Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300{\deg}C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO-LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure.Comment: 9 pages, 6 figure

(Metallo)porphyrins for potential materials science applications

The bottom-up approach to replace existing devices by molecular-based systems is a subject that attracts permanently increasing interest. Molecular-based devices offer not only to miniaturize the device further, but also to benefit from advanced functionalities of deposited molecules. Furthermore, the molecules itself can be tailored to allow via their self-assembly the potential fabrication of devices with an application potential, which is still unforeseeable at this time. Herein, we review efforts to use discrete (metallo)porphyrins for the formation of (sub)monolayers by surface-confined polymerization, of monolayers formed by supramolecular recognition and of thin films formed by sublimation techniques. Selected physical properties of these systems are reported as well. The application potential of those ensembles of (metallo)porphyrins in materials science is discussed

Surface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticles

Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm−1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal–nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced

(Metallo)porphyrins for potential materials science applications

The bottom-up approach to replace existing devices by molecular-based systems is a subject that attracts permanently increasing interest. Molecular-based devices offer not only to miniaturize the device further, but also to benefit from advanced functionalities of deposited molecules. Furthermore, the molecules itself can be tailored to allow via their self-assembly the potential fabrication of devices with an application potential, which is still unforeseeable at this time. Herein, we review efforts to use discrete (metallo)porphyrins for the formation of (sub)monolayers by surface-confined polymerization, of monolayers formed by supramolecular recognition and of thin films formed by sublimation techniques. Selected physical properties of these systems are reported as well. The application potential of those ensembles of (metallo)porphyrins in materials science is discussed

The Controlled Synthesis of Carbon Tubes and Rods by Template-Assisted Twin Polymerization

The application of porous carbon is versatile. It is used for high-performance catalyst support, electrode material in batteries, and gas storage. In each of these application fields nanostructuring improves the material properties. Supercapacitors store a high energy density. Exactly adapted carbon structures increase the life of lithium batteries and protect catalysts with increasing reaction rate and selectivity. Most of porous carbon materials have a spherical shape. To the best of our knowledge, there is no procedure to synthesize nanostructured cylindrical porous carbon systematically. Here, template glass fibres and SiO2-tubes were modified with nanostructured SiO2/phenolic resin and SiO2/poly(furfuryl alcohol) layers by surface twin polymerization (TP) of 2,2′-spirobi[4H-1,3,2-benzodioxasiline] and tetrafurfuryloxysilane. Afterwards the SiO2/polymer layer on the template is thermally transformed into a defect-free nanostructured SiO2/carbon layer. After completely removing the SiO2 components microporous carbon tubes or rods are finally achieved. The diameters of the carbon rods and the inner as well as the outer diameter of the carbon tubes are adjustable according to the shape and size of the template. Thus, a huge variety of microporous carbon materials can be easily produced by template-assisted TP

Tuning the magneto-optical response of TbPc2 single molecule magnets by the choice of the substrate

In this work, we investigated the magneto-optical response of thin films of TbPc2 on substrates which are relevant for (spin) organic field effect transistors (SiO2) or vertical spin valves (Co) in order to explore the possibility of implementing TbPc2 in magneto-electronic devices, the functionality of which includes optical reading. The optical and magneto-optical properties of TbPc2 thin films prepared by organic molecular beam deposition (OMBD) on silicon substrates covered with native oxide were investigated by variable angle spectroscopic ellipsometry (VASE) and magneto-optical Kerr effect (MOKE) spectroscopy at room temperature. The magneto-optical activity of the TbPc2 films can be significantly enhanced by one to two orders of magnitude upon changing the molecular orientation (from nearly standing molecules on SiO2/Si substrates to nearly lying molecules on perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) templated SiO2/Si substrates) or by using metallic ferromagnetic substrates (Co)