Large Polyoxotitanate Clusters: Well-Defined Models for Pure-Phase TiO₂ Structures and Surfaces

Abstract

Careful control of the temperature and duration of the reaction between titanium tert-butoxide and acetic acid leads to the formation of new polyoxotitanate clusters with 14, 18, and 28 Ti atoms. They are considered intermediates in the growth of Ti/O nanoclusters of increasing size. The Ti(28) cluster is the largest crystallized to date. UV/vis spectroscopy on this cluster reveals that the optical band gap is blue-shifted with respect to a cluster containing only 17 titanium atoms indicating that the optical properties are more heavily influenced by the internal structure of the particle than its size.

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

“…350 nm for both). [33,34] It can therefore be concluded that this series of cobalt(II)-doped cages exhibits a similar trend in optical behavior as observed in cobalt(II)-doped bulk and nanoparticulate TiO 2 [13-18, 26, 27] and that there is a trend towards increased red-shift in the absorption edge with increased cage size. However, there is clearly also a very strong structurally dependent element to the absorption edge behavior, as seen in 4 which exhibits a large red-shift in the absorption edge (ca.…”

Construction of molecular rectangles with titanium–oxo clusters and rigid aromatic carboxylate ligands

“…[16][17][18] Along this line, polyoxo-titanium clusters (PTCs) have been attracting much research attention in recent years, because they possess well-defined structures and can be used as reactivity model compounds of TiO 2 nanoparticles. [19][20][21][22][23][24][25] Another major advantage of PTCs is that they can be easily functionalized by organic ligands. 26 In the course of our research on titanium-oxo clusters, recently, we successfully applied a variety of bridging ligands to organize the 0D {Ti 6 3 ) is observed that has been reported earlier in many molecular clusters ( Fig.…”

Two Titanium-oxo-Clusters with Malonate and Succinate Ligands: Single-Crystal Structures and Catalytic Property

“…Great attentions have been paid on titanium-oxo-clusters (TOCs) because of their use as the model compounds of the nanoscale titanium oxide [1][2][3][4] and offering the opportunity to understand the information in terms of both atomic structure and chemical reactivity [5][6][7][8][9][10]. A large number of titanium-oxo-clusters based on Electronic supplementary material The online version of this article (doi:10.1007/s10876-015-0960-0) contains supplementary material, which is available to authorized users.…”

“…A large number of titanium-oxo-clusters based on Electronic supplementary material The online version of this article (doi:10.1007/s10876-015-0960-0) contains supplementary material, which is available to authorized users. alkoxides and carboxylate ligands have been described [11][12][13], including the Ti 28 cluster [Ti 28 O 40 (O t Bu) 20 (OOAc) 12 ], a larger carboxylate-substituted TOC synthesized recently [10]. Among them, however, the TOCs constituted with dicarboxylate are still rare.…”

“…However, the crystal structure was solved by ab initio on the sample using powder X-ray diffraction (XRD) data by a direct method. Later, Dai grounps successfully introduced phthalic acid into titanium-oxo-clusters and got two new compounds [15], Ti 6 O 4 (o-BDC) 2 (o-BDC-i Pr) 2 (O i Pr) 10 and Ti 6 O 3 (o-BDC) 2 (O i Pr) 14 and a photochromic effect was observed upon irradiation of the crystals in the presence of alcohol. As we know, phthalic acid is a rigid dicarboxylate ligand, but no crystal structure of TOC with only alkane dicarboxylate has been reported.…”