Metallosupramolecular thin films using a tritopic cyclam-based ligand.

We present the preparation and characterization of novel metallosupramolecular thin films on solid substrates. These films incorporate metallosupramolecular polymers based on a tritopic cyclam bis-terpyridine ligand and are formed using different deposition techniques. From layer-by-layer (LBL) method, alternate thin multilayers of this metallosupramolecule along with oppositely charged polyelectrolyte are constructed by electrostatic self-assembly. Using dip-coating method, homogenous monolayers are deposited. The monolayer thickness is controlled by withdraw velocity of substrate. In a direct-assembly approach: Langmuir-Blodgett (LB), well-ordered metallosupramolecular monolayer is achieved by using a Metallosupramolecular Polyelectrolyte Amphiphile Complex (MPAC). The structures of these metallosupramolecular thin films are characterized by X-ray reflectivity (XRR), Atomic Force Microscopy (AFM), Langmuir isotherms, and UV/Vis absorption. The results open access to fabricate novel molecular materials such as sensors and memory devices.

Characterization of strain recovery and "self-healing" in a self-assembled metallo-gel.

We report a self-assembled metallo suprapolymer gel exhibiting remarkable self-healing features. The Ni2BTC metallo suprapolymer gels result from the complexation of Ni(2+) metal ions by a tritopic ligand (bis-terpyridine cyclam) in dimethylformamide (DMF) and an annealing step at 50 °C for 24 hours. The self-healing properties are characterized by visual inspection, rheological and impedance spectroscopy measurements: the results are compared with those of a fatty acid-based molecular organogel chosen as a reference system. The creep-recovery analysis uses the Burgers model for low strains and characterizes a recovery capability of up to 72% of the deformation in Ni2BTC gels while it is only 32% for the fatty acid organogel. At very large strains, the impedance spectroscopy confirms the slow repairing process consistently with the visual observations. Rheological measurements demonstrate the restructuring of the fractured networks. The fatigue of the self-healed gel networks undergoing long sequences of strain-relaxation steps is characterized.

Salt effects in the formation of self-assembled lithocholate helical ribbons and tubes.

The formation of self-assembled nanotubes is usually accounted for by anisotropic elastic properties of membranelike precursors. We present experimental data as evidence of the role played by electrostatics in the formation of self-assembled tubes in alkaline aqueous suspensions of lithocholic acid (LCA). Striking salt effects are characterized by comparing the rheological, dynamical, and scattering properties of systems prepared either in stoichiometric neutralization conditions (SC) of LCA or in a large excess of sodium hydroxide (EOC, experimentally optimized conditions) and finally, in two steps: stoichiometric neutralization followed by an appropriate addition of NaCl (AISC). The SC liquid system is originally made up of loose helical ribbons (previous transmission electron microscopy data), and upon aging they exhibit both intra- and interordering processes. Initially, the helical ribbons are loose and progressively wind around a cylinder (R = 330 Å) with their edges exposed to the solvent. They can be temporarily organized in a centered rectangular two-dimensional lattice (pgg, a = 224 Å, b = 687 Å). Upon further aging, the ribbons wind into more compact helical ribbons (or tubes with helical grooves): their edges are less-exposed and their ordering vanishes. Upon addition of NaCl salt (as in the AISC systems), the specific screening of the intra-aggregate electrostatic repulsions induces the closure of the ribbons into tubes (R(ext) = 260 Å, R(int) = 245 Å as in the EOC systems). Simultaneously with the closure of the ribbons into plain tubes, a drastic enhancement of their interconnectivity through van der Waals attractions develops. Eventually, gels are obtained with networks having hexagonal bundles of tubes.

Correlations of properties and structures at different length scales of hydro- and organo-gels based on N-alkyl-(R)-12-hydroxyoctadecylammonium chlorides.

