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Orientation Bias of Self-Assembled Alkanes and Their derivatives Under Dynamic Lateral Nanoconfinement Conditions

CCS Chemistry 2024年第4期6卷 1024-1033页

作者： Conditions Lihua Yu Yuanzhi Xia Tianze Hu Brent Daelemans steven de feyter department of Chemistry Division of Molecular Imaging and PhotonicsKU LeuvenB-3001 Leuven

Self-assembled molecular networks(SAMNs)formed on crystalline solid substrates result from the spontaneous arrangement of individual molecules into structured *** interaction between molecules and the substrate leads to a nonrandom orientation of SAMNs with respect to the substrate’s *** the case of graphite,the sixfold rotational symmetry of the substrate results in an equivalent rotational degeneracy in the orientation of *** this study,we explored how nanoconfinement,that is,the restriction of SAMN formation to nanometersized areas,known as nanocorrals,could impact and potentially alleviate the orientational degeneracy of SAMNs,with emphasis on the influence of molecule symmetry,size,and intermolecular *** this end,we investigated the orientation distribution of n-alkanes and functionalized alkanes within nanocorrals,which were fabricated using scanning tunneling microscopy lithography(nanoshaving).We observed lifting of orientational degeneracy for long alkanes,contrary to shorter alkanes,which did not exhibit this orientation ***,functionalized alkanes with hydrogen bonding groups demonstrated preferential alignment regardless of length,highlighting the significance of stabilizing intermolecular interactions in the alignment *** study discussed the underlying principles of the molecular packing process and shed light on the complexity of molecular self-assembly in nanoconfined spaces.

关键词： self-assembly confinement condition nanocorral orientation bias scanning tunneling microscopy

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Synthesis, Aggregation and Adsorption of Poiycyclic Aromatic Hydrocarbon （PAH） Containing Shape-Persistent Macrocycles with Extrannular TriisoproplysiiyI Substituents

Synthesis, Aggregation and Adsorption of Poiycyclic Aromatic...

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中国化学会第四届有机化学学术会议

作者： HOEGER,Sigurd de feyter,steven Universitat Karlsruhe Institut für Technische Chemie und Polymerchemie Engesserstr. 18 76131 Karlsruhe Germany Katholieke Universiteit Leuven Department of ChemistryCelestijnenlaan 200 F3001 LeuvenBelgium

＜正＞Shape-persistent macrocycles containing a polycyclic aromatic backbone and extrannular triisoproplysilyl substituents 2 are synthesized by the intermolecular oxidative Glaser-coupling of the corresponding bisacetylenes （half ring, acetylene oligomer） 1 （Figure 1）. The half ring in both their protected and unproteted forms shows strong aggregation in the solution which has been investigated by 1H NMR spectroscopy. Due to the restricted solubility we could not determine any aggregation in solution.

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Processable Rylene Diimides up to 4 nm in length: Synthesis and STM Visualization

Processable Rylene Diimides up to 4 nm in length: Synthesis ...

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2015年第十四届全国应用化学年会

作者： YUAN Zhongyi LEE Shern-Long CHEN,Long LI Chen MALI Kunal S. MUELLEN Klaus de feyter steven Max Planck Institute for Polymer Research department of Chemistry KU Leuven-University

Our group has reported the syntheses of terrylene, quaterrylene,pentarylene, and hexarylene diimides over the past two decades. To achieve good solubility, four bulk alkylphenoxy groups were introduced at the bay positions. However, this method has two limitations: 1) the steric repulsion between the substituents at the bay positions causes a serious twist of the conjugated core and thus obstructs the intermolecular interactions;2) electron-rich phenoxy groups greatly raise the LUMO energy level, and hamper the role of RDIs as n-type semiconductors. To overcome these drawbacks, we designed and synthesized soluble hexarylene diimides(HDI) and octarylene diimides(ODI) with planar conjugated cores which are as long as 2.87 and 3.74 nm respectively. HDI(λ = 908 nm, ε = 256000 M)cm) shows intense NIR absorption in the range of 700-1000 nm. The absorption of ODI(λ = 1007 nm, ε = 79800 Mcm) is the range of 400-1400 nm. Electrochemical properties of HDI and ODI were investigated by cyclic voltammetry, and the LUMO energy is-3.95 eV and-3.94 eV respectively, which indicates strong electron accepting ability of the two compounds. Scanning tunneling microscopy(STM) reveals that HDI, after deposition from solution, forms a unique herringbone bilayer or stable multilayers depending on the concentration at the liquid–solid interface. We also found a simple and efficient method to fabricate well-aligned thin films of HDI over a few millimeter squares. The strategy involves use of capillary force in a two-step flow method to induce large area alignment of multilayers of molecules at the organic liquid-solid interface.

关键词： Rylene Diimides Organic semiconductors Scanning tunneling microscopy

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Self-templated covalent functionalization of graphitic surfaces with a quasi-periodic pattern

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Aggregate 2022年第4期3卷 121-130页

作者： Yuanzhi Xia Johannes Seibel steven de feyter Division of Molecular Imaging and Photonics Department of ChemistryKU LeuvenLeuvenBelgium

Patterned covalent functionalization of graphitic surfaces(GSs)is of interest in the development of devices and nanocomposite *** contrast to the strategies using external templates or control for realizing patterned covalent functionalization of GSs,here,we present a self-templated strategy by exploiting the synergistic effects of chemical and physical functionalization of ***,a diazonium salt is reduced by potassium iodide(KI)in dimethyl sulfoxide while the solution is in contact with a GS,resulting in its spatially heterogeneous,that is,chemical and physical,*** heterogeneous functionalization leads to a quasiperiodic pattern of striped corrals with three equivalent orientations in the covalent *** formation of the striped corrals is ascribed to physisorbed domains formed by self-assembled N_(2),which is produced in situ during the reduction of the diazonium salt,preventing the covalent functionalization.

关键词： diazonium chemistry graphitic surfaces patterned covalent functionalization quasi-periodic patterning self-templated strategy

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Phase behavior at the solid/liquid interface:scanning tunneling microscopy and Monte Carlo simulations

Phase behavior at the solid/liquid interface:scanning tunnel...

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中国化学会第六届全国结构化学学术会议

作者： steven de feyter Division of Molecular and Nanomaterials Department of ChemistryKatholieke Universiteit Leuven（K.U.Leuven）Celestijnenlaan 200F3001 Leuven（Belgium）

＜正＞The self-assembly of nanometer-sized building blocks on surfaces and at interfaces is a powerful way to fabricate complex molecular nanostructures following the bottom-up *** recognition at interfaces involves many simultaneous interactions based on molecular shape,size,functional groups,etc. The weak thus reversible supramolecular interactions sustaining these networks enable the system to

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