Correction: The molecular structure of the surface of water-ethanol mixtures.

Correction for 'The molecular structure of the surface of water-ethanol mixtures' by Johannes Kirschner et al., Phys. Chem. Chem. Phys., 2021, 23, 11568-11578, DOI: 10.1039/D0CP06387H.

The molecular structure of the surface of water-ethanol mixtures.

Mixtures of water and alcohol exhibit an excess surface concentration of alcohol as a result of the amphiphilic nature of the alcohol molecule, which has important consequences for the physico-chemical properties of water-alcohol mixtures. Here we use a combination of intensity vibrational sum-frequency generation (VSFG) spectroscopy, heterodyne-detected VSFG (HD-VSFG), and core-level photoelectron spectroscopy (PES) to investigate the molecular properties of water-ethanol mixtures at the air-liquid interface. We find that increasing the ethanol concentration up to a molar fraction (MF) of 0.1 leads to a steep increase of the surface density of the ethanol molecules, and an increased ordering of the ethanol molecules at the surface. When the ethanol concentration is further increased, the surface density of ethanol remains more or less constant, while the orientation of the ethanol molecules becomes increasingly disordered. The used techniques of PES and VSFG provide complementary information on the density and orientation of ethanol molecules at the surface of water, thus providing new information on the molecular-scale properties of the surface of water-alcohol mixtures over a wide range of compositions. This information is invaluable in understanding the chemical and physical properties of water-alcohol mixtures.

Region-Selective Deposition of Core-Shell Nanoparticles for 3D Hierarchical Assemblies by the Huisgen 1,3-Dipolar Cycloaddition.

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO(x)) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO(x) NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO2 NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

Blending through-space and through-bond π-π-coupling in [2,2']-paracyclophane-oligophenylenevinylene molecular wires.

A series of ZnP-pCp-oPPV-C60 conjugates covalently connected through [2,2']-paracyclophane-oligophenylenevinylene (pCp-oPPV) bridges containing one, two, and three [2,2']-paracyclophanes (pCps) has been prepared in multistep synthetic procedures involving Horner-Wadsworth-Emmons olefination reactions and/or Heck type Pd-catalyzed reactions. Molecular modeling suggests that charge transfer is effectively mediated by the pCp-oPPVs through a predominant hole-transfer mechanism. Photophysical investigation supports molecular modeling and reveals two major trends. On one hand, C60 excitation of 1, 2, and 3 leads exclusively to charge transfer between pCp and C60 to afford a ZnP-(pCp-oPPV)(•+)-C60(•-) radical ion pair state without giving rise to a subsequent charge shift to yield the ZnP(•+)-pCp-oPPV-C60(•-) radical ion pair state. On the other hand, ZnP excitation of 1, 2, and 3 results in a rather slow charge transfer between ZnP and C60, after which the ZnP(•+)-pCp-oPPV-C60(•-) radical ion pair state evolves. In temperature-dependent ZnP fluorescence experiments, which were performed in the temperature range from 273 to 338 K, two domains are discernible: low and high temperature behaviors. In the low temperature range (i.e., below 30 °C) the rate constants do not change, suggesting that a superexchange mechanism is the modus operandi. In the high temperature range (i.e., >30 °C) the rate constants increase. Moreover, we find rather strong distance dependence for 1 and 2 and weak distance dependence for 2 and 3. A damping factor of 0.145 Å(-1) is derived for the former pair and 0.012 Å(-1) for the latter.

Image-Based Chemical Structure Determination.

Chemical imaging is a powerful tool for understanding the chemical composition and nature of heterogeneous samples. Recent developments in elemental, vibrational, and mass-spectrometric chemical imaging with high spatial resolution (50-200 nm) and reasonable timescale (a few hours) are capable of providing complementary chemical information about various samples. However, a single technique is insufficient to provide a comprehensive understanding of chemically complex materials. For bulk samples, the combination of different analytical methods and the application of statistical methods for extracting correlated information across different techniques is a well-established and powerful concept. However, combined multivariate analytics of chemical images obtained via different imaging techniques is still in its infancy, hampered by a lack of analytical methodologies for data fusion and analysis. This study demonstrates the application of multivariate statistics to chemical images taken from the same sample via various methods to assist in chemical structure determination.

Driving forces for the self-assembly of graphene oxide on organic monolayers.

Graphene oxide (GO) flakes were self-assembled from solution on surfaces of self-assembled monolayers (SAMs), varying in the chemical structure of their head groups. The coverage density of GO relates to strength of attractive interaction, which is largest for Coulomb interaction provided by positively charged SAM head groups and negatively charged GO. A rough surface enhances the coverage density but with the same trend in driving force dependency. The self-assembly approach was used to fabricate field-effect transistors with reduced GO (rGO) as active layer. The SAMs as attractive layer for self-assembly remain almost unaffected by the reduction from GO to rGO and serve as ultra-thin gate dielectrics in devices, which operate at low voltages of maximum 3 V and exhibit a shift of the Dirac voltage related to the dipole moment of the SAMs.

Region-selective self-assembly of functionalized carbon allotropes from solution.

Approaches for the selective self-assembly of functionalized carbon allotropes from solution are developed and validated for 0D-fullerenes, 1D-carbon nanotubes and 2D-graphene. By choosing the right molecular interaction of self-assembled monolayers (serving the surface) with the functionalization features of carbon materials, which provide the solubility but also serve the driving force for assembly, we demonstrate a region-selective and self-terminating assembly of the materials. Active layers of the carbon allotropes can be selectively deposited in the channel region of thin-film transistor (TFT) devices by this approach. As an example for a 0D system, molecules of C60 functionalized octadecylphosphonic acids are used to realize self-assembled monolayer field-effect transistors (SAMFETs) based on a selective molecular exchange reaction of stearic acid in the channel region. For noncovalently functionalized single-walled carbon nanotubes (SWCNTs) and graphene oxide (GO) flakes, the electrostatic Coulomb interactions between the functional groups of the carbon allotropes and the charged head groups of a SAM dielectric layer are utilized to implement the selective deposition.