Single‐crystal electron diffraction has shown to be powerful for structure determination of nano‐ and submicron‐sized crystals that are too small to be studied by single‐crystal X‐ray diffraction. However, it has been very challenging to obtain high quality electron diffraction data from beam sensitive crystals such as metal–organic frameworks (MOFs). It is even more difficult to locate guest species in the pores of MOF crystals. Here, we present synthesis of a novel porous cobalt MOF with 1D channels, [Co2(Ni‐H4TPPP)]⋅2 DABCO⋅6 H2O, (denoted Co‐CAU‐36; DABCO=1,4‐diazabicyclo[2.2.2]octane), and its structure determination using continuous rotation electron diffraction (cRED) data. By combining a fast hybrid electron detector with low sample temperature (96 K), high resolution (0.83–1.00 Å) cRED data could be obtained from eight Co‐CAU‐36 crystals. Independent structure determinations were conducted using each of the eight cRED datasets. We show that all atoms in the MOF framework could be located. More importantly, we demonstrate for the first time that organic molecules in the pores, which were previously difficult to find, could be located using the cRED data. A comparison of eight independent structure determinations using different datasets shows that structural models differ only on average by 0.03(2) Å for the framework atoms and 0.10(6) and 0.16(12) Å for DABCO and water molecules, respectively.

A highly porous and stable Zr-MOF containing a planar porphyrin-based tetraphosphonic acid was synthesized and characterized regarding its sorption properties and chemical stability.

The new porphyrin-based tetraphosphonic acid (Ni-HTPPP) was employed in the synthesis of four isostructural MOFs of composition [M(Ni-HTPPP)(HO)], denoted CAU-29 (M = Mn, Co, Ni, Cd). Ni-CAU-29 was thoroughly characterized regarding its thermal and chemical stability as well as for proton conductivity.

A precursor method has been developed to synthesize Ce(iv) MOFs that could not be prepared directly from Ce(iv) salts. Starting from Ce clusters, two Ce-UiO-66 analogues and four tetracarboxylate-based Ce(iv) MOFs could be synthesized. The applied method facilitates framework formation by evading reactive individual Ce(iv)-ions thereby paving the way for further development of Ce-MOFs.