Surface state engineering of molecule–molecule interactions

Rojas, Geoffrey; Simpson, Scott; Chen, Xumin; Kunkel, Donna A.; Nitz, Justin; Xiao, Jie; Dowben, Peter A.; Zurek, Eva; Enders, Axel

doi:10.1039/c2cp40254h

Cited by 61 publications

(97 citation statements)

References 47 publications

(56 reference statements)

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“…[45][46][47]50 Such a redistribution of electronic charge around adsorbates on coinage metal surfaces has been shown experimentally in several studies, 19,28,48 and is actually visible in the STM images in Figures 4(c) and 4(d). This mechanism is often found to be more pronounced on Cu(111) than on Ag(111) or Au(111).…”

Section: Long-range Surface-mediated Interactionsmentioning

confidence: 78%

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Self-assembly of strongly dipolar molecules on metal surfaces

Kunkel

Hooper

Simpson

et al. 2015

The Journal of Chemical Physics

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The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C 6 H 2 (· · · NHR) 2 (· · · O) 2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings. C 2015 AIP Publishing LLC. [http://dx

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Section: Long-range Surface-mediated Interactionsmentioning

confidence: 78%

“…27 Electronic surface states, especially the Shockley state of the Cu(111) surface, have been shown to critically influence the molecular self-assembly. 28 Their role in this present system will be discussed in more detail in Sec. V.…”

Section: B Chains and Gratings Of Parent Zwitterionsmentioning

confidence: 99%

Self-assembly of strongly dipolar molecules on metal surfaces

Kunkel

Hooper

Simpson

et al. 2015

The Journal of Chemical Physics

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“…By comparing the spectra to previous studies it was found that: (i) the electronic transport gap is 1.85 eV, smaller than that for TPP [29]; (ii) several spectroscopic features not present in the TPP spectrum are detected in the occupied states whereas the unoccupied states are almost unchanged. Density functional theory (DFT) calculations using the B3LYP exchange correlation functional were performed on both TAPP and TPP.…”

Section: Introductionmentioning

confidence: 94%

Electronic structure of tetra(4-aminophenyl)porphyrin studied by photoemission, UV–Vis spectroscopy and density functional theory

Giovanelli

Lee

Lacaze‐Dufaure

et al. 2017

Journal of Electron Spectroscopy and Related Phenomena

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OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao. b s t r a c tThe valence and conduction bands of a thin film of tetra(4-aminophenyl)porphyrin (TAPP) are investigated by direct and inverse photoemission as well as by comparison to density functional theory (DFT) calculations. By projecting the electronic eigenfunctions onto the molecular framework it was possible to interpret the origin of each spectroscopic feature. Although the majority of the photoemission spectrum is attributed to the unsubstituted tetraphenylporphyrin (TPP) parent molecule, several features are clearly due to the amino substitution. Substitution also has important consequences for the energy positions of the frontier orbitals and therefore on the low-energy electronic excitations. The measured electronic transport energy gap (E g = 1.85 eV) between the highest occupied molecular orbital (HOMO) and lowest unoccupied (LUMO) in TAPP is found to be significantly reduced with respect to TPP. Moreover, an increased energy separation between the two highest occupied states (HOMO and HOMO−1) is found both experimentally and by DFT calculations. Such evidence is attributed to an increased HOMO orbital destabilization due to an enhanced electron-donor character of the phenyl substituents upon amino functionalization. Finally, the above findings together with further time-dependent DFT calculations are used to interpret the effect of the amino groups on the UV-Vis absorption spectrum, namely an overall red-shift of the spectrum and remarkable intensity changes within the Q band.

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“…[1][2][3] The construction of desired molecular network architectures on suitable substrates is achieved by the self-assembly of molecular building blocks, which is mainly controlled by a complex interplay between non-covalent bonds such as hydrogen bonds, van der Waals and electrostatic interactions, and the epitaxy on the substrate. [4][5][6][7][8][9][10][11][12][13][14] From the knowledge gained about the delicate balance between intermolecular and molecule-substrate interactions, the functional nano-networks can then be tuned by adjusting functional groups of the molecule to gain the desired architectures [15][16][17] and the interface electronic structure for the specific application. Therefore, it is important that the molecular orientation, configuration and conformation, and the interactions between the adsorbed molecules and the substrate as well as between molecules can be identified and understood, e.g.…”

Section: Introductionmentioning

confidence: 99%

Interplay of hydrogen bonding and molecule–substrate interaction in self-assembled adlayer structures of a hydroxyphenyl-substituted porphyrin

et al. 2014

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The formation of hydrogen-bonded organic nano-structures and the role of the substrate lattice thereby were investigated by scanning tunneling microscopy. The self-organization of 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (H 2 THPP) molecules leads to two molecular arrangements on Au(111). One of these is characterized by pair-wise hydrogen bonding between hydroxyl groups and a low packing density which enables a rotation of individual molecules in the structure. A different interaction with stronger chain-like hydrogen bonding and additional interactions of phenyl groups was observed for the second structure. The influence of the substrate on the epitaxial behavior is demonstrated by the adsorption of H 2 THPP on the highly anisotropic Ag(110) substrate. There, several balances between the occupation of favorable adsorption positions and the number of hydrogen bonds per molecule were found. The molecules form molecular chains on Ag(110) and also assemble into two-dimensional periodic arrangements of differently sized close-packed blocks similar to the second type of supramolecular ordering found on Au(111). Dispersion corrected Density Functional Theory calculations were applied to understand the adsorption and complex epitaxy of these molecules. It is shown that the azimuthal orientation of the saddle-shape deformed molecule plays an important role not only for the intermolecular but also for the molecule-substrate interaction.

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Surface state engineering of molecule–molecule interactions

Cited by 61 publications

References 47 publications

Self-assembly of strongly dipolar molecules on metal surfaces

Self-assembly of strongly dipolar molecules on metal surfaces

Electronic structure of tetra(4-aminophenyl)porphyrin studied by photoemission, UV–Vis spectroscopy and density functional theory

Interplay of hydrogen bonding and molecule–substrate interaction in self-assembled adlayer structures of a hydroxyphenyl-substituted porphyrin

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