Active Metal Research Articles

Effects of grassland degradation on soil ecological stoichiometry and soil microbial community on the South of the Greater Khingan Mountains

Grassland which covers 40% of terrestrial land is an important ecosystem having a multitude of functions, which has suffered various degrees of degradation with the interaction between global climate change and unreasonable human utilization (e.g., grazing and reclamation). Improved understanding of soil and microbial community diversity during meadow steppe degradation is crucial for predicting degradation mechanisms and restoration strategies. Here, we used Illumina sequencing technology to investigate the patterns of soil microbial community structure and the driving factors of its change across different degradation degrees of meadow steppe [i.e., non-degraded grasslands (NDG), lightly degraded grasslands (LDG), moderately degraded grasslands (MDG), and severely degraded grasslands (SDG)] south of the Greater Khingan Mountains. Our results showed a significant variation in soil properties, enzyme activity, and soil metal elements across the degraded meadows. Soil available phosphorus (AP), urease (UE), and cellulase (CL) in soils increased with the intensity of grassland degradation. Grassland degradation significantly decreased soil bacterial and fungal richness. In addition, grassland degradation significantly increased the relative abundance of Firmicutes (from 1.65% to 5.38%) and Myxococcota (from 2.13% to 3.13%). Degradation considerably increased the relative abundance of Ascomycota (from 66.54% to 75.05%), but decreased Basidiomycota (from 18.33% to 9.92%). The relative abundance of nitrogen fixation and cellulolysis decreased significantly due to grassland degradation. For fungal functional guilds, the relative abundance of pathotrophs increased while saprotrophs decreased significantly with increasing severity of degradation. Total nitrogen (TP), AP, available potassium (AK), manganese (Mn), lead (Pb), UE, sucrase (SC), and alcalase protease (ALPT) were the main drivers of soil bacterial community composition, while TP, AP, AK, Pb, UE, and SC were the main drivers of soil fungal community composition in the degraded grassland. Our findings demonstrated that severe grassland degradation has an enormous effect on soil microbial communities and soil physicochemical dynamics. These findings improve our theoretical understanding of the interactions between soil microbial populations and soil environmental variables in degraded grassland.

Synergistic Catalytic Sites in High-Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction.

The integration of multiple elements in a high-entropy state is crucial in the design of high-performance, durable electrocatalysts. High-entropy metal hydroxide organic frameworks (HE-MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal-organic framework (MOF) features a random, homogeneous distribution of cations within high-entropy hydroxide layers. HE-MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100mA cm-2 at ≈1.64 VRHE, and demonstrates remarkable durability, maintaining a current density of 10mA cm-2 for over 100 h. Notably, HE-MHOF outperforms precious metal-based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X-ray absorption spectroscopy (XAS) demonstrate that the high-entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high-entropy MOFs in developing noble metal-free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies.

Enhanced Electrocatalytic Capacity of Two POM@NH2‐MIL‐101(Fe) Composites for Oxygen Evolution Reaction

AbstractThe development and exploration of efficient bifunctional electrocatalysts for water splitting are in high demand and have garnered significant attention in recent years. Herein, by incorporating the advantages of catalytically active polyoxometalates (POMs) and structural stable metal–organic frameworks (MOFs), two POM@MOFs composite materials, Ni4Mo12@Fe and Co4Mo12@Fe, have been successfully prepared via the encapsulation of POMs anions, [MoV12O30(μ2‐OH)10H2{NiII4(H2O)12}]∙14H2O (noted as Ni4Mo12) and [MoV12O30(μ2‐OH)10 H2{CoII(H2O)3}4]∙12H2O (noted as Co4Mo12), into the cavities of MOFs NH2‐MIL‐101(Fe), respectively. Compared to each individual components, Ni4Mo12@Fe and Co4Mo12@Fe composites, as heterogeneous electrocatalysts, both showed enhanced electrocatalytic capacities for efficient oxygen evolution reaction (OER) under alkaline conditions with overpotentials of 332.64 mV for Ni4Mo12@Fe and 352.64 mV for Co4Mo12@Fe at 10 mA cm−2. Additionally, the enhanced electrocatalytic capacities of these two composites could also achieve towards hydrogen evolution reaction (HER). Such a POMs‐assisted strategy for the formation of POM@MOFs composites, described here, paves a new avenue for the development of highly economical, active nonnoble metal bifunctional electrocatalysts for OER and HER.

