Two new hexanuclear titanium oxo cluster types and their structural connection to known clusters

Abstract

Ti 6 O 6 (OiPr) 2 (OOCR 0 ) 10 (R 0 = C 4 H 7 , Et) and Ti 6 O 3 (OiPr) 14 (OOC-CHQCH-COO) 2 represent new structure types of carboxylate-substituted clusters with a Ti 6 O x core (x = 3-6). They complement the already known six structure types and thus allow conclusions on how the structures of such clusters evolve during substitution and condensation processes.

Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand

“…Crystalline polyoxo-titanium clusters (PTCs) have attracted considerable attention the last years [1][2][3][4][5][6][7][8][9][10][11][12] due to their potential applications in catalysis, medicine, electro-optics, and nanotechnology. [13][14][15][16][17][18][19] In particular, the precise structural information of PTCs can help the understanding of the binding modes of sensitizers to Ti-O 20 surfaces and potential applications in photoelectronic [21][22][23][24] and photocatalytic chemistry.…”

“…Ball-and-stick representations of the structure of the anion of 1, along with the polyhedral/ball-andstick view of the metallic core are shown in The bond distances of Ti-μ2-O 2− [1.795(1) Å] and Ti-μ3-O 2− [1.931(2) Å] are in the expected range. 3,7,[9][10][11]22,25, The d(Ti-Ohydroxylamine) = 2.002(6) Å is shorter than the d(Ti-Ooxime) = 2.088(5) Å reflecting the better donor properties of Ohydroxylamine in comparison with the Ooxime atoms (Scheme 2). The d(Ti-Ooxime) in 1 is larger than the Ti-Ooxime distances of other Ti IV -oximates reported in the literature, which is due to the different coordination mode, end-on in 1vs.…”

Metal–Organic Frameworks Based on Group 3 and 4 Metals

“…Ti–oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments. [ 48 ] The number of Ti atoms in Ti–oxo clusters ranges from 3 to 32, including Ti 3 , [ 49–52 ] Ti 4 , [ 50,52–57 ] Ti 5 , [ 57 ] Ti 6 , [ 51,52,54,55,57–64 ] Ti 7 , [ 57 ] Ti 8 , [ 54,64,65 ] Ti 9 , [ 51,55,63 ] Ti 10 , [ 66 ] Ti 11 , [ 54–56,63 ] Ti 12 , [ 57,62,66,67 ] Ti 14 , [ 50,56 ] Ti 16 , [ 54,55,61,66 ] Ti 18 , [ 51,57 ] Ti 19 , [ 63 ] Ti 20 , [ 66,68 ] and Ti 32 clusters. [ 69 ] In general, during the assembly of Ti–oxo clusters, it is vital to control the competition between acids and coordinating ligands.…”

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters

“…The bond distances and angles observed for (II) (Table SI3 †) are consistent with literature values with the bond between the (m 3 -O) and the Ti3 or Ti6 atom which is longer than the others Ti-O bonds. 23,[32][33][34] In Fig. 8 the packing of the crystal is shown.…”

“…condensation degree, is one of the most common Ti 6 type due to its robustness, while cores like the one of cluster (II), are uncommon. 23 The Ti-O distances (Table SI4 ) adopts a hexagonal column geometry and is surrounded and stabilized by six carboxylate ligands on the equatorial plane and six ethoxide ligands along the vertical direction (Fig. 12).…”