Twin monomers [Mg(2‐OCH2‐cC6H4O)][L]0.8 (2, L=diglyme) and [Mg(2‐OCH2‐cC6H4O)][L]0.66 (3, L=tmeda) form by their thermal polymerization interpenetrating organic‐inorganic hybrid materials in a straightforward manner. Carbonization (Ar) followed by calcination gave porous MgO (2: surface area 200 m2 g−1, 3: 400 m2 g−1), which showed in catalytic studies towards Meerwein‐Ponndorf‐Verley reductions excellent yields and complete conversions for cyclohexanone and benzaldehyde. However, with crotonaldehyde a mixture of C4–C8 compounds was obtained. When MgO was exposed to air then primarily crotyl alcohol was formed. The range of applications could be easily extended by twin polymerization of 3 in presence of [Cu(O2CCH2O(CH2CH2O)2Me)2] (4) or [Ag(O2CCH2‐cC4H3S)(PPh3)] (5), resulting in the formation of nanoparticle‐decorated porous CuO@MgO or Ag@MgO materials, which showed high catalytic reactivity towards the reduction of methylene blue.

The combination of in situ pair distribution function (PDF) analysis and small‐angle X‐ray scattering (SAXS) enables analysis of the formation mechanism of metal oxido nanoclusters and cluster–solvent interactions as they take place. Herein, we demonstrate the method for the formation of clusters with a [Bi38O45] core. Upon dissolution of crystalline [Bi6O5(OH)3(NO3)5]⋅3 H2O in DMSO, an intermediate rapidly forms, which slowly grows to stable [Bi38O45] clusters. To identify the intermediate, we developed an automated modeling method, where smaller [BixOy] structures based on the [Bi38O45] framework are tested against the data. [Bi22O26] was identified as the main intermediate species, illustrating how combined PDF and SAXS analysis is a powerful tool to gain insight into nucleation on an atomic scale. PDF also provides information on the interaction between nanoclusters and solvent, which is shown to depend on the nature of the ligands on the cluster surface.

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The combination of in situ pair distribution function (PDF) analysis and small-angle X-rays cattering (SAXS) enables analysis of the formation mechanism of metal oxido nanoclusters and cluster-solvent interactions as they take place. Herein, we demonstrate the method for the formation of clusters with a[ Bi 38 O 45 ]c ore.U pon dissolution of crystalline [Bi 6 O 5 (OH) 3 (NO 3 ) 5 ]•3 H 2 OinDMSO,anintermediate rapidly forms,w hich slowly grows to stable [Bi 38 O 45 ]c lusters.T o identify the intermediate,w ed eveloped an automated modeling method, where smaller [Bi x O y ]s tructures based on the [Bi 38 O 45 ]framework are tested against the data. [Bi 22 O 26 ]w as identified as the main intermediate species,i llustrating how combined PDF and SAXS analysis is ap owerfult ool to gain insight into nucleation on an atomic scale.P DF also provides information on the interaction between nanoclusters and solvent, whichisshown to depend on the nature of the ligands on the cluster surface.