Johan Hoogboom

Macroscopic Hierarchical Surface Patterning of Porphyrin Trimers via Self-Assembly and Dewetting

The use of bottom-up approaches to construct patterned surfaces for technological applications is appealing, but to date is applicable to only relatively small areas (∼10 square micrometers). We constructed highly periodic patterns at macroscopic length scales, in the range of square millimeters, by combining self-assembly of disk-like porphyrin dyes with physical dewetting phenomena. The patterns consisted of equidistant 5-nanometer-wide lines spaced 0.5 to 1 micrometers apart, forming single porphyrin stacks containing millions of molecules, and were formed spontaneously upon drop-casting a solution of the molecules onto a mica surface. On glass, thicker lines are formed, which can be used to align liquid crystals in large domains of square millimeter size.

LCD alignment layers. Controlling nematic domain properties

From simple pocket calculators, to mobile telephones and LCD-TV, over the past few decades devices based on liquid crystal display technology have proliferated into just about all conceivable aspects of everyday life. Although used in cutting-edge technology, it is surprising that a vital part in the construction of such displays relies essentially on a process invented almost 100 years ago. This essential part, the alignment layer, dictates the macroscopic uniform alignment of liquid crystalline molecules (mesogens) near its surface. The current method for manufacturing such layers is the mechanical rubbing of spin-coated polymers with a piece of velvet cloth. This very successful method is still at the basis of the production process of even the largest displays currently manufactured in industry. Unfortunately, the construction of ever larger displays with this technique is becoming a technological nightmare for engineers. Therefore, over the past decades, many alternatives to rubbing have been explored. This review will focus on advances towards achieving one of the most important goals in LCD technology: attaining rational control over the properties of nematic liquid crystal domains.

Dynamics of molecular self-ordering in tetraphenyl porphyrin monolayers on metallic substrates

A molecular model system of tetraphenyl porphyrins (TPP) adsorbed on metallic substrates is systematically investigated within a joint scanning tunnelling microscopy/molecular modelling approach. The molecular conformation of TPP molecules, their adsorption on a gold surface and the growth of highly ordered TPP islands are modelled with a combination of density functional theory and dynamic force field methods. The results indicate a subtle interplay between different contributions. The molecule-substrate interaction causes a bending of the porphyrin core which also determines the relative orientations of phenyl legs attached to the core. A major consequence of this is a characteristic (and energetically most favourable) arrangement of molecules within self-assembled molecular clusters; the phenyl legs of adjacent molecules are not aligned parallel to each other (often denoted as pi-pi stacking) but perpendicularly in a T-shaped arrangement. The results of the simulations are fully consistent with the scanning tunnelling microscopy observations, in terms of the symmetries of individual molecules, orientation and relative alignment of molecules in the self-assembled clusters.

LCD-based detection of enzymatic action

By incorporating an ester-containing substrate in a self-assembled alignment layer for liquid crystal cells, the presence of a lipase (CALB) can be directly detected through its enzymatic action on the alignment layer, without the need for fluorescent labelling or enzyme assays.

The development of self-assembled liquid crystal display alignment layers

From simple pocket calculators to mobile telephones and liquid crystal display (LCD)-TV, over the past few decades, devices based on LCD technology have proliferated and can now be found in all conceivable aspects of everyday life. Although used in cutting-edge technology, it is surprising that a vital part in the construction of such displays, namely the alignment layer, relies essentially on a mechanical rubbing process, invented almost 100 years ago. In this paper efforts to develop alignment layers (also called command layers) by processes other than rubbing, namely self-assembly of molecular and macromolecular components will be discussed. Two topics will be presented: (i) tuneable command layers formed by stepwise assembling of siloxane oligomers and phthalocyanine dyes on indium tin oxide surfaces and (ii) command layers formed by self-assembly of porphyrin trimers. The potential use of these layers in sensor devices will also be mentioned.

Novel alignment technique for LCD-biosensorsElectronic supplementary information (ESI) available: alignment layer formation and structure, FT-IR spectra and polarising microscopic images. See http://www.rsc.org/suppdata/cc/b3/b310860k/

The directional drying of a low-salt Tris-EDTA (TE)-buffer to give an alignment layer offers a simple, one-step, non-contact procedure for the construction of parallel liquid crystal displays (LCDs), which can be used to amplify the presence of DNA to scales visible to the naked eye, opening up possibilities for easy detection of bio recognition events.

(Diene)rhodium and ‐iridium Complexes of Pyridinophane Ligands

(Diene)rhodium(I) and -iridium(I) derivatives of the pyridinophane ligand L-4 and the analogous macrocycle L-6 have been prepared and characterized [diene = cyclooctadiene (COD) or norbornadiene (NBD)]. In all of the complexes, the ligand is coordinated in a x(3)-(amine)(pyridine)(2) fashion; a dynamic process, believed to be concerted, exchanges free and coordinated amine groups. [(LIr)-Ir-4(COD)](+) can be protonated at the amine nitrogen atom. It reacts with H2O2, but only in the presence of acid, to give an oxocyclooctenyl complex, formally a 4-e(-) oxidation product. X-ray structures of [(LRh)-Rh-4(COD)]PF6, [(LRh)-Rh-6(COD)]PF6, [(LRh)-Rh-6(NBD)]PF6, [((LH)-H-4)Ir(COD)](BF4)(2), and [(LIr)-Ir-4(C8H11O)](PF6)(2) are presented.