The self-assembly and gelating ability of a set of N-alkyl-(R)-12-hydroxyoctadecylammonium chlorides (NCl-n, where n = 0-6, 18 is the length of the alkyl chain on nitrogen) are described. Several are found to be ambidextrous (gelating both water and a variety of organic liquids) and very efficient (needing less than ca. 0.5 wt % at room temperature). Structure-property correlations at different distance scales of the NCl-n in their hydro- and organo-gels and neat, solid states have been made using X-ray diffraction, neutron scattering, thermal, optical, cryo-SEM and rheological techniques. The self-assembled fibrillar networks consist of spherulitic objects with fibers whose diameters and degrees of twisting differ in the hydro- and organo-gels. Increasing n (and, thus, the molecular length) increases the width of the fibers in their hydrogels; an irregular, less pronounced trend between n and fiber width is observed in the corresponding toluene gels. Time-dependent, small angle neutron scattering data for the isothermal sol-to-gel transformation of sols of NCl-18/toluene to their gels, treated according to Avrami theory, indicate heterogeneous nucleation involving rodlike growth. Rheological studies of gels of NCl-3 in water and toluene confirm their viscoelastic nature and show that the hydrogel is mechanically stronger than the toluene gel. Models for the different molecular packing arrangements within the fibrillar gel networks of the hydro- and organogels have been inferred from X-ray diffraction. The variations in the fibrillar networks provide a comprehensive picture and detailed insights into why seemingly very similar NCl-n behave very differently during their self-assembly processes in water and organic liquids. It is shown that the NCl-n provide a versatile platform for interrogating fundamental questions regarding the links between molecular structure and one-dimensional self-aggregation, leading to gelation.

Cosolvent gel-like materials from partially hydrolyzed poly(vinyl acetate)s and borax.

A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions.

Structural relationships in 2,3-bis-n-decyloxyanthracene and 12-hydroxystearic acid molecular gels and aerogels processed in supercritical CO(2).

Supercritical carbon dioxide is used to prepare aerogels of two reference molecular organogelators, 2,3-bis-n-decyloxyanthracene (DDOA) (luminescent molecule) and 12-hydroxystearic acid (HSA). Electron microscopy reveals the fibrillar morphology of the aggregates generated by the protocol. SAXS and SANS measurements show that DDOA aerogels are crystalline materials exhibiting three morphs: (1) arrangements of the crystalline solid (2D p6m), (2) a second hexagonal morph slightly more compact, and (3) a packing specific of the fibers in the gel. Aggregates specific of the aerogel (volume fraction being typically phi approximately 0.60) are developed over larger distances (approximately 1000 A) and bear fewer defaults and residual strains than aggregates in the crystalline and gel phases. Porod, Scherrer and Debye-Bueche analyses of the scattering data have been performed. The first five diffraction peaks show small variations in position and intensity assigned to the variation of the number of fibers and their degree of vicinity within hexagonal bundles of the related SAFIN according to the Oster model. Conclusions are supported by the guidelines offered by the analysis of the situation in HSA aerogels for which the diffraction pattern can be described by two coexisting lamellar-like arrangements. The porosity of the aerogel, as measured by its specific surface extracted from the scattering invariant analysis, is only 1.8 times less than that of the swollen gel and is characteristic of a very porous material.

Extended surfaces nanopatterned with functionalized cavities for positioning nanoparticles.

This contribution reports a method delivering inorganic nanopatterned and functional surfaces from the ion beam etching of mesoporous thin films. The nanoscaled patterns are spherical or cylindrical cavities that are arranged on a macroscale. A variety of chemical functions can be grafted selectively in the cavities to add specific interactions with functional nanoparticles to be positioned. The process opens a simple route to localize and organize functional spherical or linear nanoparticles on extended surfaces.

Soluble heterometallic coordination polymers based on a bis-terpyridine-functionalized dioxocyclam ligand.

Soluble homo- and heterometallic coordination polymers containing transition metal cations (Cu(2+), Fe(2+), Co(2+), and Ni(2+) ions) were prepared in a two-step procedure using a polytopic bis(terpyridine)dioxocyclam ligand 1H(2) (dioxocyclam = 1,4,8,11-tetraazacyclotetradecane-5,7-dione). These supramolecular systems incorporate two different metal complexes, the metal cations being located both between two terpyridine units and in the macrocyclic framework. The characterization of these soluble architectures was investigated by cyclic voltammetry, mass spectrometry, viscosimetry, and UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies. Our results clearly indicate the formation of well-organized heterometallic polymers in which two different metal ions alternate in the self-assembled structure. These investigations furthermore brought to light an original acid-controlled disassembling process of the homometallic copper(II) polymer into dinuclear complexes.

From specular reflectivity to time-resolved grazing incidence X-ray scattering out of the specular plane (GISAXS): equilibrium and nonequilibrium states of organic/inorganic monolayers at liquid surfaces.

The grazing incidence diffuse X-ray scattering out of the specular plane technique (GISAXS) is presented, and its capabilities are compared to the more classical X-ray specular reflectivity technique (XSR). Three experimental illustrations are given to prove the efficiency of GISAXS. First, the structure of a DPPC phospholipid monolayer is analyzed. Second, the time-resolved kinetics of lipid desorption from a monolayer interacting with a mineral gel subphase is studied. Third, the structural evolution of biomembranes at extremely low temperatures is illustrated. The GISAXS technique appears to compete efficiently with neutron reflection techniques by taking advantage of remarkably short acquisition times crucial in kinetics experiments.

