Location-Selective Work Function Engineering by Self-Assembled Monolayers.

Control over specific interfaces in devices represents a key challenge for modern organic electronics and photovoltaics. Such control is frequently gained by the use of self-assembled monolayers (SAMs), which, by selection of a proper anchoring group, are generally discriminative with respect to different materials but are not selective between different areas of the same material. In particular, selective tailoring of the work function may be useful for different functional devices in a circuit. Here we demonstrate an approach for solving this problem, opening a way to function-selective electrostatic engineering of chemically identical areas, such as source and drain electrodes in a specific type of organic transistor and, more importantly, the electrodes in different types of organic devices, such as p- and n-channel transistors, located on the same circuitry board. The approach is based on the ultraviolet-light-promoted exchange reaction of SAMs on gold, a standard electrode material in organic electronics.

Selective Quantification of Bacteria in Mixtures by Using Glycosylated Polypyrrole/Hydrogel Nanolayers.

Here, we present a covalent nanolayer system that consists of a conductive and biorepulsive base layer topped by a layer carrying biorecognition sites. The layers are built up by electropolymerization of pyrrole derivatives that either carry polyglycerol brushes (for biorepulsivity) or glycoside moieties (as biorecognition sites). The polypyrrole backbone makes the resulting nanolayer systems conductive, opening the opportunity for constructing an electrochemistry-based sensor system. The basic concept of the sensor exploits the highly selective binding of carbohydrates by certain harmful bacteria, as bacterial adhesion and infection are a major threat to human health, and thus, a sensitive and selective detection of the respective bacteria by portable devices is highly desirable. To demonstrate the selectivity, two strains of Escherichia coli were selected. The first strain carries type 1 fimbriae, terminated by a lectin called FimH, which recognizes α-d-mannopyranosides, which is a carbohydrate that is commonly found on endothelial cells. The otherE. coli strain was of a strain that lacked this particular lectin. It could be demonstrated that hybrid nanolayer systems containing a very thin carbohydrate top layer (2 nm) show the highest discrimination (factor 80) between the different strains. Using electrochemical impedance spectroscopy, it was possible to quantify in vivo the type 1-fimbriated E. coli down to an optical density of OD600 = 0.0004 with a theoretical limit of 0.00005. Surprisingly, the selectivity and sensitivity of the sensing remained the same even in the presence of a large excess of nonbinding bacteria, making the system useful for the rapid and selective detection of pathogens in complex matrices. As the presented covalent nanolayer system is modularly built, it opens the opportunity to develop a broad band of mobile sensing devices suitable for various field applications such as bedside diagnostics or monitoring for bacterial contamination, e.g., in bioreactors.

Odd-even effects in aryl-substituted alkanethiolate SAMs: nonsymmetrical attachment of aryl unit and its impact on the SAM structure.

Aryl-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) exhibit typically so-called odd-even effects, viz. systematic variations in the film structure, packing density, and molecular inclination depending on the parity of the number of the methylene units in the alkyl linker, n. As an exception to this rule, ATs carrying an anthracen-2-yl group (Ant-n) as tail group were reported to have different behavior due the non-symmetric attachment of the anthracene unit to the AT linker, providing additional degree of freedom for the molecular organization and allowing for partial compensation of the odd-even effects. In this context, the structure of SAMs formed by adsorption of anthracene-substituted ATs (Ant-n; n = 1-6) at room temperature on Au(111) substrate was investigated by high-resolution scanning tunnelling microscopy (STM). Most of these SAMs exhibit a coexistence of two different ordered phases, some of which are common for either n = odd or n = even while other vary over the series, showing a broad variety of different structures. The average packing density of the Ant-n SAMs, derived from the analysis of the STM data, varies by 7.5-10% depending on the parity of n, being, as expected, higher for n = odd. The respective extent of the odd-even effects is noticeably lower than that usually observed for other aryl-substituted monolayers (∼25%), which goes in line with the previous findings and emphasizes the impact of the non-symmetric attachment of the aromatic unit.

