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.

A new, molecular system for the light-driven production of hydrogen in aqueous solution was developed by combining a water-soluble tin porphyrin ([Sn(IV)Cl2TPPC], A) acting as photosensitizer with a cobalt-based proton-reduction catalyst ([Co(III)Cl(dmgH)2(py)], C). Under visible light illumination and with triethanolamine (TEOA) as electron source, the system evolves H2 for hours and is clearly catalytic in both dye and catalyst. A detailed analysis of the relevant redox potentials in combination with time-resolved spectroscopy resulted in the development of a Z-scheme type model for the flow of electrons in this system. Key intermediates of the proposed mechanism for the pathway leading to H2 are the porphyrin dye's highly oxidizing singlet excited state (1)A* (E ∼ +1.3 V vs NHE), its strongly reducing isobacteriochlorin analogue (E ∼ +0.95 V), and the Co(I) form of C (E ∼ -0.8 V), acting as catalyst for H2 formation. Among other results, the suggested reaction sequence is supported by the detection of a shortened excited-state lifetime for singlet (1)A* (τ ∼ 1.75 ns) in the presence of TEOA and the ultraviolet-visible detection of the Sn(IV) isobacteriochlorin intermediate at λ = 610 nm. Thus, a molecular, conceptually biomimetic, and precious-metal-free reaction chain was found which photocatalytically generates H2 in a 100% aqueous system from an electron donor with a high oxidation potential (E(TEOA) ∼ +1.1 V). On the other hand, at identical conditions, this photoreaction chain yields H2 markedly slower than a system using the photosensitizer [Re(I)(CO)3(bpy) (py)](+), probably due to the much longer excited-state lifetime (τ ∼ 120 ns) of the rhenium dye and better electron-transfer rates caused by its simple single-electron photoreduction chemistry.