Metal-organic frameworks (MOF) are becoming a more and more important class of functional materials. Yet, very often, the synthesis of MOFs is not easy to control and requires a profound knowledge and experience in solid state chemistry. One of the most frequently used metal connectors is the so-called 'paddle-wheel' (PW) unit, which is a well-known molecular compound type in inorganic coordination chemistry. Depending on the ligands, the geometry of PWs strictly directs the assembly of ordered networks. This review focuses on the question, to what extent ordered network structures can be accessed by typical molecular syntheses in solution, starting from molecular PW complexes to ordered macromolecules, finite cage compounds and finally, three-dimensional superstructures.

The dinuclear complex cis-[(CH3CN)6Mo2(O2C-Fc)2(BF4)2] (2) and the square-shaped compound [(CH3CN)4Mo2(O2C-Fc-CO2)­(BF4)2]4 (3) can be synthesized by reacting [Mo2(NCCH3)10]­[BF4]4 (1) with the corresponding ferrocenemonocarboxylic and -dicarboxylic acids (FMCA and FDCA) in a mixture of CH3CN and THF. The reaction of [Mo2(NCCH3)10] [BF4]4 (1) with tetrafluoroterephthalic acid in propionitrile solution affords the square-shaped complex [(CH3CH2CN)4Mo2(O2C-C6F4-CO2)­(BF4)2]4 (4). The interaction of 1 with 5-fluoroisophthalic acid using acetonitrile as solvent results in the isolation of the triangular complex [(CH3CN)6Mo2(m-bdc-F)(BF4)2]3 (5). The products 2–5 have been characterized by single-crystal X-ray diffraction, NMR spectroscopy (1H, 11B, 13C, 19F), IR spectroscopy, elemental analysis, TG-MS, and UV–vis spectroscopy measurements.

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The treatment of the dimeric paddle-wheel (PW) compound [Mo(2)(NCCH(3))(10)][BF(4)](4)1 with oxalic acid (0.5 equiv.), 1,1-cyclobutanedicarboxylic acid (1 equiv.), 5-hydroxyisophthalic acid (1 equiv.) (m-bdc-OH) or 2,3,5,6-tetrafluoroterephthalic acid (0.5 or 1 equiv.) leads to the formation of macromolecular dicarboxylate-linked (Mo(2))(n) entities (n = 2, 3, 4). The structure of the compounds depends on the length and geometry of the organic linkers. In the case of oxalic acid, the dimeric compound [(CH(3)CN)(8)Mo(2)(OOC-COO)Mo(2)(NCCH(3))(8)][BF(4)](6)2 is formed selectively, whereas the use of 2,3,5,6-tetrafluoroterephthalic acid affords the square-shaped complex [(CH(3)CN)(6)Mo(2)(OOC-C(6)F(4)-COO)](4)[BF(4)](8)3. Bent linkers with a bridging angle of 109° and 120°, respectively, lead to the formation of the molecular loop [(CH(3)CN)(6)Mo(2)(OOC-C(4)H(6)-COO)](2)[BF(4)](4)4 and the bowl-shaped molecular triangle [(CH(3)CN)(6)Mo(2)(m-bdc-OH)](3)[BF(4)](6)5. All complexes are characterised by X-ray single crystal diffraction, NMR ((1)H, (11)B, (13)C and (19)F) and UV-Vis spectroscopy.

Systematic investigation of filtrates and filter residues resulting from a 24 h treatment of metakaolin in different alkaline solutions were performed. On filtered metakaolin particles, inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements reveal an enrichment of iron and titanium, which suggests an inhomogeneous distribution of these cations. Since the SiO2/Al2O3 ratio remains constant in all filter residues examined, the dissolution of the Si and Al monomers is congruent. Structural differences, identified by attenuated total reflection–Fourier transform infrared spectroscopy (ATR-FTIR) as a consequence of alkali uptake, influence the X-ray scattering contribution of metakaolin, and thus quantifications with the partial or no known crystal structure (PONKCS) method. This leads to deviations between the degree of reaction calculated from Si and Al solubility from filtrate and that quantified by quantitative powder X-ray diffraction (QPXRD) using the filter residue. Nevertheless, the described changes do not cause a shift in the X-ray amorphous hump in case of congruent dissolution, and thus allow the quantification of the metakaolin before and after dissolution with the same hkl-phase model.