The Ce(NO₃)₃·6H₂O/H₂TDC/CH₃COOH/CH₃CN (H₂TDC = 2,5-thiophenedicarboxylic acid) chemical system was studied under solvothermal reaction conditions. Four different phases that successively crystallized as a function of time were observed. Three coordination networks, [Ce^IV(TDC)(CH₃COO)₂] (1), [Ce^III₄(TDC)₃(CH₃COO)₆] (2a), and [Ce^III(TDC)(CH₃COO)] (3), could be isolated as orange, beige, and white phase pure products, respectively, and their crystal structures were resolved from powder X-ray diffraction data. Another crystalline compound (2b) was observed in situ, which seems to be structurally related to compound 2a. Compound 2a is a metal–organic framework (MOF) with a pore size of ∼3 Å. The use of Ce^III(NO₃)₃ as the starting material, the different colors of the products, and the crystal structures indicated a peculiar redox behavior with a Ce(III)–Ce(IV)–Ce(III) redox transformation during product formation of 1, 2a, and 3. The oxidation states of 1 and 3 were confirmed by ex situ X-ray absorption near-edge structure (XANES) measurements, and the crystallization process was followed using quasi-simultaneous in situ powder X-ray diffraction (PXRD) and X-ray absorption spectroscopy (XAS) measurements. During the reaction, the consecutive crystallization in the order 1–2b–3 was clearly observed. Linear combination fitting (LCF) of the in situ XAS data also affirmed the formation of the title compounds.

An optimized workflow for the discovery of new porous materials was developed, combining high-throughput (HT) synthesis with automated powder X-ray diffraction (PXRD), high-throughput CO₂ sorption analysis and three-dimensional electron diffraction (3D ED). This led to the discovery of CAU-73, a new yttrium-based microporous metal–organic framework.

We present serial electron diffraction with tilt (t-SerialED), a method for fast autonomous phase and structural analysis of beam-sensitive, nano-sized polycrystalline materials. Unlike traditional workflows collecting datasets crystal by crystal, t-SerialED acquires datasets using a batch-by-batch approach, which speeds up the data acquisition. t-SerialED combines robust indexing from 3D reciprocal space with still-shot integration and merging methods from serial crystallography. t-SerialED enables high-throughput analysis of beam-sensitive, multi-phase mixtures across a wide range of materials, from nanoporous frameworks to pharmaceutical compounds. By resolving key challenges in serial crystallography such as indexing and preferred orientation, this method enables precise structure determination, including the visualization of guest molecules and non-covalent interactions like hydrogen bonding and proton charge transfer. Demonstrated on a range of samples from nanoporous materials to pharmaceuticals, t-SerialED expands the capabilities of serial chemical crystallography from single-phase to complex multi-phase systems. It can become a complementary method to traditional crystallography methods, offering a robust solution for routine quantitative phase analysis and structure determination.