Effect of the crosslinking agent on the biorepulsive and mechanical properties of polyglycerol membranes.

Polyglycerol (PG) based surfaces materials and surfaces are well-established bio-compatible materials. Crosslinking of the dendrimeric molecules via their OH groups improves their mechanical stability up to the point that free-standing materials can be attained. Here, we investigate the effect of different crosslinkers on PG films regarding their biorepulsivity and mechanical properties. For this purpose, PG films with different thicknesses (15, 50 and 100 nm) were prepared by polymerizing glycidol in a ring-opening polymerization onto hydroxyl-terminated Si substrates. These films were then crosslinked using ethylene glycol diglycidyl ether (EGDGE), divinyl sulfone (DVS), glutaraldehyde (GA), 1,11-di(mesyloxy)-3,6,9-trioxaundecane (TEG-Ms2) or 1,11-dibromo-3,6,9-trioxaundecane (TEG-Br2), respectively. While DVS, TEG-Ms2, and TEG-Br2 resulted in slightly thinned films, presumably due to loss of unbound material, increase of film thickness was observed with GA and, in particular, EDGDE, what can be explained by the different crosslinking mechanisms. The biorepulsive properties of the crosslinked PG films were characterized by water contact angle (WCA) goniometry and various adsorption assays involving proteins (serum albumine, fibrinogen, γ-globulin) and bacteria (E. coli), showing that some crosslinkers (EGDGE, DVS) improved the biorepulsive properties, while others deteriorated them (TEG-Ms2, TEG-Br2, GA). As the crosslinking stabilized the films, it was possible to use a lift-off procedure to obtain free-standing membranes if the thickness of the films was 50 nm or larger. Their mechanical properties were examined with a bulge test showing high elasticities, with the Young's moduli increasing in the order GA ≈ EDGDE < TEG-Br2 ≈ TEG-Ms2 < DVS.

Nanomechanical Stability of Laterally Heterogeneous Films of Corrosion Inhibitor Molecules Obtained by Microcontact Printing on Au Model Substrates.

Self-assembled monolayers of corrosion inhibitors of the mercaptobenzimidazole family, SH-BimH, SH-BimH-5NH2, and SH-BimH-5OMe, were formed on template-stripped ultraflat Au surfaces using microcontact printing, and subsequently analyzed using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and AFM-force spectroscopy (AFM-FS) using a quantitative imaging (QI) mode. Printing of all used inhibitor molecules resulted in clear patterns and in slightly more compact films compared to immersion. The stability of the monolayers is further probed by AFM-FS. Adhesion values of laterally heterogeneous inhibitor-modified surfaces compared to bare Au surfaces, nonpatterned areas, and fully covered surfaces are analyzed and discussed. Microcontact printing confers a superior nanomechanical stability to imidazole-modified films of the printed surface patches as compared to homogeneously covered surfaces by immersion into the inhibitor solution.

Effect of substitution on the charge transport properties of oligophenylenethiolate self-assembled monolayers.

Electrostatic effects in charge transport across the molecular framework, including those imposed by halogen atoms, have recently attracted noticeable attention of the molecular-electronics community. In this context, in the present work, we studied the effect of tail group (R) substitution on the charge transport properties of oligophenylenethiolate self-assembled monolayers (SAMs) on Au(111), with R = H, F, CH3, and CF3. The length of the molecular backbone was varied from one to three rings and the quality, basic parameters, and electrostatic properties of the SAMs were monitored. For a given length of the molecular backbone, the current density showed a strong dependence on R, being the highest for R = CH3, and then successively lower for R = H, R = CF3, and R = F. This tendency correlated neither with the molecular length of the precursors nor with the work function of the SAMs and was, therefore, exclusively ascribed to the identity of the tail group. In contrast to the current density, the tunneling decay coefficient, describing its dependence on the molecular length, was found to be independent of the identity of the tail group. The reasons behind the observed behavior are discussed and rationalized within the available experimental data and reasonable assumptions.

