In situ observation of a deprotonation driven phase transformation-4,4'-Biphenyldicarboxylic acide on Au(111)

Daniel Schwarz, Raoul van Gastel, Henricus J.W. Zandvliet, Bene Poelsema

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

We have studied the growth of 4,4′-biphenyldicarboxylic acid (BDA) domains on Au(111) by means of low-energy electron microscopy (LEEM) and selective area low-energy electron diffraction (μLEED). Between 300 and 400 K, BDA forms three different 2-D crystalline phases, which are attributed to different degrees of deprotonation. At room temperature, BDA condenses in needle-shaped domains (α-phase) with the carboxylic acid–dimer as the main molecular bonding motif. Upon annealing from room temperature to above about 330 K, the needle-shaped domains change irreversibly into more compact ones. This remarkable feature is attributed to a partial deprotonation of the carboxylic end groups and thus breaking of the dimers, which allows the molecules to establish hydrogen bonds with adjacent molecules by a slight rotation (β-phase). A third phase is formed upon direct adsorption of BDA at substrate temperatures above 330 K. In this γ-phase the deprotonated BDA molecules form an open 2-D metal–organic coordination network, probably by incorporation of thermally excited Au adatoms.
Original languageEnglish
Pages (from-to)1020-1029
Number of pages10
JournalJournal of physical chemistry C
Volume117
Issue number2
DOIs
Publication statusPublished - 2013

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Deprotonation
phase transformations
Phase transitions
acids
Acids
needles
Needles
Molecules
molecules
Adatoms
Low energy electron diffraction
room temperature
Dimers
Temperature
Electron microscopy
adatoms
electron microscopy
Hydrogen bonds
electron diffraction
dimers

Keywords

  • METIS-296592
  • IR-88890

Cite this

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title = "In situ observation of a deprotonation driven phase transformation-4,4'-Biphenyldicarboxylic acide on Au(111)",
abstract = "We have studied the growth of 4,4′-biphenyldicarboxylic acid (BDA) domains on Au(111) by means of low-energy electron microscopy (LEEM) and selective area low-energy electron diffraction (μLEED). Between 300 and 400 K, BDA forms three different 2-D crystalline phases, which are attributed to different degrees of deprotonation. At room temperature, BDA condenses in needle-shaped domains (α-phase) with the carboxylic acid–dimer as the main molecular bonding motif. Upon annealing from room temperature to above about 330 K, the needle-shaped domains change irreversibly into more compact ones. This remarkable feature is attributed to a partial deprotonation of the carboxylic end groups and thus breaking of the dimers, which allows the molecules to establish hydrogen bonds with adjacent molecules by a slight rotation (β-phase). A third phase is formed upon direct adsorption of BDA at substrate temperatures above 330 K. In this γ-phase the deprotonated BDA molecules form an open 2-D metal–organic coordination network, probably by incorporation of thermally excited Au adatoms.",
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author = "Daniel Schwarz and {van Gastel}, Raoul and Zandvliet, {Henricus J.W.} and Bene Poelsema",
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publisher = "American Chemical Society",
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In situ observation of a deprotonation driven phase transformation-4,4'-Biphenyldicarboxylic acide on Au(111). / Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Henricus J.W.; Poelsema, Bene.

In: Journal of physical chemistry C, Vol. 117, No. 2, 2013, p. 1020-1029.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - In situ observation of a deprotonation driven phase transformation-4,4'-Biphenyldicarboxylic acide on Au(111)

AU - Schwarz, Daniel

AU - van Gastel, Raoul

AU - Zandvliet, Henricus J.W.

AU - Poelsema, Bene

PY - 2013

Y1 - 2013

N2 - We have studied the growth of 4,4′-biphenyldicarboxylic acid (BDA) domains on Au(111) by means of low-energy electron microscopy (LEEM) and selective area low-energy electron diffraction (μLEED). Between 300 and 400 K, BDA forms three different 2-D crystalline phases, which are attributed to different degrees of deprotonation. At room temperature, BDA condenses in needle-shaped domains (α-phase) with the carboxylic acid–dimer as the main molecular bonding motif. Upon annealing from room temperature to above about 330 K, the needle-shaped domains change irreversibly into more compact ones. This remarkable feature is attributed to a partial deprotonation of the carboxylic end groups and thus breaking of the dimers, which allows the molecules to establish hydrogen bonds with adjacent molecules by a slight rotation (β-phase). A third phase is formed upon direct adsorption of BDA at substrate temperatures above 330 K. In this γ-phase the deprotonated BDA molecules form an open 2-D metal–organic coordination network, probably by incorporation of thermally excited Au adatoms.

AB - We have studied the growth of 4,4′-biphenyldicarboxylic acid (BDA) domains on Au(111) by means of low-energy electron microscopy (LEEM) and selective area low-energy electron diffraction (μLEED). Between 300 and 400 K, BDA forms three different 2-D crystalline phases, which are attributed to different degrees of deprotonation. At room temperature, BDA condenses in needle-shaped domains (α-phase) with the carboxylic acid–dimer as the main molecular bonding motif. Upon annealing from room temperature to above about 330 K, the needle-shaped domains change irreversibly into more compact ones. This remarkable feature is attributed to a partial deprotonation of the carboxylic end groups and thus breaking of the dimers, which allows the molecules to establish hydrogen bonds with adjacent molecules by a slight rotation (β-phase). A third phase is formed upon direct adsorption of BDA at substrate temperatures above 330 K. In this γ-phase the deprotonated BDA molecules form an open 2-D metal–organic coordination network, probably by incorporation of thermally excited Au adatoms.

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