Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide Oxidation

Abstract

Here, we systematically studied the self-assembly behavior of chiral polyoxytitanium clusters for the first time. Through the cooperative assembly of ferrocenecarboxylic acid and ketoxime ligands, we successfully incorporated the planar chirality of ferrocene (Fc) into the layered {Ti5} building blocks. The resulting {Ti5Fc} clusters can be used as structural units to assemble into large ordered structures in various ways; either a pair of {Ti5Fc} enantiomers are bridged by organic adhesive to form sandwich structures or two homochiral {Ti5Fc} units participate in the assembly to form the large clusters. Depending on the assembly modes, the chirality of {Ti5Fc} can be transferred to large nanoclusters or disappear to form mesostructures. The difference of the assembly modes between the {Ti5Fc} units can also tune the photoelectric activity of the resulting clusters, which has been verified by using {Ti 10 Fc-6/7} as catalysts for photocatalytic selective sulfide oxidation. This work not only is an important breakthrough in the study of the self-assembly of chiral nanoclusters but also provides an important reference for understanding of chiral transfer on the nanoscale.

Assembly of Titanium‐oxo Clusters from Embonic Acid‐Modified {Ti2} Molecular Building Blocks with Efficient Sulfur‐Catalyzed Oxidation Activities

“…These compounds were characterized by IR patterns in Figure S10. The characteristic peaks at 3439 cm −1 for Ti 2 ‐1 , 3414 cm −1 for Ti 2 ‐2 , 3432 cm −1 for Ti 6 , 3390 cm −1 for Ti 20 are attributed to OH stretching [27] . The characteristic peaks near 3050 cm −1 correspond to the stretching vibrations of the C−H bond of the benzene ring.…”

“…The characteristic peaks at 3439 cm À 1 for Ti 2 -1, 3414 cm À 1 for Ti 2 -2, 3432 cm À 1 for Ti 6 , 3390 cm À 1 for Ti 20 are attributed to OH stretching. [27] The characteristic peaks near 3050 cm À 1 correspond to the stretching vibrations of the CÀ H bond of the benzene ring. The band between 1490-1600 cm À 1 contributes from the stretching vibrations of the C=C bond on the naphthalene ring of H 4 L. The peaks at near 1450 cm À 1 for these compounds indicating the mono-dentate co-ordination nature of the carboxylate moiety in the ligand (H 4 L).…”

Ionothermal Synthesis and Photoactivity of Ti17 and Ti19‐Oxo Clusters Functionalized by Sulfate and 1,10‐Phenanthroline Ligands

“…Titanium‐oxo clusters (TOCs) have garnered increasing research attention due to their atomically precise structures and improved functional efficiencies compared to bulk phase TiO 2 . [ 1‐14 ] TOCs are adorned with various functional ligands, including carboxylates, phosphonates, sulfates, azoles, calixarenes, hydroxyls, and more. [ 15‐27 ] These ligands play crucial roles in modulating the cluster structures and physicochemical characteristics, while also offering abundant applications in photocatalysis, semi conductivity, environmental remediation (such as dye degradation), and wastewater treatment.…”

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)4O4 Cubane Core

“…1,1′-Ferrocene dicarboxylic acid (H 2 FcDCA) is a functional dicarboxylic acid ligand with good photoelectric and redox activity. It has flexible and reversible two carboxyl groups that can be used as a chelating ligand through regulation, making it a very suitable organic metal ligand for synthesizing high-nuclear metal oxygen clusters. ,− For instance, polynuclear indium oxo clusters (InOCs) were synthesized with H 2 FcDCA as chelating and surface-protective ligands by Zhang’s group …”