Intercalation in Layered Metal–Organic Frameworks: Reversible Inclusion of an Extended π-System

Abstract

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. Intercalation of an organic dye, DXP, leads to a reversible tilting of the planes, demonstrating the huge potential of these surface-anchored MOFs for the intercalation of large, planar molecules.

Surface anchored metal-organic frameworks as stimulus responsive antifouling coatings

“…Control experiments in which the SURMOFs are exposed to suspensions of C. marina, a solution of extracellular polymeric substance (EPS) secreted by C. marina, and supernatants of bacteria suspensions indeed reveal that there are small concentrations of Cu 2+ in the corresponding solutions (Additional file 1: Figure S1). Similar experiments using SURMOFs where the Cu ions are replaced by Zn 2+ ions [27] showed no particular effect on the bacteria.…”

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…”

Metal–organic framework growth at functional interfaces: thin films and composites for diverse applications

“…11 As a direct result of this structural and functional diversity, degree of rational design at the molecular level and relative ease 40 of preparation, interest and research in MOFs has followed an upward exponential trajectory over the last 10 -15 years. 5 The vast majority of studies this far have involved the synthesis, characterisation and to some extent optimisation of new functional materials for wide-ranging applications in (but not 45 limited to) sequestration and storage of fuel and environmental gases 12, 13 , heterogeneous catalysis 14 , molecular separation (e.g. gases 15 , enantiomers 16 ), drug delivery 17 , biomedical imaging 18 and sensing.…”

“…24 40 Addition of Au-supported SAMs to a standard solvothermal MOF synthesis is not a practical method to prepare MOF thin films (or composites) given the relative fragility of the SAM/Au interface at the elevated temperatures typically employed. In order to circumvent this difficulty, a number of alternative 45 synthesis strategies have been developed for the preparation of MOF films on SAMs; methods which have been extended to prepare diverse MOF composite materials. Two of the most successful techniques are based on immersion of SAMs into aged precursor solutions containing both the metal and ligand 50 components 33,37 or by employing a liquid-epitaxial layer-by-layer (LbL) approach to MOF growth.…”