Mixed-metal metal-organic frameworks.

Mixed-metal MOFs are metal-organic frameworks that contain at least 2 different metal ions as nodes of their frameworks. They are prepared relatively easily by either a one-pot synthesis with a synthesis mixture containing the different metals, or by a post-synthetic ion-exchange method by soaking a monometallic MOF in a concentrated solution of a different (but compatible) metal-ion. More difficult is the accurate characterization of these materials.

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach.

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 from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases.

A series of sulfonic acid functionalized mixed-linker DUT-4 analogues: synthesis, gas sorption properties and catalytic performance.

In this work, we present the successful synthesis of a series of sulfonic acid functionalized mixed-linker metal-organic frameworks (MOFs) having the DUT-4 topology by using different ratios of 2,6-naphthalenedicarboxylic acid (H-NDC) and 4,8-disulfonaphthalene-2,6-dicarboxylic acid (H-NDC-2SOH) in one-pot reactions. The obtained materials were fully characterized and their CO adsorption properties at low and high pressures were studied and compared with those of the pristine DUT-4 material. Generally, the CO adsorption capacities range from 3.

Sensing the framework state and guest molecules in MIL-53(Al) via the electron paramagnetic resonance spectrum of V dopant ions.

X-ray diffraction (XRD) and electron paramagnetic resonance spectroscopy (EPR) were combined to study the structural transformations induced by temperature, pressure and air humidity of the "breathing" metal-organic framework (MOF) MIL-53(Al), doped with paramagnetic V ions, after activation. The correlation between in situ XRD and thermogravimetric analysis measurements showed that upon heating this MOF in air, starting from ambient temperature and pressure, the narrow pore framework first dehydrates and after that makes the transition to a large pore state (lp). The EPR spectra of V[double bond, length as m-dash]O molecular ions, replacing Al-OH in the structure, also allow to distinguish the as synthesized, hydrated (np-h) and dehydrated narrow pore (np-d), and lp states of MIL-53(Al).

Microwave induced "egg yolk" structure in Cr/V-MIL-53.

Using a one pot microwave procedure, mixed-metal "egg yolk" MOFs are created, with a core of (Cr/V)-MIL-53 and a shell of Cr-MIL-53. In contrast, the solvothermal method produces homogeneous mixed-metal MOFs. The influence of Cr and V on the flexibility and breathing was studied via T-XRPD and CO adsorption measurements.

Enhanced gas sorption and breathing properties of the new sulfone functionalized COMOC-2 metal organic framework.

A new sulfone functionalized vanadium metal-organic framework (MOF), denoted as SO2-COMOC-2, has been synthesized solvothermally. Its structural and gas sorption properties towards CO2 and CH4 have been evaluated and compared to those of the pristine COMOC-2 material. The SO2-COMOC-2 shows a remarkable increase in CO2 capacity at ambient pressure (2.

Multi-frequency (S, X, Q and W-band) EPR and ENDOR Study of Vanadium(IV) Incorporation in the Aluminium Metal-Organic Framework MIL-53.

Doping the well-known metal-organic framework MIL-53(Al) with vanadium(IV) ions leads to significant changes in the breathing behaviour and might have repercussions on the catalytic behaviour as well. To understand the properties of such a doped framework, it is necessary to determine where dopant ions are actually incorporated. Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are applied to reveal the nearest environment of the paramagnetic vanadium(IV) dopant ions.