We report the use of two earth abundant molybdenum sulfide-based cocatalysts, Mo3S132– clusters and 1T-MoS2 nanoparticles (NPs), in combination with the visible-light active metal–organic framework (MOF) MIL-125-NH2 for the photocatalytic generation of hydrogen (H2) from water splitting. Upon irradiation (λ ≥ 420 nm), the best-performing mixtures of Mo3S132–/MIL-125-NH2 and 1T-MoS2/MIL-125-NH2 exhibit high catalytic activity, producing H2 with evolution rates of 2094 and 1454 μmol h–1 gMOF–1 and apparent quantum yields of 11.0 and 5.8% at 450 nm, respectively, which are among the highest values reported to date for visible-light-driven photocatalysis with MOFs. The high performance of Mo3S132– can be attributed to the good contact between these clusters and the MOF and the large number of catalytically active sites, while the high activity of 1T-MoS2 NPs is due to their high electrical conductivity leading to fast electron transfer processes. Recycling experiments revealed that although the Mo3S132–/MIL-125-NH2 slowly loses its activity, the 1T-MoS2/MIL-125-NH2 retains its activity for at least 72 h. This work indicates that earth-abundant compounds can be stable and highly catalytically active for photocatalytic water splitting, and should be considered as promising cocatalysts with new MOFs besides the traditional noble metal NPs.

The reaction of nitrous oxide (N2O) with Nheterocyclic olefins (NHOs) results in cleavage of the N-O bond and formation of azo-bridged NHO dimers. The latter represent very electron-rich compounds with a low ionization energy. Cyclic voltammetry studies show that the dimers classify as a new organic super-electrondonors, with a reducing power similar to what is found for tetraazafulvalene derivatives. Mild oxidants are able to convert the neutral dimers into radical cations, which can be isolated. Further oxidation gives stable dications.

Deprotonation of cationic azo dyes results in the formation of aminyl biradicals.

Iron­(II) cage complexes with terminal 4-pyridyl groups can be incorporated in metal–organic frameworks (MOFs) via solvent-assisted ligand exchange (SALE). Paddle-wheeled MOFs with N,N′-di-4-pyridylnaphthalenetetracarboxydiimide pillars were used as starting materials. Pillar exchange was nearly quantitative, despite the fact that the cage complexes are long (∼15 Å) and sterically demanding. The reactions provide products of high crystallinity, and the structures of daughter MOFs were determined by single crystal X-ray diffraction. The crystallographic analyses showed that some of the SALE experiments led to topological changes of the MOF structures.