Dialytic Synthesis of Two-Dimensional Cu-Based Metal-Organic Frameworks for Gas Separation: Designable MOF-Polymer Interface.

We demonstrate a dialytic strategy for the synthesis of congeneric two-dimensional metal-organic framework (2D MOF) nanosheets with a dialysis membrane using 1,4-benzenedicarboxylic acid (BDC), 1,4-naphthalenedicarboxylic acid (NDC), and 9,10-anthracenedicarboxylic acid (ADC) as organic linkers and copper(II) as a metal precursor, respectively. Polyimide (PI) membranes containing these empty 2D MOF nanosheets exhibit distinct molecular sieve effects. Molecular dynamic simulation results reveal that the structures of MOF-polymer interfaces are designable by modifying the MOF interlayer distance and aperture size, which has significant influences on gas permeability and selectivity. As a result, Cu-NDC/PI with the moderate composite interface structure shows superior performance toward H2/CH4 and CO2/CH4 separations with a selectivity of 199 and 63 over Cu-BDC (121 and 53) and Cu-ADC (135 and 54), respectively.

Concept of Embedded Dipoles as a Versatile Tool for Surface Engineering.

Controlling the physical and chemical properties of surfaces and interfaces is of fundamental relevance in various areas of physical chemistry and a key issue of modern nanotechnology. A highly promising strategy for achieving that control is the use of self-assembled monolayers (SAMs), which are ordered arrays of rodlike molecules bound to the substrate by a suitable anchoring group and carrying a functional tail group at the other end of the molecular backbone. Besides various other applications, SAMs are frequently used in organic electronics for the electrostatic engineering of interfaces by controlling the interfacial level alignment. This is usually achieved by introducing a dipolar tail group at the SAM-semiconductor interface. Such an approach, however, also changes the chemical character of that interface, for example, affecting the growth of subsequent layers. A strategy for avoiding this complication is to embed polar groups into the backbones of the SAM-forming molecules. This allows disentangling electronic interface engineering and the nucleation of further layers, such that both can be optimized independently. This novel concept was successfully demonstrated for both aliphatic and aromatic SAMs on different application-relevant substrates, such as gold, silver, and indium tin oxide. Embedding, for example, ester and pyrimidine groups in different orientations into the backbones of the SAM-forming molecules results in significant work-function changes. These can then be fine-tuned over a wide energy range by growing mixed monolayers consisting of molecules with oppositely oriented polar groups. In such systems, the variation of the work function is accompanied by pronounced shifts of the peaks in X-ray photoelectron spectra, which demonstrates that electrostatically triggered core-level shifts can be as important as the well-established chemical shifts. This illustrates the potential of X-ray photoelectron spectroscopy (XPS) as a tool for probing the local electrostatic energy within monolayers and, in systems like the ones studied here, makes XPS a powerful tool for studying the composition and morphology of binary SAMs. All these experimental observations can be rationalized through simulations, which show that the assemblies of embedded dipolar groups introduce a potential discontinuity within the monolayer, shifting the energy levels above and below the dipoles relative to each other. In molecular and monolayer electronics, embedded-dipole SAMs can be used to control transition voltages and current rectification. In devices based on organic and 2D semiconductors, such as MoS2, they can reduce contact resistances by several orders of magnitude without adversely affecting film growth even on flexible substrates. By varying the orientation of the embedded dipolar moieties, it is also possible to build p- and n-type organic transistors using the same electrode materials (Au). The extensions of the embedded-dipole concept from hybrid interfaces to systems such as metal-organic frameworks is currently underway, which further underlines the high potential of this approach.

Substituted Dibenzodiazocines: Rapid Synthesis and Photochemical Properties.

