Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO2 Conversion with H2 O.

It is still a challenging target to achieve photocatalytic CO2 conversion to valuable chemicals with H2 O as an electron donor. Herein, 2D imide-based covalent organic polymer nanosheets (CoPcPDA-CMP NSs), which integrate cobalt phthalocyanine (CoPc) moiety for reduction half-reaction and 3,4,9,10-perylenetetracarboxylic diimide moiety for oxidation half-reaction, are constructed as a Z-scheme artificial photosynthesis system to complete the overall CO2 reduction reaction. Owing to the outstanding light absorption capacity, charge separation efficiency, and electronic conductivity, CoPcPDA-CMP NSs exhibit excellent photocatalytic activity to reduce CO2 to CO using H2 O as a sacrificial agent with a CO production rate of 14.27 µmol g-1 h-1 and a CO selectivity of 92%, which is competitive to the state-of-the-art visible-light-driven organic photocatalysts towards the overall CO2 reduction reaction. According to a series of spectroscopy experiments, the authors also verify the photoexcited electron transfer processes in the CoPcPDA-CMP NSs photocatalytic system, confirming the Z-scheme photocatalytic mechanism. The present results should be helpful for fabricating high-performance organic photocatalysts for CO2 conversion.

Self-assembly of PcOC8 and its sandwich lanthanide complex Pr(PcOC8)(2) with oligo(phenylene-ethynylene) molecules.

Self-assemblies of octakis(octyloxy) phthalocyanine (PcOC8) and its sandwich lanthanide complex, substituted praseodymium bis(phthalocyanine) (Pr(PcOC8)(2)), with oligo(phenylene-ethynylene) (OPE) have been investigated by scanning tunneling microscopy (STM) on a highly oriented pyrolytic graphite (HOPG) surface. The assemblies were prepared by dissolving the molecules in phenyloctane solution. It was found that both PcOC8 and Pr(PcOC8)(2) can form 4-fold or 6-fold symmetrical adlayers on HOPG. The intramolecular structure of Pr(PcOC8)(2) molecule was revealed by a high-resolution STM image. When OPE molecules are added into phenyloctane solvent, Pr(PcOC8)(2) molecules prefer to form an ordered adlayer at the top of the OPE adlayer, while PcOC8 molecules adsorb on HOPG surface directly and form separated domains with OPE. These results may be helpful to construct surface assemblies and develop molecular electronic devices in the future.

Tuning the arrangement of mono-crown ether-substituted phthalocyanines in Langmuir-Blodgett films by the length of alkyl chains and the cation in subphase.

Amphiphilic phthalocyanines with one crown ether and three alkyl chain substitutions can form stable monolayers on a water surface. This monolayer can be transferred to a substrate by a vertical dipping method. The arrangement of phthalocyanine molecules in LB films was affected by the length of alkyl chains and the coordination of alkali ions in crown ether. Davydov splitting was observed in the absorption spectra of the LB films of phthalocyanine with the shortest alkyl chain substitutions, and this splitting was affected by the alkali ions in the subphase.

Water Dispersible and Biocompatible Porphyrin-Based Nanospheres for Biophotonics Applications: A Novel Surfactant and Polyelectrolyte-Based Fabrication Strategy for Modifying Hydrophobic Porphyrins.

The hydrophobility of most porphyrin and porphyrin derivatives has limited their applications in medicine and biology. Herein, we developed a novel and general strategy for the design of porphyrin nanospheres with good biocompatibility and water dispersibility for biological applications using hydrophobic porphyrins. In order to display the generality of the method, we used two hydrophobic porphyrin isomers as starting material which have different structures confirmed by an X-ray technique. The porphyrin nanospheres were fabricated through two main steps. First, the uniform porphyrin nanospheres stabilized by surfactant were prepared by an interfacially driven microemulsion method, and then the layer-by-layer method was used for the synthesis of polyelectrolyte-coated porphyrin nanospheres to reduce the toxicity of the surfactant as well as improve the biocompatibility of the nanospheres. The newly fabricated porphyrin nanospheres were characterized by TEM techniques, the electronic absorption spectra, photoluminescence emission spectra, dynamic light scattering, and cytotoxicity examination. The resulting nanospheres demonstrated good biocompatibility, excellent water dispersibility and low toxicity. In order to show their application in biophotonics, these porphyrin nanospheres were successfully applied in targeted living cancer cell imaging. The results showed an effective method had been explored to prepare water dispersible and highly stable porphyrin nanomaterial for biophotonics applications using hydrophobic porphyrin. The approach we reported shows obvious flexibility because the surfactants and polyelectrolytes can be optionally selected in accordance with the characteristics of the hydrophobic material. This strategy will expand the applications of hydrophobic porphyrins owning excellent properties in medicine and biology.