Carboxylic acid-doped SBA-15 silica as a host for metallo-supramolecular coordination polymers.

The adsorption of a metallo-supramolecular coordination polymer (Fe-MEPE) in the cylindrical pores of SBA-15 silica with pure and carboxylic acid (CA) carrying pore walls has been studied. Fe-MEPE is an intrinsically stiff polycation formed by complexation of Fe(II)-acetate with an uncharged ditopic bis-terpyridine ligand. The adsorption affinity and kinetics of the Fe-MEPE chains is strongly enhanced when the pore walls are doped with CA, and when the pH of the aqueous medium or temperature is increased. The initial fast uptake is connected with a decrease of pH of the aqueous solution, indicating an ion-exchange mechanism. It is followed by a slower (presumably diffusion-controlled) further uptake. The maximum adsorbed amount of Fe-MEPE in the CA-doped material corresponds to a monolayer of Fe-MEPE chains disposed side-by-side along the pore walls. The stoichiometry of Fe-MEPE in the pores (determined by XPS) was found to be independent of the loading and similar to that of the starting material. The mean chain length of Fe-MEPE before and after embedding in the CA-doped matrix was studied by solid-state 15N NMR using partially 15N-labeled Fe-MEPE. It is shown that the average chain length of Fe-MEPE is reduced when the complex is incorporated in the pores.

Structure and temperature behavior of metallo-supramolecular assemblies.

A detailed structural analysis of a Langmuir-Blodgett (LB) multilayer composed of a polyelectrolyte-amphiphile complex (PAC) is presented. The PAC is self-assembled from metal ions, ditopic bis-terpyridines, and amphiphiles. The vertical structure of the LB multilayer is investigated by X-ray reflectometry. The multilayer has a periodicity of 57 A, which corresponds to an architecture of flat lying metallo-supramolecular coordination polyelectrolyte (MEPE) rods and upright-standing amphiphiles (dihexadecyl phosphate, DHP). In-plane diffraction reveals hexagonal packing of the DHP molecules. Using extended X-ray absorption fine structure (EXAFS) experiments, we prove that the central metal ion is coordinated to the terpyridine moieties in a pseudo-octahedral coordination environment. The Fe-N bond distances are 1.82 and 2.0 A, respectively. Temperature resolved measurements indicate a reversible phase transition in a temperature range up to 55 degrees C. EXAFS measurements indicate a lengthening of the average Fe-N bond distance from 1.91 to 1.95 A. The widening of the coordination cage upon heating is expected to lower the ligand field stabilization, thus giving rise to spin transitions in these composite materials.

Controlling wettability by light: illuminating the molecular mechanism.

The functionalisation of a surface with an organic monolayer containing photoactive moieties such as the azobenzene chromophore opens an elegant route for controlling its wettability by light. In this paper we investigate the microscopic origin of the macroscopic change in wettability upon photo-induced cis-trans isomerization of a copolymeric diphenyl-diazene Langmuir-Blodgett monolayer. Polarised UV-Vis and FTIR spectroscopy have been used to monitor the orientational order of various functional groups, Atomic Force Microscopy and Imaging Ellipsometry is employed for the quantification of the surface roughness and morphology, contact angle and surface potential measurements are carried out for a characterisation of the polar ordering. The data analysis is further supported by semi-empirical and ab-initio calculations of the molecular dipole moments and the normal IR-modes of the fluorinated chromophore. The combination of all these techniques provides a detailed molecular picture. The data suggest that changes in the projection of the dipole moment onto the surface normal caused by isomerization of the azobenzene are responsible for the observed changes in the surface energy. This knowledge allowed us to predict guidelines for the synthesis of molecules in order to maximize the wetting contrast upon photo-irradiation.

Temperature- and time-resolved X-ray scattering at thin organic films.

