Designed Cluster Assembly of Multidimensional Titanium Coordination Polymers: Syntheses, Crystal Structure and Properties

Abstract

The exploitation of new titanium-based coordination polymers (Ti CPs) with high crystallinity is difficult but highly desirable for their potential applications in photocatalysis. Herein, a cluster-cooperative assemble strategy is developed to synthesize Ti CPs. By utilizing various bifunctional ligands containing carboxylate acids and N-donor groups, we successfully assembled the zero-dimensional (0D) [(Ti O)(iPrO) ] or [(Ti O )(iPrO) ] clusters into one-dimensional (1D) tube-, ribbon-, or helical chain-shape architectures, two-dimensional (2D) layered structures, and a rare parallel 2D→three-dimensional (3D) polycatenation framework with various copper iodide dopants, including rhombus- or wing-shaped Cu I and tetrahedron- or ladder-shaped Cu I . The as-synthesized compounds display strong absorption in the visible region with narrow band gaps ranging from 1.70 to 2.72 eV and exhibit good photocatalytic activities in the degradation of organic pollutants.

Synthesis, Structural, and Physicochemical Characterization of a Ti6 and a Unique Type of Zr6 Oxo Clusters Bearing an Electron-Rich Unsymmetrical {OON} Catecholate/Oxime Ligand and Exhibiting Metalloaromaticity

“…The precise knowledge of the structures of PTCs, since these oxide clusters are soluble analogues of discrete fragments of solid TiO 2 , originates from the necessity to understand the binding modes of sensitizers to Ti–O surfaces . The large band gap (3.20 eV) of anatase (TiO 2 ) limits its applications in photocatalysis . The employment of organic chelators could allow the manipulation of the band gap and presumably the subsequent visible light absorption by PTCs …”

Ferrocene-sensitized titanium-oxo clusters with effective visible light absorption and excellent photoelectrochemical activity

“…We have been working on the synthesis, structure, and photorelated properties of Ti-oxo clusters. 62–67 In continuation of our research and in consideration of the characteristics of the ferrocene ligands, we carried out research on the synthesis of ferrocene-sensitized Ti-oxo clusters and their photoelectrochemical properties. Herein, two novel ferrocene-sensitized Ti-oxo clusters, namely, [Ti 8 (μ 3 -O) 4 (Dipa) 2 (Fcdc) 4 (O i Pr) 10 ]·2HO i Pr (Dipa = diisopropanolamine and HO i Pr = isopropanol, Ti 8 Fcdc 4 ) and [Ti 10 (μ 4 -O) 2 (μ 3 -O) 4 (Fcdc) 2 (μ 2 -OEt) 8 (OEt) 10 ]·2HOEt (HOEt = ethanol, Ti 10 Fcdc 2 ), are successfully synthesized and structurally characterized.…”

Cd-Doped Polyoxotitanium Nanoclusters with a Modifiable Organic Shell for Photoelectrochemical Water Splitting

“…The lack of a detailed understanding of the structure hinders the depiction of the relationship between the structure and performance, which helps to further regulate the water oxidation activity. Titanium oxo clusters (TOCs), as the structural model of TiO 2 nanoparticles, provide an opportunity to understand its structure–performance relationship. − To date, a large number of TOCs with nuclearities between 2 and 52 have been synthesized, with representative clusters such as the [Ti 28 ] nanocage, 3.6 nm {Ti 52 }, fullerene-like {Ti 42 }, and Ag–Ti bimetallic clusters {Ag 6 @Ti 16 }, {Ag 14 @Ti 16 }, and {Ag 10 Ti 28 } . TOCs can be used as building units to construct nanocomposites, from which materials with improved photoelectrocatalytic activity have been generated .…”