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Steven De Feyter

Publications and source records attributed to Steven De Feyter.

At least 19 recordsLinked to original sources
PubMed2006

Two-dimensional porous molecular networks of dehydrobenzo[12]annulene derivatives via alkyl chain interdigitation.

The self-assembly of a series of hexadehydrotribenzo[12]annulene (DBA) derivatives has been scrutinized by scanning tunneling microscopy (STM) at the liquid-solid interface. First, the influence of core symmetry on the network structure was investigated by comparing the two-dimensional (2D) ordering of rhombic bisDBA 1a and triangular DBA 2a (Figure 1). BisDBA 1a forms a Kagomé network upon physisorption from 1,2,4-trichlorobenzene (TCB) onto highly oriented pyrolytic graphite (HOPG). Under similar experimental conditions, DBA 2a shows the formation of a honeycomb network. The core symmetry and location of alkyl substituents determine the network structure. The most remarkable feature of the DBA networks is the interdigitation of the nonpolar alkyl chains: they connect the pi-conjugated cores and direct their orientation. As a result, 2D open networks with voids are formed. Second, the effect of alkyl chain length on the structure of DBA patterns was investigated. Upon increasing the length of the alkyl chains (DBAs 3c-e) a transition from honeycomb networks to linear networks was observed in TCB, an observation attributed to stronger molecule-substrate interactions. Third, the effect of solvent on the structure of the nonpolar DBA networks was investigated in four different solvents: TCB as a polar aromatic solvent, 1-phenyloctane as a solvent having both aromatic and aliphatic moieties, n-tetradecane as an aliphatic solvent, and octanoic acid as a polar alkylated solvent. The solvent dramatically changes the structure of the DBA networks. The solvent effects are discussed in terms of factors that influence the mobility of molecules at the liquid-solid interface such as solvation.

Alkylation↗
PubMed2006

Chiral alignment of OPV chromophores: exploitation of the ureidophthalimide-based foldamer.

The ability of foldamers to adopt a secondary structure in solution has been exploited to organize peripheral functionality. Our previously reported poly(ureidophthalimide) foldamer proved to be an excellent scaffold for the chiral organization of peripherally positioned oligo(p-phenylenevinylene) (OPV) chromophores. Facile high-yielding synthesis gave access to the required OPV-decorated building blocks. A condensation polymerization provided polymers of sufficient length to allow construction of a helical architecture comprising several turns. Short and long chains were separated by chromatography. Circular dichroism studies in THF of the longer chains indicate the presence of helically arranged OPVs. However, such an effect is not observed in CHCl3. Remarkable are the measurements of the OPV foldamers in heptane. A bisignate Cotton effect is observed in heptane of a sample with a THF history. No Cotton effect is observed in heptane of a sample with a CHCl3 history. In this example of supramolecular synthesis, the solvent dictates the expression of supramolecular chirality in a secondary structure. The short-chain oligomeric fractions that are unable to create a full turn revealed on scanning tunneling microscopy analysis the presence of circular architectures at the graphite/1-phenyloctane interface. This is in full agreement with the proposed conformation of the decorated foldamers.

Journal Article↗
PubMed2006

Hydrogen-bonded oligo(p-phenylenevinylene) functionalized with perylene bisimide: self-assembly and energy transfer.

We describe the synthesis, supramolecular ordering on surfaces and in solution, and photophysical characterization of OPV4UT-PERY, an oligo(p-phenylenevinylene) (OPV) with a covalently attached perylene bisimide moiety. In chloroform, the molecule forms dimers through quadruple hydrogen bonding of the ureido-s-triazine array. This is supported by scanning tunneling microscopy (STM) studies, which reveal dimer formation at the liquid (1,2,4-trichlorobenzene)/solid (graphite) interface. Moreover, contrast reversal in bias-dependent STM imaging provides information on the ordering and different electronic properties of the oligo(p-phenylenevinylene) and perylene bisimide moieties. In dodecane, the molecule self-assembles into H-type aggregates that are still soluble as a result of the hydrophobic shell formed by the dodecyloxy wedges. The donor-acceptor molecule is characterized by efficient energy transfer from the photoexcited OPV to the perylene bisimide. Mixed assemblies with analogous OPVs lacking the perylene bisimide unit have been prepared in dodecane solution and energy transfer to the incorporated perylene bisimides has been studied by fluorescence spectroscopy.

Journal Article↗
PubMed2006

Noncovalent control for bottom-up assembly of functional supramolecular wires.

Noncovalent bonds have been used to assemble stacks of pi-electron-rich moieties at a surface, generating a pathway for charge transport. The system is comprised of a tetrathiafulvalene (TTF) derivative incorporating two amide groups which fasten the relative orientations of the electroactive moieties in the supramolecular polymer that is formed at the surface of graphite in octanoic acid. Scanning tunneling microscopy (STM) combined with molecular mechanics calculations has been used to prove the structure of the wires, and theory, corroborated with STS experiments, predicts that they are promising superstructures for charge transport.

Journal Article↗
PubMed2006

Molecule-molecule versus molecule-substrate interactions in the assembly of oligothiophenes at surfaces.

