In order to reliably predict and understand the breathing behavior of highly flexible metal-organic frameworks from thermodynamic considerations, an accurate estimation of the free energy difference between their different metastable states is a prerequisite. Herein, a variety of free energy estimation methods are thoroughly tested for their ability to construct the free energy profile as a fun...

In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting f...

We have developed a generic two-step post-functionalisation technique for transforming amino-functionalised MOFs into their isocyanate analogues. The first part of the synthetic pathway consists in the conversion of the amino moieties into azido groups. Next, the thermal activation of these azido groups leads to nitrene species that can react with carbon monoxide to yield the desired products. ...

The concept of biomineralization implies control of crystallization in terms of phase and orientation through interactions with organic macromolecules. This is of particular interest for the synthesis of biomimetic materials. If one strives to mimic the enormous structure-directing power of biomineralization in materials science, an artificial organic interface is needed. For example, functiona...

The robust gallium carboxylate Ga(OH)(btec)·0.5H2O (MIL-61) is selected as a parent MOF to prepare Ln-MIL-61 by PSM. This work investigates the luminescence of Ln-doped MIL-61 (Ln = Eu3+, Tb3+, Sm3+, Dy3+) in the visible light region. Upon 314 nm excitation, the emission spectra of Eu-MIL-61, Tb-MIL-61 and Eu/Tb-MIL-61 all exhibit their respective strong sharp emission bands. However, Sm-MIL-61...