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

Abstract

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 nm2 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. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

Surface anchored metal-organic frameworks as stimulus responsive antifouling coatings

“…This hypothesis is supported by the fact that the investigated MOF materials, while stable in clean water and artificial seawater, react strongly to phosphate buffer or protein-rich media resulting in a structural rearrangement or decomposition, respectively. Since short peptides and small biomolecules are sufficiently small to fit within the SURMOF pores with a size of 1.1 nm [26], we propose that extracellular polymeric substances (EPS) and other macromolecules secreted by bacteria diffuse into the porous support. This leads to a structural rearrangement and partly destruction within the crystalline coordination polymer and subsequently a loss of crystalline order.…”

Mechanistic Insights into Growth of Surface‐Mounted Metal‐Organic Framework Films Resolved by Infrared (Nano‐) Spectroscopy

“…Surface‐anchored films of metal‐organic frameworks (SURMOFs) can be synthesized in a straightforward manner by using a liquid phase layer‐by‐layer (LbL) synthesis approach 8, 9. The benefits of this method include the growth of highly homogeneous and oriented films at room temperature,8, 10 with diverse topologies,11, 12 enabling at the same time controlled mechanistic studies of MOF assembly13, 14 and guest‐induced framework changes 15, 16, 17…”

In Silico Discovery of High Deliverable Capacity Metal–Organic Frameworks

“…By calculating several typical linear organic linkers of SURMOF-2, 24 we find that the largest standard deviation of pairwise distance is 0.24Å. In this study we used a conservative standard deviation of pairwise distance of 0.5Å as our cutoff.…”