Sebastian Polarz

A new class of surfactants with multinuclear, Inorganic Head Groups

The main ability of amphiphilic molecules is to alter the energy of interfaces. They aid in the formation of various materials characterized by a high surface to volume ratio. Furthermore, amphiphiles tend to self-organize into structures of higher complexity. In the current study anionic surfactants containing a purely inorganic multinuclear head group of the polytungstate type R-[PW(11)O(39)](3-) were synthesized. Alkyl chains of different length were attached to the head group via siloxy bridges. Furthermore, the counterions could be varied. Ultimately, a heteropolyacid surfactant (H(+) as the counterion) could be prepared. The self-assembly behavior of the polyoxometalate surfactants into micelles and even lyotropic phases was studied. For instance, the formation of a phase with P6/mm symmetry containing hexagonally packed cylinders has been observed. Finally, it was possible to extend the functionality of classical amphiphiles. The polyoxometalate amphiphiles have been used for the emulsification of and, at the same time, as the initiator for the cationic polymerization of styrene. As a result, interesting organic-inorganic hybrid polymer latexes with surfaces containing heteropolyacid entities were prepared.

Open and shut for guests in molybdenum-oxide-based giant spheres, baskets, and rings containing the pentagon as a common structural element

A novel exchange between ligands and/or guest molecules can be accomplished in giant molecular spheres (an example is shown in the picture) which are in equilibrium with the corresponding giant baskets in solution.

Effects of Primary and Secondary Surface Groups in Enantioselective Catalysis Using Nanoporous Materials with Chiral Walls

Mesoporous materials are valuable supports for the immobilization of various molecular catalysts. Cases in which the performance of the catalyst improves after immobilization have seldom been reported, especially when it comes to enantioselective synthesis. Knowledge of how the presence of the support surface alters the properties of a bound catalyst is therefore very important. In the current article, a new periodically ordered mesoporous organosilica material (PMO) with walls exclusively made of a chiral building block is presented. The attachment of Al(III) as a Lewis acid center to the chiral group furnishes the material with catalytic activity, for instance, for the asymmetric carbonyl ene reaction. Thus, the presented materials are valuable model systems for studying the effect of the chiral surface and also neighboring groups attached to the silanol groups in the network. It is reported that surface-bound Al(III) exhibits significantly better performance (higher ee values) than an analogous molecular reference catalyst. Furthermore, it could be shown that the ee values increase even further when more bulky secondary groups are attached to the pore walls. Therefore, the main conclusion of the current report is that for cases in which steric conditions of a catalyst play a crucial role its immobilization inside a tailor-made mesoporous organosilica material is beneficial with respect to cooperative effects between the catalytic center and neighboring surface groups.

Lithium related deep and shallow acceptors in Li-doped ZnO nanocrystals

We study the existence of Li-related shallow and deep acceptor levels in Li-doped ZnO nanocrystals using electron paramagnetic resonance (EPR) and photoluminescence (PL) spectroscopy. ZnO nanocrystals with adjustable Li concentrations between 0% and 12% have been prepared using organometallic precursors and show a significant lowering of the Fermi energy upon doping. The deep Li acceptor with an acceptor energy of 800 meV could be identified in both EPR and PL measurements and is responsible for the yellow luminescence at 2.2 eV. Additionally, a shallow acceptor state at 150 meV above the valence band maximum is made responsible for the observed donor-acceptor pair and free electron-acceptor transitions at 3.235 and 3.301 eV, possibly stemming from the formation of Li-related defect complexes acting as acceptors.