In this paper we present a joint experimental and theoretical approach for the study of the assembly of end-substituted oligothiophenes at surfaces with different polarities (i.e., mica vs graphite). Scanning probe microscopy studies of (sub)monolayer deposits show various types of structures (one-dimensional fibrils, two-dimensional regular layers, and monolayers), depending on the nature of the end groups and the substrate. Using molecular modeling with an atomistic approach, we focus on the interplay between the molecule-molecule (and segment-segment) interactions and the molecule-substrate interactions and their influence on the observed morphologies and the stacking geometry. Such information is relevant for controlling the structural order in thin layers of thiophene oligomers for use in field-effect transistor applications, for example, by modifying the nature of dielectric material over which those compounds are deposited.

Journal Article↗
PubMed2006

Molecular geometry directed Kagomé and honeycomb networks: toward two-dimensional crystal engineering.

We present here the formation of a molecular Kagomé network within a two-dimensional (2D) crystal on a surface. This system provides a clear example of how, by design, molecular geometry can be expressed at the level of the 2D crystal lattice, leading to the formation of open networks. Key elements to control molecular network formation are core symmetry, location and orientation of interacting and connecting substituents, as well as symmetry matching between the networks and the surface.

Journal Article↗
PubMed2006

Two-dimensional self-assembly and phase behavior of an alkoxylated sandwich-type bisphthalocyanine and its phthalocyanine analogues at the liquid-solid interface.

Lanthanide bisphthalocyanine complexes are interesting objects for the construction of two-dimensional (2D) ordered arrays with prospective applications in molecular electronics due to their unique semiconductor and electrochromic properties as well as their double-decker architecture. The 2D self-assembly of dodecyloxy-substituted (bisphthalocyaninato)erbium(III) has been studied at the solid (highly oriented pyrolytic graphite)-liquid interface by scanning tunneling microscopy. The results show that the bisphthalocyanine molecules form an ordered quadratic 2D lattice (a = b = 3.0 +/- 0.1 nm, gamma = 90 +/- 3 degrees), which is nearly identical to that formed by its (phthalocyaninato)cobalt(II) analogue bearing alkoxy chains of the same length. This clearly shows that sandwich molecules adsorb to the graphite surface by one of the phthalocyanine disks and its eight alkoxy groups. Despite the very similar mode of interaction with the surface, mixtures of alkoxylated (bisphthalocyaninato)erbium(III) with its (phthalocyaninato)cobalt(II) analogue show partial phase separation on the nanoscale: areas are enriched in one of the compounds. A much clearer phase separation between (bisphthalocyaninato)erbium(III) and (phthalocyaninato)cobalt(II) molecules was achieved by mixing molecules containing alkoxy groups of different length. The results provide insight for the development of well-ordered nanostructures of bisphthalocyanines in the presence of phthalocyanines, which could be of importance for future nanometer-scale functional materials.

Journal Article↗
PubMed2006

[Ru(TAP)3]2+-photosensitized DNA cleavage studied by atomic force microscopy and gel electrophoresis: a comparative study.

Topological modifications of plasmid DNA adsorbed on a variety of surfaces were investigated by using atomic force microscopy (AFM). On mica modified with 3-aminopropyltriethoxysilane (APS) or poly-L-lysine, the interaction between the plasmid DNA and the surface "freezes" the plasmid DNA conformation deposited from solution, and the AFM images resemble the projection of the three-dimensional conformation of the plasmid DNA in solution. Modified mica with low concentrations of Mg(2+) leads to a decrease in the interaction strength between plasmid DNA and the substrate, and the AFM images reflect the relaxed or equilibrium conformation of the adsorbed plasmid DNA. Under these optimized deposition conditions, topological modifications of plasmid DNA were produced under irradiation in the presence of [Ru(TAP)(3)](2+) (TAP = 1,4,5,8-tetraazaphenanthrene), which is a non-intercalating complex, and were followed as a function of illumination time. The observed structural changes correlate well with the conversion of the supercoiled covalently closed circular form (ccc form) into the open circular form (oc form), induced by a single-strand photocleavage. The AFM results obtained after fine-tuning of the plasmid DNA-substrate interaction compare well with those observed from gel electrophoresis, indicating that under the appropriate deposition conditions, AFM is a reliable technique to investigate irradiation-induced topological changes in plasmid DNA.

DNA, Superhelical↗
PubMed2006

Solvent controlled self-assembly at the liquid-solid interface revealed by STM.

The effect of solvent on the two-dimensional (2D) supramolecular ordering of monodendron 1 at the liquid-solid interface has been systematically investigated by means of scanning tunneling microscopy (STM). Solvents range from those with hydrophilic solvating properties, such as alkylated alcohols and acids, to hydrophobic solvents such as alkylated aromatics and alkanes. Dramatic differences in the 2D ordering are observed depending on the nature of the solvent. Of particular interest is the fact that in hydrophobic solvating solvents, such as aliphatic and aromatic hydrocarbons, solvent molecules are coadsorbed in the 2D molecular network while this is not the case for alkylated alcohols or acids. Furthermore, in the case of the coadsorbing solvents, a striking influence of the alkyl chain length has been observed on the 2D pattern formed. The solvent and alkyl chain length dependences are discussed in terms of molecule-molecule interactions (homo and hetero) and molecule-substrate interactions.