11,12-Dihydrodibenzo[c,g]-1,2-diazocines have been established as a viable alternative to azobenzene for photoswitching, in particular, as they show an inverted switching behavior: the ground state is the Z isomer. In this paper, we present an improved method to obtain dibenzodiazocine and its derivatives from the respective 2-nitrotoluenes in two reaction steps, each proceeding in minutes. This fast access to a variety of derivatives permitted the study of substitution effects on the synthesis and on the photochemical properties. With biochemical applications in mind, methanol was chosen as a protic solvent system for the photochemical investigations. In contrast to the azobenzene system, none of the tested substitution patterns resulted in more efficient switching or in significantly prolonged half-lives, showing that the system is dominated by the ring strain.

Highly oriented and polyoxometalate-incorporating surface-attached metal-organic frameworks for efficient dye adsorption and water oxidation.

We present a facile protocol for the controlled growth of highly oriented and polyoxometalate-incorporating HKUST-1 SURMOFs. Combining the spin-coating technique with alcohol-vapour induced growth, film thickness, crystallite orientation and crystal size can be precisely tuned. The SURMOFs exhibit excellent abilities in selective adsorption of cationic dyes and water oxidation.

Electron Transfer Dynamics and Structural Effects in Benzonitrile Monolayers with Tuned Dipole Moments by Differently Positioned Fluorine Atoms.

To understand the influence of the molecular dipole moment on the electron transfer (ET) dynamics across the molecular framework, two series of differently fluorinated, benzonitrile-based self-assembled monolayers (SAMs) bound to Au(111) by either thiolate or selenolate anchoring groups were investigated. Within each series, the molecular structures were the same with the exception of the positions of two fluorine atoms affecting the dipole moment of the SAM-forming molecules. The SAMs exhibited a homogeneous anchoring to the substrate, nearly upright molecular orientations, and the outer interface comprised of the terminal nitrile groups. The ET dynamics was studied by resonant Auger electron spectroscopy in the framework of the core-hole clock method. Resonance excitation of the nitrile group unequivocally ensured an ET pathway from the tail group to the substrate. As only one of the π* orbitals of this group is hybridized with the π* system of the adjacent phenyl ring, two different ET times could be determined depending on the primary excited orbital being either localized at the nitrile group or delocalized over the entire benzonitrile moiety. The latter pathway turned out to be much more efficient, with the characteristic ET times being a factor 2.5-3 shorter than those for the localized orbital. The dynamic ET properties of the analogous thiolate- and selenolate-based adsorbates were found to be nearly identical. Finally and most importantly, these properties were found to be unaffected by the different patterns of the fluorine substitution used in the present study, thus showing no influence of the molecular dipole moment.

Smart Molecular Nanosheets for Advanced Preparation of Biological Samples in Electron Cryo-Microscopy.

Transmission electron cryo-microscopy (cryoEM) of vitrified biological specimens is a powerful tool for structural biology. Current preparation of vitrified biological samples starts off with sample isolation and purification, followed by the fixation in a freestanding layer of amorphous ice. Here, we demonstrate that ultrathin (∼10 nm) smart molecular nanosheets having specific biorecognition sites embedded in a biorepulsive layer covalently bound to a mechanically stable carbon nanomembrane allow for a much simpler isolation and structural analysis. We characterize in detail the engineering of these nanosheets and their biorecognition properties employing complementary methods such as X-ray photoelectron and infrared spectroscopy, atomic force microscopy as well as surface plasmon resonance measurements. The desired functionality of the developed nanosheets is demonstrated by in situ selection of a His-tagged protein from a mixture and its subsequent structural analysis by cryoEM.

Concentration-Dependent Seeding as a Strategy for Fabrication of Densely Packed Surface-Mounted Metal-Organic Frameworks (SURMOF) Layers.

