DFT Study on Effect of Metal Type and Coordination Environment on CO2 ECR to C1 Products over M-N-C Catalysts.

Electrocatalytic reduction (ECR) of CO2 to chemical products is an important carbon emission reduction method. This work uses DFT to study the stability of N-doped graphene-supported four metal single-atom catalysts (M-N-C) and the effects of the coordination environment and metal centers on the selectivity of CO2 ECR to C1 products. The results show that Fe, Co, Ni, and Cu have good stability. The coordination environment has a significant modulating effect on product selectivity, and the change of the number of ligand nitrogen atoms will affect the size of the potential-limiting step of each product. When the number of nitrogen ligands is the same, the different metal centers of the M-N-C catalyst have a significant effect on the selectivity of different products. In addition, the introduction of nitrogen atom ligands can adjust the electronic structure of the graphene-supported metal center, increase the d-band center of most metals, and improve the reaction activity.

Electron-Rich Triazine-Conjugated Microporous Polymers for the Removal of Dyes from Wastewater.

Conjugated microporous polymers (CMP) as porous functional materials have received considerable attention due to their unique structures and fascinating properties for the adsorption and degradation of dyes. Herein, a triazine-conjugated microporous polymer material with rich N-donors at the skeleton itself was successfully synthesized via the Sonogashira-Hagihara coupling by a one-pot reaction. These two polymers had Brunauer-Emmett-Teller (BET) surface areas of 322 and 435 m2g-1 for triazine-conjugated microporous polymers (T-CMP) and T-CMP-Me, respectively. Due to the porous effects and the rich N-donor at the framework, it displayed a higher removal efficiency and adsorption performance compared to cationic-type dyes and selectivity properties for (methylene blue) MB+ from a mixture solution of cationic-type dyes. Furthermore, the T-CMP-Me could quickly and drastically separate MB+ and (methyl orange) MO- from the mixed solution within a short time. Their intriguing absorption behaviors are supported by 13C NMR, UV-vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies. This work will not only improve the development of porous material varieties, but also demonstrate the adsorption or selectivity of porous materials for dyes from wastewater.

Thermally Activated Fluorescence vs Long Persistent Luminescence in ESIPT-Attributed Coordination Polymer.

Excited-state intramolecular proton transfer (ESIPT) molecules demonstrating specific enol-keto tautomerism and the related photoluminescence (PL) switch have wide applications in displaying, sensing, imaging, lasing, etc. However, an ESIPT-attributed coordination polymer showing alternative PL between thermally activated fluorescence (TAF) and long persistent luminescence (LPL) has never been explored. Herein, we report the assembly of a dynamic Cd(II) coordination polymer (LIFM-101) from the ESIPT-type ligand, HPI2C (5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic acid). For the first time, TAF and/or color-tuned LPL can be achieved by controlling the temperature under the guidance of ESIPT excited states. Noteworthily, the twisted structure of the HPI2C ligand in LIFM-101 achieves an effective mixture of the higher-energy excited states, leading to ISC (intersystem crossing)/RISC (reverse intersystem crossing) energy transfer between the high-lying keto-triplet state (Tn(K*)) and the first singlet state (S1(K*)). Meanwhile, experimental and theoretical results manifest the occurrence probability and relevance among RISC, ISC, and internal conversion (IC) in this unique ESIPT-attributed coordination polymer, leading to the unprecedented TAF/LPL switching mechanism, and paving the way for the future design and application of advanced optical materials.

Supramolecular Assembly of Organoplatinum(II) Complexes for Subcellular Distribution and Cell Viability Monitoring with Differentiated Imaging.

The ability to precisely control the subcellular distribution of luminous materials presents unprecedented advantages for understanding cell biology and disease therapy. We introduce a luminescence tool for subcellular distribution imaging and differentiation of live and dead cells, utilizing cationic organoplatinum(II) complexes that exhibit well-defined monomeric to aggregate nanostructures along with concentration-dependent switchable luminescence from green to red due to assembly via PtII ⋅⋅⋅PtII and π-π stacking interactions. One of the complexes was chosen to demonstrate the unique lysosome-to-nucleus subcellular re-distribution and imaging capability in live and dead cells, respectively, which represents the first example to discriminate the subcellular localization of platinum(II) complexes through differential luminescence response. These new findings facilitate the fundamental understanding of self-assembly behaviors of platinum(II) complexes for potential subcellular detection assays.

Phosphorescent Cyclometalated Platinum(II) Enantiomers with Circularly Polarized Luminescence Properties and Their Assembly Behaviors.