Self-assembly of bile steroid analogues: molecules, fibers, and networks.

Structural and rheological features of a series of molecular hydrogels formed by synthetic bile salt analogues have been scrutinized. Among seven gelators, two are neutral compounds, while the others are cationic systems among which one is a tripodal steroid derivative. Despite the fact that the chemical structures are closely related, the variety of physical characteristics is extremely large in the structures of the connected fibers (either plain cylinders or ribbons), in the dynamical modes for stress relaxation of the associated SAFINs, in the scaling laws of the shear elasticity (typical of either cellular solids or fractal floc-like assemblies), in the micron-scale texture and the distribution of ordered domains (spherulites, crystallites) embedded in a random mesh, in the type of nodal zones (either crystalline-like, fiber entanglements, or bundles), in the evolution of the distribution and morphology of fibers and nodes, and in the sensitivity to added salt. SANS appears to be a suitable technique to infer all geometrical parameters defining the fibers, their interaction modes, and the volume fraction of nodes in a SAFIN. The tripodal system is particularly singular in the series and exhibits viscosity overshoots at the startup of shear flows, an "umbrella-like" molecular packing mode involving three molecules per cross section of fiber, and scattering correlation peaks revealing the ordering and overlap of 1d self-assembled polyelectrolyte species.

Metallo-supramolecular gels based on a multitopic cyclam bis-terpyridine platform.

The domain of soluble metallopolymers (i.e., polymers spontaneously obtained from the self-assembly of metal ions and polytopic bridging ligands) is promising for the construction of novel materials with perspectives in magnetic, redox, optical, electrochromic, or mechanical properties. We report the preparation and characterization of metallo-supramolecular gels based on a multitopic cyclam bis-terpyridine platform (CHTT) that are representative of a second generation of molecular gels exhibiting "intelligent" properties. The systems were characterized by UV-visible spectroscopy, cyclic voltammetry, viscosimetry, rheology, and small-angle neutron scattering (SANS). A basic analysis of the viscosity taking into account the interplay of hydrodynamic versus Brownian motions of 1D species is proposed. SANS data demonstrate the formation of rod-like species whose radius R and aspect ratio f = L/R were extracted. Rheological features are typical of weak gels having storage moduli of more than 1 order of magnitude weaker than for ordinary molecular organogels. These new molecular materials exhibit interesting properties: (i) chemosensitivity, with the gelation being dependent on the type of metal, stoichiometry M/CHTT, solvent, and counterion; (ii) electro-sensitivity: the Co(II)/CHTT system can be electrochemically and reversibly commuted between the gel (red) and liquid (green) states; and (iii) mechanical sensitivity, with the system being able to cycle from weakly to highly viscous states upon fast application/suppression of a shearing stress.

Structural and rheological properties of aqueous viscoelastic solutions and gels of tripodal cholamide-based self-assembled supramolecules.

A tripodal cholic steroid ( TCS+) derivative forms hydrogels in acidic conditions that are studied by the small-angle neutron scattering and rheometry techniques. The self-assembled systems exhibit particular scattering and flow properties unusual in the class of molecular gels. The scattering data show separated form- and structure-factor features with, respectively, a low-Q correlation peak and a large-Q secondary oscillation. A probable aggregation model is deduced involving 3 TCS+ molecules per cross-section of fibrillar aggregates packed in a tail-to-tail fashion. The fibers have monodisperse cross-sections (40 A diameter) and result from a versatile mechanism taking advantage of the free articulation of the three hydrophobic steroid pods ("umbrella-like" packing) around the N+ charge. The N+ charges are distributed at the periphery of the cylinders and give rise to a moderate linear charge density (nu approximately 0.16 e/A). The variation with concentration of the static scattering structure factor peak S(Q) reveals ordering properties typical of 1d polyelectrolytes. The fibers further organize into fractal clusters characterized by their scattering signature at low-Q and also by the exponent of the scaling of the elastic shear modulus with the concentration. It is suggested that the TCS+ polyion fibers extend under shear (or in a concentrated environment) by varying the angle between the pods along the fiber axis. Viscosity overshoots appear at the startup of shear flow experiments. Analogies with the phenomenology observed with DNA solutions are discussed.

Acid-base-driven interconversion between a mononuclear complex and supramolecular coordination polymers in a terpyridine-functionalized dioxocyclam ligand.