Bolaform surfactants with polyoxometalate head groups and their assembly into ultra-small monolayer membrane vesicles

Surfactants are indispensable in established technologies as detergents or emulsification agents, and also in recent studies for controlling the growth of nanoparticles or for creating nanocarriers. Although the properties of conventional, organic surfactants are thoroughly explored, strong interest persists in surfactants that possess unique features inaccessible for ordinary systems. Here we present dipolar, bolaform surfactants with a head group comprising of 11 tungsten atoms. These novel compounds are characterized by an exceptionally low critical self-organization concentration, which leads to monolayer vesicles with a diameter of only 15 nm, that is, substantially smaller than for any other system. The membrane of the vesicles is impermeable for water-soluble and oil-soluble guests. Control over release kinetics, which can be followed via the quantitative fluorescence quenching of confined fluorophores, is gained by means of pH adjustments.

Hierarchical Zinc Oxide Materials with Multiple Porosity Prepared by Ultrafast Temperature Gradient Chemical Gas-Phase Synthesis

The preparation of materials characterized by three types of porosity could be prepared by a continuous chemical gas-phase method. The multistep formation mechanism involves a critical temperature gradient and occurs within seconds. The resulting hollow aerogel materials show superior properties as gas sensors in comparison to materials constructed from compact nanoparticles.

Hybrid Surfactant Systems with Inorganic Constituents

Surfactants are molecules of enormous scientific and technological importance, which are widely used as detergents, emulsifiers, and for the preparation of diverse nanostructures. Their fascinating ability to form self-organized structures, such as micelles or liquid crystals, originate from their amphiphilic architecture-a polar head group linked to a hydrophobic chain. While almost all known surfactants are organic, a new family of surfactants is now emerging, which combines amphiphilic properties with the advanced functionality of transition-metal building blocks, for example, redox or catalytic activity and magnetism. These hybrid surfactants exhibit novel self-organization features because of the unique size and electronic properties of the metal-containing entities.

Chemistry in Confining Reaction Fields with Special Emphasis on Nanoporous Materials

The everyday routine of most chemists is dictated by large numbers. The chemical rules for ensembles of molar size (N approximately N(A)=6.022 x 10(23)) are well known and can be understood in most cases by using Boltzmann distribution. It is an interesting question how a small ensemble of a chemical system behaves and if it differs from the respective large-ensemble counterpart. The experimental approach presented in the current paper involves the division of a macroscopic volume into compartments that contain only a small number of reactants. The compartments represent the pores of tailor-made nanoporous materials.

Porous and Shape‐Anisotropic Single Crystals of the Semiconductor Perovskite CH3NH3PbI3 from a Single‐Source Precursor

Significant progress in solar-cell research is currently made by the development of metal-organic perovskites (MOPs) owing to their superior properties, such as high absorption coefficients and effective transport of photogenerated charges. As for other semiconductors, it is expected that the properties of MOPs may be significantly improved by a defined nanostructure. However, their chemical sensitivity (e.g., towards hydrolysis) prohibits the application of methods already known for the synthesis of other nanomaterials. A new and general method for the synthesis of various (CH3NH3)PbI3 nanostructures from a novel single-source precursor is presented. Nanoporous MOP single crystals are obtained by a crystal-to-crystal transformation that is accompanied by spinodal demixing of the triethylene glycol containing precursor structure. Selective binding of a capping agent can be used to tune the particle shape of the MOP nanocrystals.

Adsorption in periodically ordered mesoporous organosilica materials studied by in situ small-angle X-ray scattering and small-angle neutron scattering.

Modified periodically ordered mesoporous organosilica materials were prepared starting from a recently introduced type of sol-gel precursor, containing both organic moieties and hydrolyzable Si-OR groups. In order to thoroughly characterize the mesoporosity and its accessibility, different probe gases were used in conventional gas adsorption experiments. Furthermore, in situ small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) were applied to study the mesoporosity and the sorption processes, taking advantage of scattering contrast matching conditions. Thereby, the materials were characterized not only by different probe molecules but also at different temperatures (nitrogen at 77 K, dibromomethane at 290 K and perfluoropentane at 276 K). The comparison between the standard and in situ SAXS/SANS adsorption experiments revealed valuable information about the porosity and microstructure of the materials. It is demonstrated that the organic moieties are homogeneously distributed; that is, they do not phase-separate from silica on the nanometer scale.