Metal-organic framework-based self-supported electrodes for oxygen evolution reaction

Oxygen evolution reactions (OER), commonly employed in applications such as metal-air batteries, water electrolysis, fuel cells, etc. , often suffer from slow kinetics, thus leading to ultra-high potentials that severely affect device energy efficiency. Metal-organic frameworks (MOFs) have garnered massive attention as electrodes for OER, benefiting from their highly ordered porous frameworks, abundant accessible active metal sites, and adjustable lattice structures. However, using powdered MOFs in OER poses a challenge, limiting the exposure of numerous active sites and resulting in suboptimal efficiency. To address this limitation, the trend towards designing MOF-based self-supported electrodes with enhanced contact between MOFs and the current collector has gained considerable attention for OER applications. This review highlights recent advancements and future prospects in developing MOF-based self-supported electrodes for OER. We delve into various aspects, including preparation methods, optimization strategies, catalytic efficiencies, and OER mechanisms with MOF-based electrocatalysts. Furthermore, we explore the existing challenges associated with MOF-based self-supported electrodes for OER. This comprehensive overview provides valuable insights into the evolving landscape of MOF-based materials in advancing OER.

Fluorine-Induced Lattice Oxygen Participation in 2D Layered Double Hydroxide/MXene Hybrids for Efficient Oxygen Evolution.

In oxygen evolution reaction (OER), the participation of lattice oxygen can break the limitation of adsorption evolution mechanism, but the activation of lattice oxygen remains a critical challenge. Herein, a surface fluorinated highly active 2D/2D FeNi layered double hydroxide/MXene (F-LDH/MX) is demonstrated, boosting OER with the enhanced lattice-oxygen-mediated path. The introduction of fluorine promotes the self-evolution of catalyst in an alkaline environment, even without an external current. It further accelerates the formation of active metal oxyhydroxides with abundant oxygen vacancies under the operating potential. The introduced oxygen vacancy activates the lattice oxygen, increasing the proportion of lattice oxygen mechanism in OER. Owing to the synergistic effects of the 2D/2D hierarchical structure and the modulated active surface, F-LDH/MX possesses excellent electrochemical performances, including a low overpotential of 251 mV at 10 mA cm-2, a low Tafel slope of 40.28 mV dec-1, and robust stability. The water electrolyzer system with F-LDH/MX as the anode offers the benchmark current density at a low cell voltage of 1.53 V, while the Zn-air battery with F-LDH/MX as the air electrode exhibits a higher power density of 75.43 mW cm-2. This study presents a promising strategy to design highly active electrocatalysts for energy conversion and storage.

Theoretical Investigation of Single-, Double-, and Triple- p-block Metals Anchored on g-CN Monolayer for Oxygen Electrocatalysis.

The design and development of highly active non-noble metal electrocatalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are crucial for metal-air batteries. In this work, the electrocatalytic performance of different p-block metal (PM = Sn, Sb, Pb and Bi) atoms embedded in the g-CN monolayer (PMx@g-CN, x = 1-3) for the OER and ORR was systematically investigated by density functional theory (DFT). The strong interaction between PMx atoms and g-CN substrates indicates the good stability of PMx@g-CN catalysts. Among all the designed catalysts, Bi3@g-CN is found to be a promising bifunctional electrocatalyst for both the OER and ORR with the calculated overpotential ηOER and ηORR of 0.23 and 0.25 V, respectively. With the atomic active sites of PMx increasing from x = 1 to 3, the OER and ORR catalytic activity is enhanced. The correlations between the overpotentials of the OER/ORR and Bader charge values of the anchored PMx atoms of the catalysts were established. Our findings contribute to searching for noble metal-free bifunctional electrocatalysts and shed light on the rational design of atomic active sites on electrocatalysts.

