Graphene hybrid materials? The role of graphene materials in the final structure of hydrogels.

Graphene (G), graphene oxide (GO) and graphene quantum dots (GQDs) have been introduced into a three-dimensional polymeric network based on polyacrylamide in order to ascertain the role of each nanomaterial in hydrogels. The hydrogel structure is not affected by the introduction of GQDs, since these nanoparticles do not form part of the polymeric network. G and GO modify the structure of the hydrogels but in a different way. GO seems to interact by hydrogen bonding to form non-homogeneous gels in which the mechanical properties are not markedly improved. However, G takes an active part in the formation of the polymeric network, which leads to improved mechanical properties and stability of the final material to give rise to truly hybrid hydrogels and not mere two-phase composite materials.

Physically Cross-Linked Hydrogel Based on Phenyl-1,3,5-triazine: Soft Scaffold with Aggregation-Induced Emission.

A phenyltriazine compound has been used for the first time as a monomer in the construction of a hydrogel. This physically cross-linked soft material showed blue fluorescence when excited under UV-light. Polymer formation and intermolecular H-bonds arising from triazine moieties operate as aggregation-induced emission (AIE) mechanisms. The combination of soft materials and AIE properties expands the applications of these materials. As a proof of concept, two luminescent dyes have been incorporated into the hydrogel to produce a white-light-emitting material.

Graphene Quantum Dot-Aerogel: From Nanoscopic to Macroscopic Fluorescent Materials. Sensing Polyaromatic Compounds in Water.

Fluorescence based on quantum confinement is a property restricted to the nanoscopic range. The incorporation of nanoparticles in a three-dimensional polymeric network could afford macroscopic scaffolds that show nanoscopic properties. Moreover, if these scaffolds are based on strong bonds, the stability of the resulting materials can be preserved, thus enhancing their final applications. We report for the first time the preparation of a graphene quantum dot (GQD) composite based on a cationic covalent network. This new material has unusual features: (i) the final composite remains stable after several swelling-deswelling cycles, thus demonstrating strong interactions between GQDs and the polymeric material, and therefore it could be used as a portable system. (ii) Fluorescence emission in the composite and in solution is quasi-independent to the excitation wavelength. (iii) However, and in contrast to the behavior observed in GQD solutions, the fluorescence of the composite remains unaltered over a wide pH range and in the presence of different ions commonly found in tap water. (iv) Fluorescence quenching is only observed as a consequence of molecules that bear aromatic systems, and this could be applied to the preparation of in situ water sensors.

Synthesis and characterization of metallodendritic palladium-biscarbene complexes derived from 1,1'-methylenebis(1,2,4-triazole).

The syntheses of first generation dendritic compounds bearing 1,1'-alkane-1,1-diylbis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)palladium(II) dibromide on the periphery are described. The metallabiscarbene moieties have also been studied separately from the dendrimer. These compounds display a non-symmetric boat-to-boat conformational equilibrium that has axial and equatorial arrangements. The predominance of the axial conformer in the equilibrium is supported by DFT calculations. The X-ray solid state structures of axial conformers of 3-hydroxy- and 3-mesyloxy-1,1'-propane-1,1-diylbis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)palladium(II) dibromide are reported. These complexes display modest catalytic activity in the Heck reaction with activated aryl bromides and the dendritic catalysts were more active than the corresponding non-dendritic mononuclear species, a finding indicative of a cooperative effect.

Control of surface functionality in poly(phenylenevinylene) dendritic architectures.

The efficient synthesis of new asymmetric poly(phenylenevinylene) dendritic macromolecules using a stepwise convergent-growth approach is described. By an iterative methodology that made use of the Horner-Wadsworth-Emmons (HWE) reaction, dendrons and dendrimers up to the third generation, with eight different functional groups located at the periphery, were prepared in good yields. Both the number and placement of functionalities can be accurately controlled to afford a large variety of dendritic architectures.

Electron transfer in nonpolar solvents in fullerodendrimers with peripheral ferrocene units.

Two new fullerodendrimers, with two and four ferrocene units on their periphery, have been synthesized by 1,3-dipolar cycloaddition reactions between the corresponding azomethine ylides and C(60). These new compounds have been studied by using cyclic voltammetry and UV/Vis spectroscopy. Weak intramolecular interactions between the fullerene cage and the ferrocene groups have been found. The photochemical events of both fullerene-ferrocene dendrimers have been probed by means of steady-state and time-resolved techniques. The steady-state emission intensities of the fulleropyrrolidine-ferrocene dendrimers 1 and 2 were found to be quenched relative to the N-methylfulleropyrrolidine without substituents that was used as a model. The nanosecond transient absorption spectral studies revealed efficient charge separation in both systems, even in toluene. The lifetimes of the (C(60))(*-)-(dendron)(*+) are higher for the second-generation fullerodendrimer (with four ferrocene units) and they are of the order of tens of nanoseconds in toluene and hundreds of nanoseconds in polar solvents.

Synthesis and photoluminescent properties of 1,1'-binaphthyl-based chiral phenylenevinylene dendrimers.

New chiral, soluble binaphthyl derivatives that incorporate stilbenoid dendrons at the 6,6'-positions have been prepared. The synthesis of the new enantiopure dendrimers was performed in a convergent manner by Horner-Wadsworth-Emmons (HWE) reaction of the appropriately functionalized 1,1'-binaphthyl derivative (R)-1 and the appropriate dendrons (R)(2n)G(n)-CHO. Different electroactive units were incorporated in the peripheral positions of the dendrons in order to tune both the optical and electrochemical behavior of these systems. Fluorescence measurements on the chiral dendrimers reveal a strong emission with maxima between 409 and 508 nm depending upon the substitution pattern. Finally, the redox properties of the dendrimers were determined by cyclic voltammetry, showing the influence of the functional groups at the peripheral positions of the dendrimer on the redox behavior of these systems.

Synthesis of novel cross-conjugated dendritic fluorophores containing both phenylenevinylene and phenyleneethynylene moieties.

New dendrons and dendrimers with dendritic arms composed of alternate phenyleneethynylene and phenylenevinylene moieties have been efficiently synthesized using orthogonal and convergent syntheses that combine Sonogashira and Horner-Wadsworth-Emmons reactions. Two different iterative routes have been developed that allow specific control over the placement of double and triple bonds within the interior of the dendrimers. A preliminary study of the UV and photoluminescence (PL) properties of the resulting compounds is also described. All of the examples prepared are blue-luminescent.