Platinum(II) complexes as supramolecular luminescent materials have received considerable attention due to their unique planar structures and fascinating photophysical properties. However, the molecular design of platinum(II) complexes with impressive circularly polarized luminescence properties still remains challenging and rarely explored. Herein, we reported a series of cyclometalated platinum(II) complexes with benzaldehyde and its derived imine-containing alkynyl ligands to investigate their phosphorescent, chiroptical, and self-assembly behaviors. An isodesmic growth mechanism is found for their temperature-dependent self-assembly process. The chiral sense of the enantiomers can be transferred from the chiral alkynyl ligands to the cyclometalated platinum(II) dipyridylbenzene N^C^N chromophore and further amplified through supramolecular assembly via intermolecular noncovalent interactions. Notably, distinctive phosphorescent properties and nanostructured morphologies have been found for enantiomers 4R and 4S. Their intriguing self-assembled nanostructures and phosphorescence behaviors are supported by crystal structure determination, 1H NMR, emission, and UV-vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies.

Visual Detection of Triethylamine and a Dual Input/Output Logic Gate Based on a Eu3+-Complex.

A series of Ln3+-metal centered complexes, Ln(TTA)3(DPPI) (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3; or Ln = Gd, 4) [(DPPI = N-(4-(1H-imidazo [4,5-f][1,10]phenanthrolin-2-yl)phenyl)-N-phenylbenzenamine) and (TTA = 2-Thenoyltrifluoroacetone)] have been synthesized and characterized. Among which, the Eu3+-complex shows efficient purity red luminescence in dimethylsulfoxide (DMSO) solution, with a Commission International De L' Eclairage (CIE) coordinate at x = 0.638, y = 0.323 and ΦEuL = 38.9%. Interestingly, increasing the amounts of triethylamine (TEA) in the solution regulates the energy transfer between the ligand and the Eu3+-metal center, which further leads to the luminescence color changing from red to white, and then bluish-green depending on the different excitation wavelengths. Based on this, we have designed the IMPLICATION logic gate for TEA recognition by applying the amounts of TEA and the excitation wavelengths as the dual input signal, which makes this Eu3+-complex a promising candidate for TEA-sensing optical sensors.

Interplay of Dual-Proton Transfer Relay to Achieve Full-Color Panel Luminescence in Excited-State Intramolecular Proton Transfer (ESIPT) Fluorophores.

A new design was applied for the facile synthesis of pure organic photoluminescent molecules with dual excited-state intramolecular proton transfer (ESIPT) sites. In this novel class of emitters, full-color panel emission from blue, green, and yellow to red, including white light, can be achieved in different solvents as modulated by the enol-keto(1st)-keto(2nd) tautomer emissions. A comprehensive transient photophysical study verifies that keto(1st) and keto(2nd) have a precursor (<0.8 ps)-successor (∼20 ps)-relayed absorbance relationship, and then a fast equilibrium between the two is established, resulting in dual emissions in the nanosecond scale (∼1900 ps). Through the research on copper ions' selective PL response, the dual-ESIPT mechanism was further verified; in addition, the study of solid-state PL changes upon the stimulus of organic vapor manifests the potential application sensitivity of the molecules as dual-ESIPT sensors. Theoretical results including reaction potential energy surface analyses manifest the fact that dual-proton transfer goes along a sequential route with a smaller energy barrier, firmly supporting the experimental results. An intrinsic system that undergoes intramolecular double proton relayed transfer is thus established for the achievement of much broadened optical responses and full-color display, providing reference for the design and application of advanced dual-ESIPT optical materials.

Efficient catalytic degradation of methylene blue by a novel Fe3+-TiO2@CGS three-dimensional photoelectric system.

In this study, a novel three-dimensional photoelectric system was designed and constructed for the degradation of methylene blue (MB) via photocatalysis, electrocatalysis, and photoelectric catalysis. To this end, a Ti/RuO2-IrO2-SnO2-CeO2 electrode was prepared via a thermal oxidation coating method and used as a dimensionally-stable anode (DSA). The cathode was made of a titanium sheet with Fe3+-doped TiO2 loaded on coal gasification slag (CGS) (Fe3+-TiO2@CGS) as a photocatalyst. The factors affecting the degradation efficiency, such as the supporting electrolyte, current density, and initial pH were systematically investigated. The results revealed Fe3+-TiO2@CGS three-dimensional photoelectric system exhibiting efficient synergistic performance of photocatalysis and electrocatalysis with a synergistic factor of 1.11. Photo-generated holes (h+) were generated by light irradiation and direct anodic oxidation. Furthermore, hydroxyl radicals (HO·) radicals were induced via other pathways. Such active species showed highly-oxidizing abilities, beneficial to the degradation of methylene blue (MB). The representative Fe3+-TiO2@CGS three-dimensional photoelectric system showed super high degradation efficiency at pH 11 and current density of 18.76 mA cm-2. Using NaCl as a supporting electrolyte, the degradation yield reached 99.98% after 60 min of photoelectrical treatment. Overall, the novel Fe3+-TiO2@CGS three-dimensional photoelectrical system looks very promising for the highly efficient catalytic degradation of organic contaminants.