Self-Organization of Phenyleneethynylene into Wire-Like Molecular Materials on Surfaces

Yoosaf, K.; James, P. V.; Ramesh, A. R.; Suresh, C. H.; Thomas, K. George

doi:10.1021/jp075542i

Cited by 23 publications

(23 citation statements)

References 36 publications

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“…The rigid, planar, and highly conducting nature of these molecules makes them ideal for our study. − In STM images one can easily distinguish between the aromatic backbones of the host molecules and the aliphatic side chains. The former are imaged as bright rod-like features, corresponding to a high tunneling current, whereas the latter are imaged as dark regions, due to the large energy difference between the electronic states of the aliphatic chain and the Fermi level of the substrate …”

Section: Resultsmentioning

confidence: 99%

Descriptor-Based Rational Design of Two-Dimensional Self-Assembled Nanoarchitectures Stabilized by Hydrogen Bonds

et al. 2017

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The self-assembly of supramolecular architectures bound together by noncovalent interactions offers, at present, the most promising route to constructing devices at the nanoscale. However, the ability to pick molecular components that will result in a desired supramolecular structure and functionality remains a challenge. We suggest these goals can be met by using easily computed descriptors that correlate molecular form and formula with supramolecular architecture and energetics. Using a combination of theory and experiment, we show the feasibility of such an approach for a set of molecules comprised of three hosts (carboxylic acid derivatives of phenyleneethynylene) and five guests (naphthalene, phenanthrene, benzo-c-phenanthrene, benzo-ghi-perylene, and coronene), self-assembled on highly oriented pyrolitic graphite. Both scanning tunneling microscopy experiments and density functional theory calculations show that the host–guest combinations display rich structural diversity, assembling in hexagonal, linear, or random glass-like patterns. For certain host–guest combinations, the introduction of the guest triggers structural reorganization, including a disorder-to-order transition. By correlating with computed free energies, we formulate host and guest descriptors. These descriptors can be evaluated at essentially zero computational cost, as they depend only on the geometry and number of chemical motifs of specific types in the isolated molecules. However, they can successfully predict the structures and energetics of the host–guest assemblies, including systems not included in the original database used when determining the form of the descriptors. Structures of the same kind are found to cluster in the descriptor space. This suggests the way forward for the descriptor-based rational design of self-assembled nanostructured systems on surfaces.

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Section: Resultsmentioning

confidence: 99%

Descriptor-Based Rational Design of Two-Dimensional Self-Assembled Nanoarchitectures Stabilized by Hydrogen Bonds

et al. 2017

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“…For the monomer 4 a (Figure 1 a) and the acyclic dimer [ 5 a ] 2 (Figure 2 A (b)), O‐ and S‐shaped polymorphs are observed concurrently, while for the higher ( n >2) acyclic oligomers, solely S‐shaped geometries are adopted. The backbone distances in lamellar alignments of linear oligo‐PE(B)s are determined by the alkyl/alkoxy substituent chain lengths,4 and the corner units of 4 a and [ 5 a ] 2–6 perfectly match the expected distances for hexyloxy‐substituted oligo‐PEBs 4f. The intramolecular and intermolecular rod–rod distances (1.3 nm) cannot be distinguished at the experimental resolution.…”

Section: Methodsmentioning

confidence: 92%

Oligomers and Cyclooligomers of Rigid Phenylene–Ethynylene–Butadiynylenes: Synthesis and Self‐Assembled Monolayers

et al. 2010

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Ausgehend vom gleichen Bisacetylen entstanden abhängig von den Reaktionsbedingungen (Palladium‐ oder Kupferkatalyse) selektiv cyclische oder acyclische Oligomere mit n=2–6 (siehe Bild für den Fall n=3), die durch frei rotierende Eckstücke verknüpft sind. Aus STM‐Bildern der selbstorganisierten Monoschichten folgt der Unterschied im Adsorptionsverhalten der acyclischen und cyclischen Oligomere.

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“…1,2 Apart from the conventional interactions like hydrogen bonds, salt bridges and hydrophobic interactions, 3,4 other weak nonconventional interactions like CHÁÁÁp, OHÁÁÁp, NHÁÁÁp, and CationÁÁÁp interactions also play vital roles in protein stability. [5][6][7][8][9][10][11] The high incidence of such noncovalent interactions in large biological systems along with their key roles in chemical [12][13][14] and biological recognition processes 15,16 has led to an increasing number of theoretical 17,18 and experimental studies 19,20 devoted to the quantification and characterization of such interactions. Although useful to a certain extent, an accurate experimental description of noncovalent interactions is difficult 21 despite the enormous progress made in experimental techniques in the last decades.…”

Section: Introductionmentioning

confidence: 99%

Comparison of aromatic NH···π, OH···π, and CH···π interactions of alanine using MP2, CCSD, and DFT methods

et al. 2010

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A comparison of the performance of various density functional methods including long-range corrected and dispersion corrected methods [MPW1PW91, B3LYP, B3PW91, B97-D, B1B95, MPWB1K, M06-2X, SVWN5, ωB97XD, long-range correction (LC)-ωPBE, and CAM-B3LYP using 6-31+G(d,p) basis set] in the study of CH···π, OH···π, and NH···π interactions were done using weak complexes of neutral (A) and cationic (A(+)) forms of alanine with benzene by taking the Møller-Plesset (MP2)/6-31+G(d,p) results as the reference. Further, the binding energies of the neutral alanine-benzene complexes were assessed at coupled cluster (CCSD)/6-31G(d,p) method. Analysis of the molecular geometries and interaction energies at density functional theory (DFT), MP2, CCSD methods and CCSD(T) single point level reveal that MP2 is the best overall performer for noncovalent interactions giving accuracy close to CCSD method. MPWB1K fared better in interaction energy calculations than other DFT methods. In the case of M06-2X, SVWN5, and the dispersion corrected B97-D, the interaction energies are significantly overrated for neutral systems compared to other methods. However, for cationic systems, B97-D yields structures and interaction energies similar to MP2 and MPWB1K methods. Among the long-range corrected methods, LC-ωPBE and CAM-B3LYP methods show close agreement with MP2 values while ωB97XD energies are notably higher than MP2 values.

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Self-Organization of Phenyleneethynylene into Wire-Like Molecular Materials on Surfaces

Cited by 23 publications

References 36 publications

Descriptor-Based Rational Design of Two-Dimensional Self-Assembled Nanoarchitectures Stabilized by Hydrogen Bonds

Descriptor-Based Rational Design of Two-Dimensional Self-Assembled Nanoarchitectures Stabilized by Hydrogen Bonds

Oligomers and Cyclooligomers of Rigid Phenylene–Ethynylene–Butadiynylenes: Synthesis and Self‐Assembled Monolayers

Comparison of aromatic NH···π, OH···π, and CH···π interactions of alanine using MP2, CCSD, and DFT methods

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