autor(en): Schwarz M, Mohr S, Xu T, Döpper T, Weiß C, Civale K, Hirsch A, Görling A, Libuda J
Zeitschrift: Journal of Chemical Physics
Jahr der Veröffentlichung: 2017
Band: 121
Seitenbereich: 11508-11518
ISSN: 0021-9606
Sprache: Englisch


Abstract

We have investigated the anchoring of the molecular energy carrier norbornadiene (NBD) to an atomically defined oxide surface. To this end, we synthesized a carboxyl-functionalized NBD derivative, namely 1-(2$\prime$-norbornadienyl)pentanoic acid (NBDA), and deposited it by physical vapor deposition (PVD) under ultrahigh vacuum (UHV) conditions onto a well-ordered Co3O4(111) film grown on Ir(100). In addition, we performed a comparative growth study with benzoic acid (BA) under identical conditions which was used as a reference. The interaction and orientation of NBDA and BA with the oxide surface were monitored in situ during film growth by isothermal time-resolved infrared reflection--absorption spectroscopy (TR-IRAS), both below and above the multilayer desorption temperature. The thermal behavior and stability of the films were investigated by temperature-programmed IRAS (TP-IRAS), with help of density functional (DF) calculations. BA binds to Co3O4(111) under formation of a symmetric chelating carboxylate with the molecular plane oriented nearly perpendicular to the surface. At low temperature (130 K), intact BA physisorbs in form of dimers on top of the saturated monolayer. Upon annealing to 155 K, a reordering transition is observed, in which BA in the multilayer adopts a more flat-lying orientation. The BA multilayer desorbs at 220 K, whereas the surface-anchored BA monolayer is stable up to 400 K. At higher temperature (400--550 K), desorption and decomposition are observed. Very similar to BA, NBDA binds to Co3O4(111) by formation of a symmetric chelating carboxylate. In the multilayer, which desorbs at 240 K, hydrogen-bonded NBDA dimers are formed. Upon PVD of NBDA at 300 K, only a surface anchored carboxylate is stable. The anchored NBDA film shows a characteristic restructuring behavior as a function of coverage. At low coverage the NBDA, adopts a flat-lying structure in which the norbornadiene unit interacts with the Co3O4 surface. With increasing coverage, the norbornadiene units detach from the oxide and the NBDA adopts an upright-standing orientation. Similar to BA, the anchored film is stable up to 400 K and decomposes in the temperature region between 400 and 550 K, leaving behind hydrocarbon residues on the oxide surface.


FAU-Autoren / FAU-Herausgeber

Döpper, Tibor
Lehrstuhl für Theoretische Chemie
Görling, Andreas Prof. Dr.
Lehrstuhl für Theoretische Chemie
Hirsch, Andreas Prof. Dr.
Lehrstuhl für Organische Chemie II
Libuda, Jörg Prof. Dr.
Professur für Physikalische Chemie
Mohr, Susanne
Lehrstuhl für Physikalische Chemie II
Schwarz, Matthias
Lehrstuhl für Physikalische Chemie II
Weiß, Cornelius
Lehrstuhl für Organische Chemie II
Xu, Tao
Lehrstuhl für Physikalische Chemie II


Zusätzliche Organisationseinheit(en)
Exzellenz-Cluster Engineering of Advanced Materials


Zitierweisen

APA:
Schwarz, M., Mohr, S., Xu, T., Döpper, T., Weiß, C., Civale, K.,... Libuda, J. (2017). Anchoring of a Carboxyl-Functionlized Norbornadiene Derivative to an Atomically-Defined Cobalt Oxide Surface. Journal of Chemical Physics, 121, 11508-11518. https://dx.doi.org/10.1021/acs.jpcc.7b02620

MLA:
Schwarz, Matthias, et al. "Anchoring of a Carboxyl-Functionlized Norbornadiene Derivative to an Atomically-Defined Cobalt Oxide Surface." Journal of Chemical Physics 121 (2017): 11508-11518.

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Zuletzt aktualisiert 2019-14-03 um 12:45

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