Enhanced Photocatalytic CO Reduction through Hydrophobic Microenvironment and Binuclear Cobalt Synergistic Effect in Metallogels.

Assemblies that mimic natural lipid bilayers are theoretically efficient for photocatalytic CO reduction; however, such an approach has not been yet explored. Herein, metallogels (LG/Nico-Co) based on the co-assembly of L-glutamic acid lipid (LG/Nico) and cobalt ions exhibited excellent photocatalytic CO reduction, with 208 724 μmol g CO production within 24 h and 90 % CO/H selectivity, or 166 826 μmol g CO production within 12 h and 46 % CO/H selectivity, depending on the water content of the solvent. The alkyl chains of LG/Nico provide a hydrophobic microenvironment for efficient gas transfer, and the assembled bilayers induce a synergistic effect between two adjacent Co ions for catalyzing the CO reduction reaction.

Perspectives on Ligand Properties of N-Heterocyclic Carbenes in Iron Porphyrin Complexes.

There has been considerable research interest in the ligand nature of N-heterocyclic carbenes (NHCs). In this work, two six-coordinate NHC iron porphyrin complexes [Fe(TTP)(1,3-MeImd)] (TTP = tetratolylporphyrin, 1,3-MeImd = 1,3-dimethylimidazol-2-ylidene) and [Fe(TDCPP)(1,3-MeImd)]ClO (TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin) are reported. Single-crystal X-ray characterizations demonstrate that both complexes have strongly ruffled conformations and relatively perpendicular ligand orientations which are forced by the sterically bulky 1,3-MeImd NHC ligands.

Intermolecular Chirality Modulation of Binaphthalene-Bridged Bisporphyrins With Chiral Diamines.

A new pair of 2,2'-diamino-1,1'-binaphthyl linked porphyrin dimers, ()-/()-, were synthesized to study their supramolecular interactions with a pair of chiral diamines (()-/()-PPDA) by using UV-Vis absorption, fluorescence and NMR titrations. The spectroscopic titrations indicated that sandwich-type 1:1 complexes were formed at low guest concentration and then transformed to 1:2 open complexes at high guest concentration. The supramolecular interactions afforded sensitive circular dichroism responses, and the CD signs of the 1:1 complexes are decided by the stereostructure of chiral diamine guests.

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging.

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) (n=1-3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.

Ultrathin Phthalocyanine-Conjugated Polymer Nanosheet-Based Electrochemical Platform for Accurately Detecting HO in Real Time.

As a vital biological mediator and a widely used industrial oxidant, the accurate detection of hydrogen peroxide (HO) is of significance for both academic purpose and practical applications. Herein, we report a novel approach for the development of a high-performance electrochemical HO sensor constructed by iron phthalocyanine (FePc)-based diyne-linked conjugated polymeric nanosheets (NSs), FePc-CP NSs. The FePc-CP NSs were delaminated from the bulk material via a defect- and disorder-induced synthetic strategy.

Two-Photon Excited FRET Dyads for Lysosome-Targeted Imaging and Photodynamic Therapy.

Two-photon excitable fluorescent dyes with integrated functions of targeted imaging and photodynamic therapy (PDT) are highly desired for the development of cancer theranostic agents. Herein, fluorescence resonance energy transfer (FRET) dyads, AceDAN-HPor-Lyso (1a) and AceDAN-ZnPor-Lyso (1b), were developed for two-photon excited (TPE) lysosome-targeted fluorescence imaging and PDT of cancer cells. Under one-photon or two-photon excitation, the AceDAN donor can effectively transfer the excited state energy to the porphyrin acceptor via high efficient FRET, leading to the generation of deep-red fluorescence and singlet oxygen for cell imaging and PDT, respectively.