Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study.

Understanding host-guest interactions is one of the key requirements for adjusting properties in metal-organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of 13C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. The 13C MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water < diethylamine ≈ 2-aminopyridine < 3-aminopyridine. Assignments were done by exploiting distance sum relations derived from spin-lattice relaxation data and 13C{1H} REDOR spectral editing. The experimental data were used to validate NMR shifts computed for the Cr-MIL-101 derivatives, which contain Cr3O clusters with magnetically coupled metal centers. While both approaches provide an unequivocal assignment and the arrangement of the guests at the open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure-property relationships.

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.