Journal Article↗
PubMed2005

Scanning tunneling microscopy and spectroscopy of donor-acceptor-donor triads at the liquid/solid interface.

By means of scanning tunneling microscopy (STM), the self-assembly of two organic donor-acceptor-donor triads (donor=oligo(p-phenylene vinylene) (OPV); acceptor=perylene diimide (PDI)) and their mixtures has been investigated at the liquid/solid interface. Both triads differ in the nature of the substituents and, therefore, in the redox properties of the central perylene diimide unit (H or Cl). Thanks to the submolecular resolution, the distinct electronic properties of the units, within a triad and between the two triads, are reflected by the relative STM contrast in the bias-dependent imaging experiments. Moreover, scanning tunneling spectroscopy reveals an inverse rectifying behavior of the OPV and H-substituted PDI units, which is discussed in the framework of quasi-resonant tunneling. A striking difference is observed for the Cl-substituted triad.

Journal Article↗
PubMed2005

Self-assembly at the liquid/solid interface: STM reveals.

The liquid/solid interface provides an ideal environment to investigate self-assembly phenomena, and scanning tunneling microscopy (STM) is the preferred methodology to probe the structure and the properties of physisorbed monolayers on the nanoscale. Physisorbed monolayers are of relevance in areas such as lubrication, patterning of surfaces on the nanoscale, and thin film based organic electronic devices, to name a few. It's important to gain insight in the factors which control the ordering of molecules at the liquid/solid interface in view of the targeted properties. STM provides detailed insight into the importance of molecule-substrate (epitaxy) and molecule-molecule interactions (hydrogen bonding, metal complexation, and fluorophobic/fluorophilic interactions) to direct the ordering of both achiral and chiral molecules on the atomically flat surface. By controlling the location and orientation of functional groups, chemical reactions can be induced at the liquid/solid interface, via external stimuli, such as light, or by controlled manipulation with the STM tip. The electronic properties of the self-assembled physisorbed molecules can be probed by taking advantage of the operation principle of STM, revealing spatially resolved intramolecular differences within these physisorbed molecules.

Journal Article↗
PubMed2005

2D self-assembly of oligo(p-phenylene vinylene) derivatives: from dimers to chiral rosettes.

Enantiomerically pure oligo(p-phenylene vinylene) diaminotriazine derivatives and a short structurally related achiral diaminotriazine derivative, all having a rigid backbone in common, are studied to self-assemble at the solution-graphite interface by scanning tunneling microscopy. As a function of the length of the backbone, different two-dimensional motifs are formed (dimers and rosettes) that are rationalized in terms of the balance between different intermolecular interactions, in this case, intermolecular hydrogen bonding and the packing requirements of the alkyl chains on a graphite surface. In addition, the effect of molecular chirality on monolayer chirality is investigated, revealing molecular size-dependent expressions of the monolayer chirality.

Macromolecular Substances↗
PubMed2005

Two-dimensional self-assembly into multicomponent hydrogen-bonded nanostructures.

By means of scanning tunneling microscopy, we have explored the two-dimensional self-assembly of functional bicomponent hydrogen-bonding dye systems, leading to well-defined patterns, different from those of the individual components, and providing design rules to immobilize multicomponent systems at the liquid-solid interface.

Journal Article↗
PubMed2004

Hydrogen bond directed self-assembly of core-substituted naphthalene bisimides with melamines in solution and at the graphite interface.

A series of red and blue highly fluorescent core-substituted naphthalene bisimide dyes has been synthesized and they have been investigated as supramolecular building blocks. NMR and UV-Vis titration experiments of these dyes with complementary melamines revealed the formation of triple hydrogen bonds (DAD-ADA arrays) in solution. At stoichiometric ratios, ditopic melamine receptors could dissolve otherwise insoluble bisimides by means of hydrogen bonding, even in aliphatic solvents. At the solution/graphite interface, one-dimensional chains of hydrogen bonded naphthalene bisimides and two-dimensional adlayers of ditopic melamines are formed for the pure compounds but little evidence for heterocomplexes between the two complementary building blocks could be obtained.

Journal Article↗
PubMed2004

Photophysical study of photoinduced electron transfer in a bis-thiophene substituted peryleneimide.

Based on femtosecond time-resolved spectroscopy and single photon timing experiments, intramolecular photoinduced charge transfer has been investigated in two systems containing a peryleneimide chromophore (P) and thiophene (T) groups. The first compound bearing a single thiophene ring (PT1) is used as model and shows a behavior similar to P, studied previously, while in the compound with two thiophene rings attached (PT2) electron transfer from the thiophene donor to the peryleneimide acceptor is observed in benzonitrile. Femtosecond fluorescence upconversion and femtosecond transient absorption experiments in benzonitrile indicate that this ion-pair state formation occurs in 19 ps. This ion-pair state then decays with two time constants of 1400 and 820 ps, probably corresponding to different conformations of the thiophene rings.

Electrochemistry↗