The layer-by-layer (LbL) method is a well-established method for the growth of surface-attached metal-organic frameworks (SURMOFs). Various experimental parameters, such as surface functionalization or temperature, have been identified as essential in the past. In this study, inspired by these recent insights regarding the LbL SURMOF growth mechanism, the impact of reactant solutions concentration on LbL growth of the Cu2 (F4 bdc)2 (dabco) SURMOF (F4 bdc2- =tetrafluorobenzene-1,4-dicarboxylate and dabco=1,4-diazabicyclo-[2.2.2]octane) in situ by using quartz-crystal microbalance and ex situ with a combination of spectroscopic, diffraction and microscopy techniques was investigated. It was found that number, size, and morphology of MOF crystallites are strongly influenced by the reagent concentration. By adjusting the interplay of nucleation and growth, we were able to produce densely packed, yet thin films, which are highly desired for a variety of SURMOF applications.

Liquid-Phase Epitaxial Growth of Highly Oriented and Multivariate Surface-Attached Metal-Organic Frameworks.

Multivariate metal-organic frameworks (MTV-MOFs) incorporating multiple chemical functionalities within single-phase crystalline materials show superior properties that arise from synergistic effects. Herein, we report an efficient and versatile method for the growth of highly oriented multivariate surface-attached MOFs (MTV-SURMOFs) by the combination of the liquid-epitaxial growth method (LPE) and the mixed-linker strategy. Twenty-six MTV-SURMOFs of the [M2L2P] type with a maximum of five different dicarboxylate linkers (L) were deposited onto suitably functionalized surfaces. Systematic studies by infrared reflection absorption (IRRA) spectroscopy and surface XRD provide evidence for the formation of highly oriented MTV-SURMOFs. Interestingly, the pKa's of the dicarboxylate linkers play a crucial role for the orientational quality of the MTV-SURMOFs. In addition, benzene uptake experiments showed that the MTV-SURMOFs exhibit up to 2.6 times higher adsorption capacity as compared to the single-linker SURMOFs, demonstrating the synergistic effects in these surface systems.

Heterochiral recognition among functionalized heptahelicenes on noble metal surfaces.

Chiral recognition among three differently functionalized heptahelicene derivatives on Ag(111) and Au(111) surfaces has been studied with scanning tunnelling microscopy. All three species were found to self-assemble into racemic zigzag structures, with alternation of (M)- and (P)-enantiomers.

Noncovalent Functionalization of Carbon Substrates with Hydrogels Improves Structural Analysis of Vitrified Proteins by Electron Cryo-Microscopy.

In electron cryo-microscopy, structure determination of protein molecules is frequently hampered by adsorption of the particles to the support film material, typically amorphous carbon. Here, we report that pyrene derivatives with one or two polyglycerol (PG) side chains bind to the amorphous carbon films, forming a biorepulsive hydrogel layer so that the number of protein particles in the vitreous ice drastically increases. This approach could be extended by adding a hydrogel-functionalized carbon nanotube network (HyCaNet, the hydrogel again being formed from the PG-pyrene derivatives), which stabilized the protein-containing thin ice films during imaging with the electron beam. The stabilization resulted in reduced particle motion by up to 70%. These substrates were instrumental for determining the structure of a large membrane protein complex.

Bottom-Up Synthesis of Graphene Monolayers with Tunable Crystallinity and Porosity.

We present a method for a bottom-up synthesis of atomically thin graphene sheets with tunable crystallinity and porosity using aromatic self-assembled monolayers (SAMs) as molecular precursors. To this end, we employ SAMs with pyridine and pyrrole constituents on polycrystalline copper foils and convert them initially into molecular nanosheets-carbon nanomembranes (CNMs)- via low-energy electron irradiation induced cross-linking and then into graphene monolayers via pyrolysis. As the nitrogen atoms are leaving the nanosheets during pyrolysis, nanopores are generated in the formed single-layer graphene. We elucidate the structural changes upon the cross-linking and pyrolysis down to the atomic scale by complementary spectroscopy and microscopy techniques including X-ray photoelectron and Raman spectroscopy, low energy electron diffraction, atomic force, helium ion, and high-resolution transmission electron microscopy, and electrical transport measurements. We demonstrate that the crystallinity and porosity of the formed graphene can be adjusted via the choice of molecular precursors and pyrolysis temperature, and we present a kinetic growth model quantitatively describing the conversion of molecular CNMs into graphene. The synthesized nanoporous graphene monolayers resemble a percolated network of graphene nanoribbons with a high charge carrier mobility (∼600 cm2/(V s)), making them attractive for implementations in electronic field-effect devices.

