Molecular Recognition of Titanium(IV) Alkoxides by 2,6-Bis(hydroxymethyl)-p-cresol in the Crystal Engineering of Hybrid Organic−Inorganic Networks

Nonempirical Quantification of Molecular Interactions in Supramolecular Assemblies

“…Even if the oxygen atom is found to be negatively charged, it should have absolutely no affinity for protons (pK a % À 8.5 according to a previously derived empirical relationship). [5] For covalent interactions, (coordination chemistry) the largest f index is found on the carbon atom and not the oxygen atom, which explains the preferred coordination mode MÀCO and not M À O C. Fortunately enough, all these predictions are confirmed by experiments. The interesting point is that these properties were derived without any reference to any MO scheme or to the occurrence of a carbon ± oxygen triple bond in this molecule.…”

“…Using the Ewald method, [12] we get M ij A ij B ij , where A ij is the reciprocal space contribution, given by Equation (5), and B ij is the direct space contribution, Equation (6).…”

Synthesis and Characterization of Ti Complexes Using 4‐tert‐Butyl‐2,6‐bis(hydroxymethyl)phenol: X‐ray Structures of a Confacial Bioctahedron with Terminal Nucleophilic Phenylmethoxide Ligands, and a Ti4O16 Core Protected by Two Hydrophobic Binding Pockets

“…The Ti 4 O 16 core found in the dianion of 2 represents a relatively common structural motif in TiϪoxygen chemistry since it has been observed in several complexes constructed from varying kinds of alkoxide ligands from monodentate to tridentate. [4,12] These compounds can be used as molecular precursors for metal oxides in sol-gel chemistry or for thin-film preparation.…”

“…[3,4] Furthermore, a search of the Cambridge Structural Database indicates that the structural coordination chemistry of phenylmethoxide ligands has, in general, not 1.83 Å and for Ti−µ 2 -OPh ca. 2.11 Å .…”

Thermodynamics of Hydrogen Bond Patterns in Supramolecular Assemblies of Water Molecules

“…Figure 13 a shows another interesting case with intramolecular hydrogen bonds in a hybrid organic ± inorganic divergent association of six 2,6-bis(hydroxymethyl)-pcresol ligands (H 3 BHMPC) around a Ti 4 O 2 core (doubly fused calix [3] shape). [24] Here, by rotating the two OH groups of the chelating [H 2 BHMPC] À ligand and the free OH group of the chelating bridging [HBHMPC] 2À ligand around the ÀH 2 CÀOÀ bonds, one may probe the relative strength of these intramolecular hydrogen bond interactions. Figure 13 b shows the rather deep potential well (E HB À 98 kJ mol À1 ) for the hydrogen atom which bridges the chelating arm of one [H 2 BHMPC] À ligand with the free OH group of one chelating bridging [HBHMPC] 2À ligand.…”