Multilayers of an Fe(II)-polyelectrolyte-amphiphile complex (Fe-PAC) were investigated simultaneously by energy-dispersive X-ray reflectivity and in-plane diffraction at the bending-magnet beamline at BESSY II. By recording spectra between room temperature and about 348 K with a time resolution of about 60 s, two phase transitions were identified and the respective activation energies were determined. Owing to a fixed geometrical set-up, an energy-dispersive experiment is suitable for measuring X-ray reflectivity and in-plane X-ray diffraction of thin organic films simultaneously. Installed at a bending magnet at BESSY II and using an energy range of 4 < E < 25 keV, both reflectivity and diffraction spectra can be collected within about 60 s. The performance is demonstrated by temperature- and time-resolved measurements of the phase transition behaviour of multilayers of an Fe-PAC deposited on a silicon support by means of the Langmuir-Blodgett (LB) technique. By measuring the X-ray reflectivity while increasing the temperature, it is shown that the original LB phase is not stable and transforms irreversibly into a liquid-crystalline (LC)-like phase at about 318 K. At the same temperature the in-plane diffraction signal vanishes reversibly, reflecting rotational disorder of the hexagonal arrangement of amphiphilic chains. Its activation energy is determined to be about 1.3 eV. At about 338 K a second irreversible phase transition occurs to another LC phase with smaller vertical layer spacing. This transition is reversible between 329 K and 338 K.

Structural analysis of a metallosupramolecular polyelectrolyte-amphiphile complex at the air/water interface.

A detailed analysis of a metallosupramolecular coordination polyelectrolyte-amphiphile complex (PAC) at the air/water interface is presented based on Langmuir isotherm measurements, Brewster angle microscopy as well as X-ray reflectance and diffraction measurements. The PAC is prepared in solution by metal-ion coordination of Fe(OAc)2 and 1,4-bis(2,2':6',2"-terpyridin-4'-yl)benzene followed by self-assembly with dihexadecyl phosphate (DHP). The spreading of the PAC at the air/water interface results in a Langmuir film with a stratified architecture, such that DHP forms a monolayer on the water surface, while the metallosupramolecular coordination polyelectrolyte (MEPE) is immersed in the aqueous subphase. Electrostatic interactions of MEPE and DHP force the alkyl chains into an upright, hexagonal lattice even at low surface pressures. This work illustrates how supramolecular, colloidal, and surface chemistry can be combined to create complex architectures with tailored characteristics that may not be accessible through self-organization in the liquid phase.

A route to hierarchical materials based on complexes of metallosupramolecular polyelectrolytes and amphiphiles.

Anisotropic thin film materials of metallosupramolecular polyelectrolyte-amphiphile complexes (denoted PACs) with structures at several length scales were fabricated through a multistep self-assembly process. Metal ion-mediated self-assembly of the ditopic ligand 1,4-bis(2,2':6',2"-terpyridine-4'-yl)benzene and electrostatic binding with the amphiphile dihexadecyl phosphate result in a PAC with tailored surface chemical properties, including solubility and surface activity. The PAC forms a stable monolayer at the air-water interface that is readily transferred and oriented on solid supports with the Langmuir-Blodgett technique. The presented strategy unifies colloid and metallosupramolecular chemistry and opens a versatile route to hierarchical materials with tailored structures and functions.

Surfactant-encapsulated clusters (SECs): (DODA)20(NH4)[H3Mo57V6(NO)6O183(H2O)18], a case study.

We present a comprehensive study of the partially reduced polyoxomolybdate [H3-Mo57V6(NO)6O183(H2O)18]21-encapsulated in a shell of dimethyldioctadecylammonium (DODA) surfacmolecules. Treatment of an aqueous solution of (NH4)21[H3Mo57V6-(NO)6O183(H2O)18] . 65H2O (1a) with a trichloromethane solution of the surfactant leads to instant transfer of the encapsulated complex anion into the organic phase. Results from vibrational spectroscopy. analytical ultracentrifugation, small-angle X-ray scattering, transmission electron microscopy, elemental analysis, and Langmuir compression isotherms are consistent with a single polyoxometalate core encapsulated within a shell of 20 DODA molecules. The molar mass of the supramolecular assembly is 20249 gmol(-1) and the diameter is 3.5 nm. A material with the empirical formula (DODA)20(NH4)[H3-Mo57V6NO)6O183(H2O)18] (2) was isolated as a dark violet solid, which readily dissolves in organic solvents. Slow evaporation of solutions of 2 on solid substrates forces the hydrophobic particles to aggregate into a cubic lattice. Annealing these so-formed films at elevated temperature causes de-wetting with terrace formation similar to liquid crystals and block copolymers. Compound 2 forms a stable Langmuir monolayer at the air-water interface; Langmuir-Blodgett multilayers are readily prepared by repeated transfer of monolayers on solid substrates. The films were characterized by optical ellipsometry, Brewster angle microscopy, transmission electron microscopy, and X-ray reflectance.