Titanium phosphonate oxo-alkoxide “clusters”: solution stability and facile hydrolytic transformation into nano titania

Abstract

Oligonuclear Ti(iv) oxo-alkoxide-phosphonate complexes, produced by reaction of tBuPO(OH)2 with Ti(OR)4, are easily topotactically hydrolyzed forming intricate nanostructures.

Titanium‐Oxo Clusters with Bi‐ and Tridentate Organic Ligands: Gradual Evolution of the Structures from Small to Big

“…The cluster core of Ti 4 O(OEt) 12 (O 3 PR′′) (R′′= t Bu,[ 134 , 136 ] Ph; [137] Figure 17 , left), with the lowest O/Ti ratio ( d c 0.25) among all TOC, is very similar to that of Ti 4 O 2 (OR) 10 (O 2 CR’) 2 (cf. Figure 2 ), with the four [TiO 6 ] octahedra centered around a μ 4 ‐O.…”

“…There is only one example for the former, viz. Ti 6 O 3 (OEt) 11 (O 3 P t Bu) 3 [O 2 P(OH) t Bu] [134] . As a 3.111 R′′PO 3 ligand occupies three coordination sites but a μ 2 ‐O only two, one terminal OR group is replaced by a μ 2 ‐R′′P(OH)O 2 ligand.…”

“…Another 3+2 structure, with a different arrangement of the [TiO 6 ] octahedra in the Ti 2 unit is Ti 5 O 2 (OEt) 4 (O 3 P t Bu) 5 [O 2 P(OH) t Bu] 2 [134] (Figure 16 , center right). The octahedra in the Ti 2 unit are corner‐sharing (μ 2 ‐O), and the Ti 3 O and Ti 2 units are not only interlinked via three 3.111 R′′PO 3 ligands but additionally via two R′′P(OH)O 2 ligands.…”

Self-Assembly of Asymmetrically Functionalized Titania Nanoparticles into Nanoshells

“…As ligands for functionalization, glucose-6-phosphate (G6P, hydrophilic) and n-dodecylphosphonic acid (DPA, hydrophobic) were chosen. Both the phosphate and phosphonate functions have documented affinity for titania surfaces [30,31], even at lowered pH [32]. In addition, their presence is easily confirmed from phosphorous by elemental analysis compared to the carboxylate function.…”

Nucleation and growth of mixed vanadium-titanium oxo-alkoxy nanoparticles in sol-gel synthesis

“…Despite of a long history of the related research [2,3], the nucleation-growth stage of the sol-gel process has not received a necessary attention. This can be partially explained by a limited power of calculation methods, which are restricted to small clusters of radius below 1 nm [4][5][6] and synthesis with a significant polydispersity of the condensed species, making unrealistic monitoring of a selective size population evolution. Moreover, the most effe ctive light scattering methods of the insitu nanoparticles observation provide a weak signal in the Rayleigh size domain (R<<) due to the scattered light intensity Im 2 , where m is the particle mass.…”