A polytopic cyclam-bis-terpyridine ligand has been used to accomplish an acid-base-triggered formation of either a mononuclear neutral complex or metallopolymers with Cu(2+) ions. A controlled interconversion between these two forms was achieved through the reversible displacement of a Cu(2+) cation from the macrocycle to the terpyridine units.

Distinct kinetic pathways generate organogel networks with contrasting fractality and thixotropic properties.

The kinetics of the isothermal transformation of sols, comprised of a low molecular-mass organogelator (LMOG) and an organic liquid, to their organogel phases have been followed by circular dichroism (CD), fluorescence, small angle neutron scattering (SANS), and rheological methods. The thixotropic properties (in the sense that severe shearing followed by rest lead to reestablishment of viscoelasticity) of the gels have been examined as well by rheological measurements. The compositions of the samples were either 5alpha-cholestan-3beta-yl N-(2-naphthyl) carbamate (CNC) in an n-alkane (n-octane or n-dodecane) or 3beta-cholesteryl N-(2-naphthyl) carbamate (CeNC) in ethyl acetate. Values of Df, the mass fractal dimension of the microcrystalline self-assembled fibrillar networks (SAFINs) in the gels, have been extracted from the kinetic data using a model developed by Dickinson (J. Chem. Soc., Faraday Trans. 1997, 93, 111). The Df values, 1.1-1.3 for the CeNC gels and 1.3-1.4 or 1.6-1.8 (depending on the temperature of incubation of the sol phase) for CNC gels, are consistent with the gel network structures observed by optical microscopy. In addition, comparison of the temperature dependence of both n (the Avrami component) and K (the Avrami "rate constant") for CeNC/ethyl acetate gelation with those reported previously for gelation of CNC/n-alkane sols demonstrate that the very small change of a single bond in CNC to a double bond in CeNC causes significant differences in their gelation abilities and gel properties. The rheological measurements on CNC/n-alkane gels with spherulitic SAFIN units, formed by incubation of their sols at < or =28 degrees C, indicate that they are thixotropic. Gels with the same chemical composition but formed by incubation of their sols at > or =30 degrees C, leading to fiberlike SAFIN units, remain liquidlike after shearing regardless of the periods they are at rest. The time-dependent viscoelastic properties of the gel networks are treated according to a stretched exponential model. The observations from these studies provide detailed insights into the mechanisms of formation of molecular organogel phases and demonstrate the extreme sensitivity of the SAFINs and viscoelastic properties of such organogels to slight modifications in LMOG structure or sample history.

Structural variations in a family of orthodialkoxyarenes organogelators.

A series of low mass organic gelators (LMOGS) 1 to 6 whose chemical structures have in common an orthodialkoxyarene feature was prepared in order to compare the shape of their fibrillar network as investigated by small-angle neutron scattering (SANS) experiments. All members of the family exhibit a pronounced tendency to bundle formation by merging isolated fibers in extended packets of average diameter >500 A. Variations of the 2D packing symmetry are observed from hexagonal to square orderings with close derivatives of the reference member 2,3-didecyloxyanthracene (DDOA). Networks in which the fraction of isolated fibers is significant enough to allow for their SANS identification are those for 6,7-dichloro-2,3-didecyloxyanthracene (Cl(2)DDOA) and 2,3-dodecyloxy-9,10-anthraquinone (5). For this latter, the monodispersity of the cross-sections (thickness=74 A) is remarkable and the rectangular shape (b/a approximately 0.12) accounts for a merging mechanism into anisotropic bundles (ribbons).

Molecular hydrogels from bile acid analogues with neutral side chains: network architectures and viscoelastic properties. Junction zones, spherulites, and crystallites: phenomenological aspects of the gel metastability.

Structural and rheological properties of hydrogels made up of neutral bile acid derivatives are studied. Complementary scattering, diffraction, and microscopy techniques provide a precise structural description of the network architecture and its variation as a function of concentration, aging time, composition of the solvent, and type of gelator. Two derivatives (TH and PH) are considered as presenting favorable scattering features to approach the issue of the competition between gelation versus crystallization. PH and TH fibers are semirigid cylinders with monodisperse cross-sections (R(0) = 92 and 80 A, respectively) involving 25 or 12 molecules per cross-sectional repeating unit along the fiber axis. Bundles are cross-links in the networks, and a scattering protocol is developed to determine the nodal and fibrillar fractions in the networks. The effects of alcoholic mixtures, dimethylsulfoxide, and temperature on the network properties are analyzed in terms of the bending modulus of the fibers, the degree of nonaffine character of the regime of deformation, and the dispersion degree of the nodal heterogeneities. It is shown that fibers are semirigid and the scaling laws of the elasticity of the gels with the concentration (exponent (5)/(2)) also support the theoretical context. Head-to-tail molecular arrangements are shown to be similar in the solid and gel phases. Birefringent textures show that spherulitic microdomains coexist in the network texture and are the seeds for a slow crystallization process. The whole pattern might be more general for numerous other self-assembled fibrillar networks found in molecular gels.

