Monodomain Liquid Crystals of Two-Dimensional Sheets by Boundary-Free Sheargraphy.

Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials. However, liquid crystals are metastable and sensitive to external stimuli, such as flow, confinement, and electromagnetic fields, which cause their intrinsic polycrystallinity and topological defects. Here, we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy. The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets, which has the same optical polarized angle and intensity. The monodomain liquid crystals provide bidirectionally ordered skeletons, which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity. Furthermore, we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals. Topological structures with defect strength from - 2 to + 2 were realized. This work provides a facile methodology to study the structural order of soft matter at a macroscopic level, facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.

Brodie's or Hummers' Method: Oxidation Conditions Determine the Structure of Graphene Oxide.

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers' method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols "according to Brodie's/Hummers' method" is not sufficient.

Spin-Crossover Iron(II) Coordination Polymer with Fluorescent Properties: Correlation between Emission Properties and Spin State.

A spin-crossover coordination polymer [Fe(L1)(bipy)]n (where L = a N2O22- coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4'-bipyridine) was synthesized and exhibits a 48 K wide thermal hysteresis above room temperature (T1/2↑ = 371 K and T1/2↓ = 323 K) that is stable for several cycles. The spin transition was characterized using magnetic measurements, Mössbauer spectroscopy, and DSC measurements. T-dependent X-ray powder diffraction reveals a structural phase transition coupled with the spin transition phenomenon. The dimeric excerpt {(µ-bipy)[FeL1(MeOH)]2}·2MeOH of the coordination polymer chain crystallizes in the triclinic space group P1̅ and reveals that the packing of the molecules in the crystal is dominated by hydrogen bonds. Investigation of the emission properties of the complexes with regard to temperature shows that the spin crossover can be tracked by monitoring the emission spectra, since the emission color changes from greenish to a yellow color upon the low spin-to-high spin transition.

Synthesis of [Fe(Leq)(Lax)] n coordination polymer nanoparticles using blockcopolymer micelles.

Spin-crossover compounds are a class of materials that can change their spin state from high spin (HS) to low spin (LS) by external stimuli such as light, pressure or temperature. Applications demand compounds with defined properties concerning the size and switchability that are maintained when the compound is integrated into composite materials. Here, we report the synthesis of [Fe(Leq)(Lax)]n coordination polymer (CP) nanoparticles using self-assembled polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) micelles as template. Variation of the solvent (THF and toluene) and the rigidity of the axial ligand Lax (Lax = 1,2-di(pyridin-4-yl)ethane) (bpea), trans-1,2-di(pyridin-4-yl)ethene (bpee), and 1,2-di(pyridin-4-yl)ethyne) (bpey); Leq = 1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedionato)(2-)) allowed the determination of the preconditions for the selective formation of nanoparticles. A low solubility of the CP in the used solvent and a high stability of the Fe-L bond with regard to ligand exchange are necessary for the formation of composite nanoparticles where the BCP micelle is filled with the CP, as in the case of the [FeLeq(bpey)] n @BCP. Otherwise, in the case of more flexible ligands or ligands that lead to high spin complexes, the formation of microcrystals next to the CP-BCP nanoparticles is observed above a certain concentration of [Fe(Leq)(Lax)] n . The core of the nanoparticles is about 45 nm in diameter due to the templating effect of the BCP micelle, independent of the used iron complex and [Fe(Leq)(Lax)] n concentration. The spin-crossover properties of the composite material are similar to those of the bulk for FeLeq(bpea)] n @BCP while pronounced differences are observed in the case of [FeLeq(bpey)] n @BCP nanoparticles.

Synthesis of [Fe(L)(bipy)]n spin crossover nanoparticles using blockcopolymer micelles.

Nowadays there is a high demand for specialized functional materials for specific applications in sensors or biomedicine (e.g. fMRI). For their implementation in devices, nanostructuring and integration in a composite matrix are indispensable. Spin crossover complexes are a highly promising family of switchable materials where the switching process can be triggered by various external stimuli. In this work, the synthesis of nanoparticles of the spin crossover iron(ii) coordination polymer [Fe(L)(bipy)]n (with L = 1,2-phenylenebis(iminomethylidyne)bis(2,4-pentanedionato)(2-) and bipy = 4,4'-bipyridine) is described using polystyrene-poly-4-vinylprididine blockcopolymer micelles as the template defining the final size of the nanoparticle core. A control of the spin crossover properties can be achieved by precise tuning of the crystallinity of the coordination polymer via successive addition of the starting material Fe(L) and bipy. By this we were able to synthesize nanoparticles with a core size of 49 nm and a thermal hysteresis loop width of 8 K. This is, to the best of our knowledge, a completely new approach for the synthesis of nanoparticles of coordination polymers and should be easily transferable to other coordination polymers and networks. Furthermore, the use of blockcopolymers allows a further functionalization of the obtained nanoparticles by variation of the polymer blocks and an easy deposition of the composite material on surfaces via spin coating.