Recovery of gold ions from thiosulfate solution using an electrogenerative process

Traditional zinc powder cementation method for recovering gold ions from thiosulfate solution has the disadvantages such as high consumption of active metal, surface passivation, and co-deposition of copper ions. The key to solving these issues is providing the necessary electrons for the reduction of Au(S2O3)23- while avoiding direct contact between zinc powder and the leaching solution. In this study, a novel electrogenerative device with ion exchange membranes separating the anode and cathode is developed for the recovery of gold ions from thiosulfate solution. The oxidation reaction of zinc electrode occurs in the anode chamber, while the reduction reaction of gold ions occurs on a platinum electrode in the cathode chamber. The optimal experimental conditions for the gold recovery are determined to be using a cation exchange membrane, with the anode solution of 0.08 M ZnSO4, pH = 6, and the cathode solution of 0.10 M Na2S2O3, 5 mM CuSO4, 0.5 M NH3·H2O, pH = 10, with an initial gold concentration of 10 mg/L. It obtains the gold recovery of 99.59 %. Compared the zinc powder cementation method with the similar gold recovery, the electrogenerative process reduces zinc consumption by 67 % and prevents the passivation on the zinc surface caused by copper, oxygen, and sulfur.

Iron-molybdenum cofactor synthesis by a thermophilic nitrogenase devoid of the scaffold NifEN

The maturation and installation of the active site metal cluster (FeMo-co, Fe7S9CMo-R-homocitrate) in Mo-dependent nitrogenase requires the protein product of the nifB gene for production of the FeS cluster precursor (NifB-co, [Fe8S9C]) and the action of the maturase complex composed of the protein products from the nifE and nifN genes. However, some putative diazotrophic bacteria, like Roseiflexus sp. RS-1, lack the nifEN genes, suggesting an alternative pathway for maturation of FeMo-co that does not require NifEN. In this study, the Roseiflexus NifH, NifB, and apo-NifDK proteins produced in Escherichia coli are shown to be sufficient for FeMo-co maturation and insertion into the NifDK protein to achieve active nitrogenase. The E. coli expressed NifDKRS contained P-clusters but was devoid of FeMo-co (referred to as apo-NifDKRS). Apo-NifDKRS could be activated for N2 reduction by addition of preformed FeMo-co. Further, it was found that apo-NifDKRS plus E. coli produced NifBRS and NifHRS were sufficient to yield active NifDKRS when incubated with the necessary substrates (homocitrate, molybdate, and S-adenosylmethionine [SAM]), demonstrating that these proteins can replace the need for NifEN in maturation of Mo-nitrogenase. The E. coli produced NifHRS and NifBRS proteins were independently shown to be functional. The reconstituted NifDKRS demonstrated reduction of N2, protons, and acetylene in ratios observed for Azotobacter vinelandii NifDK. These findings reveal a distinct NifEN-independent pathway for nitrogenase activation involving NifHRS, NifBRS, and apo-NifDKRS.

Single-atom Barium Promoter Enormously Enhanced Non-noble Metal Catalyst for Ammonia Decomposition.

As a well-established topic, single-atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single-atom form, the intrinsic roles of single-atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co-Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co-Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat-1·min-1 at very low temperature (500 °C, GHSV = 840,000 mL·g-1·h-1) and Co-Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non-noble catalysts, and reaches or even exceeds numerous reported Ru-based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co-O-Ba-Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N-H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Single‐atom Barium Promoter Enormously Enhanced Non‐noble Metal Catalyst for Ammonia Decomposition

As a well‐established topic, single‐atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single‐atom form, the intrinsic roles of single‐atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co‐Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co‐Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat−1·min−1 at very low temperature (500 °C, GHSV = 840,000 mL·g−1·h−1) and Co‐Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non‐noble catalysts, and reaches or even exceeds numerous reported Ru‐based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co‐O‐Ba‐Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N‐H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Roles of Divinylbenzene Co‐Cross‐Linker in a Threefold Cross‐Linked Polystyrene–Phosphine Hybrid Monolith: Impact of Cross‐linking Degree on Catalytic Performance

AbstractContinuous‐flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross‐linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous‐flow reactions via transition‐metal catalysis. Additionally, the cross‐linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material‐based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono‐coordination and effective stabilization of metal complexes. We developed threefold cross‐linked polystyrene‐triphenylphosphine hybrid monoliths with cross‐linking structures adjusted by varying the content of divinylbenzene as co‐cross‐linker. The coordination behaviors and metal‐support interactions of these monoliths were evaluated, highlighting the importance of co‐cross‐linker content in site‐isolating phosphine units and stabilizing metal centers via arene‐metal interactions on the polystyrene network. By optimizing the cross‐linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd‐catalyzed C−Cl transformations, such as Suzuki–Miyaura cross‐couplings and Buchwald‐Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition‐metal catalysis.

