A periodic metallo-supramolecular polymer from a flexible building block: self-assembly and photocatalysis for organic dye degradation

Abstract

A water-soluble metallo-supramolecular polymer MSP-f-6Np, which possesses a regular pore aperture of 1.4 nm, has been assembled from a structurally flexible naphthalene-appended [Ru(bipy)3]2+ complex and cucurbit[8]uril. As the first periodic metallo-supramolecular polymer formed by a flexible building block, MSP-f-6Np exhibits a hydrodynamic diameter of 122 and 164 nm at 0.1 and 2.0 mM of the monomer concentrations. Synchrotron small angle X-ray scattering experiments confirm that MSP-f-6Np possesses porosity periodicity in both the solution and solid states. Compared with a control, the new highly ordered porous system displays enhanced photocatalytic activity for the degradation of organic dyes.

Self‐Assembly of a Bilayer 2D Supramolecular Organic Framework in Water

“…Theremarkable increase of the binding stability between the DPB units of M1 compared with that of C1 strongly supported great cooperativity of the four DPB units in binding to CB [8],which was observed previously for the co-assembly between tetra-and hexatopic components and CB [8]. [57,58] Diffusion ordered spectroscopic (DOSY) 1 HNMR experiments of the 1:2mixture of M1 (1.0 mM) and CB [8] in D 2 Oa fforded ad iffusion coefficient of 1.06 10 À10 m 2 s À1 ,w hich was notably lower than that of M1 of the same concentration (1.62 10 À10 m 2 s À1 )(Figure S6). Dynamic light scattering (DLS) experiments for the solution of M1 and CB [8] (1:2) gave rise to ah ydrodynamic diameter (D H ) ranging from 220 nm to 295 nm, depending on the concentration of the mixture ([M1] = 0.03 mM to 1.0 mM) (Figure 2c).…”

Self‐Assembly of a Bilayer 2D Supramolecular Organic Framework in Water

“…ITC experiment gave rise to an apparent K a of 3.82×10 14 M −2 for this 2:1 complex (Figure 2 b). The remarkable increase of the binding stability between the DPB units of M1 compared with that of C1 strongly supported great cooperativity of the four DPB units in binding to CB[8], which was observed previously for the co‐assembly between tetra‐ and hexatopic components and CB[8] [57, 58] . Diffusion ordered spectroscopic (DOSY) 1 H NMR experiments of the 1:2 mixture of M1 (1.0 mM) and CB[8] in D 2 O afforded a diffusion coefficient of 1.06×10 −10 m 2 s −1 , which was notably lower than that of M1 of the same concentration (1.62×10 −10 m 2 s −1 ) (Figure S6).…”

Hierarchical Pd@PC-COFs as Efficient Catalysts for Phenol Hydrogenation

“…Therefore, an appropriate support is extremely important for the preparation of high-performance phenol hydrogenation catalysts . Covalent organic frameworks (COFs) have many advantages, such as high porosity, large specific surface area, low density, adjustable structure and pore size, , apparent modification ability, and adaptive combination of covalent structural units. − Therefore, COFs are ideal support materials for loading Pd NPs for phenol hydrogenation. In our previous work, an imine COF (TpPa-1) was prepared by a solvothermal method for the synthesis of Pd@TpPa-1 catalysts applied in liquid-phase phenol hydrogenation.…”