Surface anchored metal-organic frameworks as stimulus responsive antifouling coatings.

Surface-anchored, crystalline and oriented metal organic frameworks (SURMOFs) have huge potential for biological applications due to their well-defined and highly-porous structure. In this work we describe a MOF-based, fully autonomous system, which combines sensing, a specific response, and the release of an antimicrobial agent. The Cu-containing SURMOF, Cu-SURMOF 2, is stable in artificial seawater and shows stimulus-responsive anti-fouling properties against marine bacteria.

Post-synthetic modification of metal-organic framework thin films using click chemistry: the importance of strained C-C triple bonds.

In this work, we demonstrate that strain-promoted azide-alkyne cycloaddition (SPAAC) yields virtually complete conversion in the context of the post-synthetic modification (PSM) of metal-organic frameworks (MOFs). We use surface-anchored MOF (SURMOF) thin films, [Zn2(N3-bdc)2(dabco)], grown on modified Au substrates using liquid-phase epitaxy (LPE) as a model system to first show that, with standard click chemistry, presently, the most popular method for rendering additional functionality to MOFs via PSM, quantitative conversion yields, cannot be reached. In addition, it is virtually impossible to avoid contaminations of the product by the cytotoxic Cu(I) ions used as a catalyst, a substantial problem for applications in life sciences.

A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy.

A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 × 3 nm(2) is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu(++))(2)- carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry.

Surface-anchored MOF-based photonic antennae.

The loading of a metal-organic framework (MOF), [Cu(3)(btc)(2)xH(2)O] HKUST-1, with europium β-diketonate complexes is studied with the goal to using the porous molecular framework as a photonic antenna. Whereas loading of HKUST-1 powder particles produced via the conventional solvothermal synthesis method was strongly hindered, for HKUST-1 SURMOFs, thin MOF films fabricated using the liquid phase epitaxy method, a high filling factor can be achieved. The optical properties of the HKUST-1-MOFs before and after loading were analysed with the aid of luminescence spectroscopy.

The biocompatibility of metal-organic framework coatings: an investigation on the stability of SURMOFs with regard to water and selected cell culture media.

Highly porous thin films based on a [Cu(bdc)(2)](n) (bdc = benzene-1,4-dicarboxylic acid) metal-organic framework, MOF, grown using liquid-phase epitaxy (LPE) show remarkable stability in pure water as well as in artificial seawater. This opens the possibility to use these highly porous coatings for environmental and life science applications. Here we characterize in detail the stability of these SURMOF 2 thin films under aqueous and cell culture conditions.

Post-synthetic modification of epitaxially grown, highly oriented functionalized MOF thin films.

Thin films of MOFs grown on solid substrates offer a huge potential with regard to tailoring the properties of a surface, in particular if used in connection with post-synthesis modification (PSM). Here, we report on the PSM of surface-supported crystalline MOFs, with target molecules using an amine-based coupling strategy.

Intercalation in layered metal-organic frameworks: reversible inclusion of an extended π-system.

We report the synthesis of layered [Zn(2)(bdc)(2)(H(2)O)(2)] and [Cu(2)(bdc)(2)(H(2)O)(2)] (bdc = benzdicarboxylate) metal-organic frameworks (MOF) carried out using the liquid-phase epitaxy approach employing self-assembled monolayer (SAM) modified Au-substrates. We obtain Cu and Zn MOF-2 structures, which have not yet been obtained using conventional, solvothermal synthesis methods. The 2D Cu(2+) dimer paddle wheel planes characteristic for the MOF are found to be strictly planar, with the planes oriented perpendicular to the substrate.