The use of the coupling agent, 3-aminopropyltriethoxysilane (APTES), in the silanization reaction with silanol-terminated silicon is an important surface modification reaction. Of particular importance is that the terminal amine functionalities of APTES are sufficiently exposed to the gas or liquid phase for further modifications, such as amide coupling reactions. Here, metastable induced electron spectroscopy (MIES) and UV photoelectron spectroscopy (UPS) were used to study the composition of the outermost layer of a silanol-terminated Si surface after silanization with APTES. High-resolution X-ray photoelectron spectroscopy (XPS) was used to validate the attachment of APTES to the surface. Density of States (DOS) calculations were employed for interpreting the MIE spectra. Findings showed that amine functionalities covered only a small fraction of the APTES-modified Si surface.

The templated synthesis of porphyrin dimers, oligomers, and tapes has recently attracted considerable interest. Here, we introduce a clean, temperature-induced covalent dehydrogenative coupling mechanism between unsubstituted free-base porphine units yielding dimers, trimers, and larger oligomers directly on a Ag(111) support under ultrahigh-vacuum conditions. Our multitechnique approach, including scanning tunneling microscopy, near-edge X-ray absorption fine structure and photoelectron spectroscopy complemented by theoretical modeling, allows a comprehensive characterization of the resulting nanostructures and sheds light on the coupling mechanism. We identify distinct coupling motifs and report a decrease of the electronic gap and a modification of the frontier orbitals directly associated with the formation of triply fused dimeric species. This new on-surface homocoupling protocol yields covalent porphyrin nanostructures addressable with submolecular resolution and provides prospective model systems towards the exploration of extended oligomers with tailored chemical and physical properties.

The surface functionalization of TiO2-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release of bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) is able to self-assemble to form monolayers on TiO2 surfaces, but its adsorption geometry and solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, and FT-IR) and theoretical (plane-wave DFT) tools to investigate the preferential interaction mode of APTES on anatase TiO2. We demonstrate that monomeric APTES chemisorption should proceed through covalent Si–O–Ti bonds. Although dimerization of the silane through Si–O–Si bonds is possible, further polymerization on the surface is scarcely probable. Terminal amino groups are expected to be partially involved in strong charge-assisted hydrogen bonds with surface hydroxyl groups of TiO2, resulting in a reduced propensity to react with other species. Solar-induced mineralization proceeds through preferential cleavage of the alkyl groups, leading to the rapid loss of the terminal NH2 moieties, whereas the Si-bearing head of APTES undergoes slower oxidation and remains bound to the surface. The suitability of employing the silane as a linker with other chemical species is discussed in the context of controlled degradation of APTES monolayers for drug release and surface patterning.

We present strong evidence for the oxidation of conjugated polymers in the formation of conjugated polymer dots (CPdots) using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Although recent studies show that folding of the polymer chain into a compact 3D structure is involved in the formation of these nanoparticles, the process by which these intrinsically hydrophobic nanoscale particles circumvent aggregation in water is still not well understood. Zeta potential results show that these dots have a negatively charged surface at neutral pH, with a zeta potential and surface charge density of approximately -40 mV and (1.39 - 1.70) × 10(-2) C/m(2), respectively. In addition, quantitative elemental analysis of CPdots indicates that oxygen composes 7-13% of these nanoparticles. The overall results support the presence of chemical defects in forming a hydrophilic surface of CPdots. As a consequence, the charged surface contributes to inhibiting the aggregation of CPdots in water, leading to colloidal stability.

The fabrication and control of coordination compounds or architectures at well-defined interfaces is a thriving research domain with promise for various research areas, including single-site catalysis, molecular magnetism, light-harvesting, and molecular rotors and machines. To date, such systems have been realized either by grafting or depositing prefabricated metal-organic complexes or by protocols combining molecular linkers and single metal atoms at the interface. Here we report a different pathway employing metal-organic chemical vapor deposition, as exemplified by the reaction of meso-tetraphenylporphyrin derivatives on atomistically clean Ag(111) with a metal carbonyl precursor (Ru3(CO)12) under vacuum conditions. Scanning tunneling microscopy and X-ray spectroscopy reveal the formation of a meso-tetraphenylporphyrin cyclodehydrogenation product that readily undergoes metalation after exposure to the Ru-carbonyl precursor vapor and thermal treatment. The self-terminating porphyrin metalation protocol proceeds without additional surface-bound byproducts, yielding a single and thermally robust layer of Ru metalloporphyrins. The introduced fabrication scheme presents a new approach toward the realization of complex metal-organic interfaces incorporating metal centers in unique coordination environments.