F. Vermoortele

The synthesis of titanium-carboxylate metal-organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium-based MOFs by the use of titanocene dichloride to synthesize COK-69, the first breathing Ti MOF, which is built up from trans-1,4-cyclo-hexanedicarboxylate linkers and an unprecedented [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster. The photoactive properties of COK-69 were investigated in depth by proton-coupled electron-transfer experiments, which revealed that up to one Ti-IV center per cluster can be photoreduced to Ti-III while preserving the structural integrity of the framework. The electronic structure of COK-69 was determined by molecular modeling, and a band gap of 3.77 eV was found.

The catalytic activity of the Zr-benzenedicarboxylate (Zr-BDC) UiO-66 can be drastically increased in the absence of part of the linkers, as it removes the full coordination of the framework metal ions and leads to open sites. As a result, metal centers become more accessible and thus more active for Lewis acid catalysed reactions. Addition of modulators (MDL) to the synthesis mixture can create more linker deficiencies (Vermoortele et al., J Am Chem Soc, 2013, 135, 11465) and can lead to a significant increase of the catalytic activity due to the creation of a larger number of open sites. In this paper, we rationalize the function of the modulators under real synthesis conditions by the construction of free energy diagrams. The UiO-66 type materials form a very appropriate test case as the effect of addition of modulators HCl and trifluoroacetate (TFA) has been intensively investigated experimentally for the synthesis process and post-synthetic thermal activation. In synthesis conditions, direct removal of BDC linkers requires a high free energy but replacement of such linker by one or more TFA species might occur especially at high TFA:BDC ratios in the reaction mixture. The presence of HCl furthermore enhances the creation of defect structures. Post-synthesis activation procedures at higher temperatures lead to a substantial removal of the species coordinated to the Zr bricks creating open metal sites. A mechanistic pathway is presented for the dehydroxylation process of the hexanuclear Zr cluster. For the citronellal cyclization, we show that the presence of some residual TFA in the structure may lead to faster reactions in complete agreement with experiment. Hirshfeld-e partial charges for the Zr ions have been computed to investigate their sensitivity to substituent effects; a strong correlation with the experimental Hammett parameters, and with the rates of the citronellal cyclization is found. The theoretical rationalization may serve as a basis for detailed active site engineering studies.