Organogels with Fe(III) complexes of phosphorus-containing amphiphiles as two-component isothermal gelators.

The properties of thermally reversible organogels in which the gelators consist of a phosphonic acid monoester, phosphonic acid, or phosphoric acid monoester and a ferric salt are probed by IR and NMR spectroscopies, optical microscopy, X-ray diffraction, rheology, and light and small-angle neutron scattering (SANS) techniques. This is one of a small number of two-component molecular gelator systems in which gelation can be induced isothermally. The data indicate that complexation between the phosphonate moieties and Fe(III) is accompanied by their in situ polymerization to form self-assembled fibrillar networks that encapsulate and immobilize macroscopically the organic liquid component. From SANS measurements, the cross-sectional radii of the cyclindrical fibers are ca. 15 A. The efficiencies of the gelators (based on the diversity of the liquids gelated, the minimum concentration of gelator required to make a gel at room temperature, and the temporal and thermal stabilities of the gels) have been determined. With a common ferric salt and liquid component, phosphonic acid monoesters are generally more efficient than phosphinic acids or phosphoric acid esters. Of the phosphonic acid monoesters, monophosphonates are better gelator components than bisphosphonates, and introduction of an omega-hydroxy group on the alkyl chain directly attached to phosphorus reduces significantly gelation ability. Several of the gels are stable for very long periods at room temperature. When heated, they revert to sols over wide temperature ranges. The structures of the gelator complexes and the mechanism of their formation and transformation to gels in selected liquids are examined as well.

Long-range molecular organization of an organic monolayer grafted on a mineral substrate.

Structured and functional materials are of the utmost importance for the development of microelectronic technology. We report on a method to obtain a highly ordered organic molecular layer on a mineral substrate. We took advantage of the regular array of reactive sites present at the single-crystal surface of topaz to perform a liquid-phase silanization reaction. The grazing-incidence diffraction technique was used to characterize the bare and covalently coated surfaces. The ordering of the monomolecular organic layer reproduces the perfect single-crystal structure of the cleaved surface over millimeter distances.

Ammonium lithocholate nanotubes: stability and copper metallization.

Ammonium lithocholate nanotubes (NHLC) have been prepared in alkaline ammonia solutions and exhibited remarkable monodisperse cross-sectional dimensions (external diameter = 52 nm) as shown by cryo-transmission electron microscopy measurements. A classical electroless metallic replication method was used with a single poly(ethylene-imine) PEI layer coating the negatively charged NHLC nanotubes. Short copper rods (external diameter ∼ 80 nm) were observed by scanning electron microscopy that corresponded to the original organic templates. The results obtained in acidic conditions are analyzed in terms of the lifetime of the self-assembled structures and formation of bundles of tubes. Dynamic light scattering measurements and optical observations show that the system in the presence of controlled amounts of hydrochloric acid is stable enough to account for a metallic replication in acidic conditions. An average apparent diffusion coefficient of the organic NHLC assemblies is extracted (∼ 9.8 × 10 nm s) in homogeneous suspensions where bundles have been dispersed by the acidic additions.

Gelation of perfluorinated liquids by N-alkyl perfluoroalkanamides.

Gels comprised of low-molecular-mass organic gelators (LMOGs), N-alkyl perfluoroalkanamides [F(CF2)(m)CONH(CH2)(n)H; FmNHn], and several perfluorinated liquids are described. The gelation ability of the amides has been compared to that of two analogous alkyl perfluoroalkanoates. The properties of these gels have been correlated with the N-alkyl and (to a lesser extent) perfluoroalkyl chain lengths in the FmNHn by X-ray diffraction, polarizing optical microscopy, infrared spectroscopy, and small-angle neutron scattering. The gels are thermally reversible and require generally very low concentrations (<2 wt %) of LMOG. Several of the gels have been stable at room temperature for >1 year, thus far. The incompatibility of the fluorocarbon and hydrocarbon segments causes the LMOGs to aggregate into lamellae within the fibrils that constitute the basic unit of the gel networks. IR spectroscopic studies of these gels indicate that additional ordering within the aggregate units is enforced by intermolecular H-bonding among amide groups.