Stepwise assembly of a semiconducting coordination polymer [Cd₈S(SPh)₁₄(DMF)(bpy)]_n and its photodegradation of organic dyes

Abstract

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

Interlinking supertetrahedral chalcogenolate clusters with bipyridines to form two-dimensional coordination polymers for photocatalytic degradation of organic dye

“…Recently, we have developed a stepwise assembly approach for the design of semiconducting 1D and 3D coordination polymers by joining SCC clusters of Cd 8 S (SPh) 14 (DMF) 3 or Cd 6 Ag 4 (SPh) 16 (DMF) 4 with rigid bipyridines. 35,36 Obviously, the stepwise assembly approach offers opportunities for the design of such coordination polymers with tailored topologies and properties at the molecular level by controlling the molecular size and composition of the SCC clusters, shape and rigidity of the organic linkers, and their spatial arrangements. Herein, we present the stepwise assembly approach with the capability of dimensional control for the formation of 2D coordination polymers built from discrete clusters of Cd 6 Ag 4 (EPh) 16 8 ] n (E = S, Se) with coin metal complexes for the syntheses of the ternary chalcogenolate clusters and the stepwise assembly for the coordination polymers.…”

Construction and photocatalytic properties of two metal-mediated coordination polymers based on benzene-1,3,5-tricarboxylic acid and trans-1-(pyridin-3-yl)-2-(pyridin-4-yl)ethene

“…As shown in Fig. 6, the energy band gaps (E g ) of (I) and (II) obtained by extrapolation of the linear portion of the absorption edges were calculated to be 2.22 and 2.36 eV, respectively, indicating that these two title compounds could be semiconductors (Xu et al, 2015;Yang et al, 2017). Thus, compounds (I) and (II) may also possess potential photocatalytic capacities.…”

“…Among these contaminants, organic dyes might cause a high risk to the environment because they were carcinogenic and difficult to degrade (Li et al, 2013). Some Ag and Cd coordination polymers have been reported to possess narrow band gaps and thus to exhibit semiconductive behaviour (Xu et al, 2015;Yang et al, 2017). These coordination polymers are good photocatalytic materials that can be used to degrade organic dyes (Xu et al, 2015;Yang et al, 2017).…”

“…Some Ag and Cd coordination polymers have been reported to possess narrow band gaps and thus to exhibit semiconductive behaviour (Xu et al, 2015;Yang et al, 2017). These coordination polymers are good photocatalytic materials that can be used to degrade organic dyes (Xu et al, 2015;Yang et al, 2017). On the assumption that compounds (I) and (II) possess similar properties -an assumption that we have not proved experimentally -we undertook to measure their putative band gaps before proceeding to a study of their catalytic properties.…”

The Quest for Sulfur‐Containing Photoactive Materials: Molecular Precursors, Structures and Applications

“…In addition, this framework was an efficient photocatalyst, under visible light, of the degradation of Rhodamine B. This work was expanded on by the synthesis of a Cd‐based chalcogenolate cluster and polymer for the specific use of degradation of organic dyes . The synthesis of the CP avoided the use of typical solvothermal techniques, and was instead created using a step‐wise assembly method.…”