Photoisomerization of azobenzene-substituted alkanethiolates on Au(111) substrates in the context of work function variation: the effect of structure and packing density.

Photoisomerization of a series of custom-designed, azobenzene-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) on Au(111) substrates was studied in the context of work function variation, using Kelvin probe measurements as a transduction technique. These SAMs featured variable packing density (by ∼14%; due to the odd-even effects) and, as an option, were additionally decorated with the electron donating/withdrawing -CH3 and -CF3 tail group, respectively, which induce additional dipole moments. The efficiency of photoisomerization and the respective extent of work function variation (ΔΦ) were found to be quite low and independent of the packing density in the SAMs, within the given odd-even packing density variation. They could only be increased, up to ca. 40 meV for ΔΦ, by mixing the azobenzene-substituted ATs with shorter "matrix" molecules, which were introduced for a partial release of the sterical constraints. The ΔΦ values for the SAMs decorated with the -CH3 and -CF3 tail groups were found to be lower than those for the monolayers without such a decoration, which correlated well with the theoretical estimates for the change of the dipole moment of the relevant molecules upon the photoisomerization.

The fate of bromine after temperature-induced dehydrogenation of on-surface synthesized bisheptahelicene.

The on-surface synthesis of bisheptahelicene by Ullmann coupling of 9-bromoheptahelicene on Au(111) and its temperature-induced dehydrogenation is studied using temperature-programmed reaction spectroscopy and time-of-flight secondary ion mass spectrometry. Specific dehydrogenation products of bisheptahelicene after loss of 6, 8 and 10 hydrogen atoms are identified, corresponding to molecules having undergone Diels-Alder transformations and intramolecular C-C coupling reactions. By combining with atomic hydrogen produced by dehydrogenation, the Ullmann coupling side-product bromine desorbs as HBr. H2 desorption emerges only after all Br has desorbed. Such characteristic behavior is explained by a kinetic model which explicitly considers the coverage of transient atomic H on the surface. Heating experiments performed with saturated layers of different Br-containing molecules reveal that the onset of HBr desorption depends strictly on the dehydrogenation step and therefore on the structure of the molecules.

The role of the dihedral angle and excited cation states in ionization and dissociation of mono-halogenated biphenyls; a combined experimental and theoretical coupled cluster study.

We present a combined theoretical and experimental study on the ionization and primary fragmentation channels of the mono-halogenated biphenyls; 2-chlorobiphenyl, 2-bromobiphenyl and 2-iodobiphenyl. The ionization energies (IEs) of the 2-halobiphenyls and the appearance energies (AEs) of the principal fragments are determined through electron impact ionization, while quantum mechanical calculations at the coupled cluster level of theory are used to elucidate the observed processes and the associated dynamics. The primary fragmentation channels are the direct loss of the halogen upon ionization, the loss of the respective hydrogen halides (HX) as well as loss of the hydrogen halide and an additional hydrogen. We find that the dihedral angle strongly influences the relative potential energy of the neutral and the cation on their respective ground state surfaces, an effect caused by the strong influence of the nuclear motion on the conjugation between the phenyl rings. For the principal dissociative ionization channels from the mono-halogenated biphenyls we reason that these can not be described as statistical decay from the ground state cation, but must rather be understood as direct, state-selective processes from specific excited cationic states characterized through local ionization of either the halogenated or the non-substituted phenyl ring.