Triphenylamine-Functionalized Metal Nanoclusters for Efficient and Stable Perovskite Solar Cells.

Reported herein is a ligand engineering strategy to develop photoelectric active metal nanoclusters (NCs) with atomic precision. Triphenylamine (TPA), a typical organic molecule in the photoelectric field, is introduced for the first time to prepare atomically precise metal NCs that prove effective in the fabrication of perovskite solar cells (PSCs). The scalable synthetic prototype, unique electronic strucuture, and atomically precise structure of the cluster ([(AgCu)37(PPh3)8(TPA-C≡C)24]5+) are illustrated in this work. When being employed as a buffer layer in the perovskite/HTL interface of PSCs, significantly enhanced performance is observed. The resultant n-i-p devices achieved a substantial power conversion efficiency as high as 25.1% and long-term stability. The findings offer valuable insights into preparing functionalized metal NCs that play multiple roles in improving the performance of the device: while the inorganic metal core enhances conductivity, the organic TPA shell promotes the "carrier transfer" between the perovskite and HTL layer and prevents the perovskite from corrosion.

Hollow silicalite-1 encapsulated nickel nanoparticles as highly stable catalysts in maleic anhydride hydrogenation

Anchoring active metal particles in zeolite cages can significantly improve catalytic stability. In this study, hollow silicalite-1 (HoS-1) encapsulated Ni nanoparticles catalyst (Ni@HoS-1) was prepared using the impregnation method and applied in MA hydrogenation. The encapsulation mechanism was explained as the zeolite wall restricting the evaporation of water in HoS-1, hence Ni particles would be spontaneously enriched within the zeolite cage after drying and calcination. Experiments revealed the specially designed structure effectively protected Ni particles from leaching, and after 5 cycles in liquid-phase batch reactions, the final MA conversion of Ni@HoS-1 is 40.8 % higher than that of Ni/S-1 (85.5 % vs 44.7 %). Moreover, the low acidity of Ni@HoS-1 also delayed the accumulation of carbon deposits, extending the continuous reaction lifespan from 128 h of Ni/S-1 to 188 h. These findings provided a new perspective for the controllable locating of active metal sites against the supports.

Research on the Strengthening Mechanism of MWCNTs-Cuf Composite Interlayer for Si3N4/TC4 Brazed Joints

With the rapid development of aerospace technology, the high-quality brazing connection between Si3N4 ceramic and TC4 titanium alloy has become a key factor in advancing the development of aircraft antenna covers. To improve the mechanical strength of the joints, this study used the electrophoretic deposition method to prepare a multi-walled carbon nanotubes-foam copper (MWCNTs-Cuf) composite interlayer and selected the optimal deposition parameters. The most suitable brazing parameters under this interlayer were also determined. The joints’ formation mechanism and fracture mode were revealed to elucidate the synergistic strengthening mechanism of the composite interlayer. The results showed that MWCNTs, based on their phase characteristics, produced high-density dislocations and fine crystal strengthening effects during the brazing cooling process. This effectively resisted the corrosion of the brazing material on the foam copper (Cuf), protected the integrity of the foam copper framework, and exerted the excellent plastic deformation ability of foam copper (Cuf). It reduced the residual stress in the joints, resulting in the highest shear strength of the MWCNTs- Cuf composite interlayer, reaching 96.23 MPa. Compared with only adding Ag-Cu-Ti active brazing filler metal and adding ordinary foam copper interlayer, the shear strength increased by 78.2% and 44.7%, respectively.

Synergy strategy of multi-metals confined in heteroatom framework toward constructing high-performance water oxidation electrocatalysts

The development of a low-cost, highly active, and non-precious metal catalyst for oxygen evolution reaction (OER) is of great significance. Multi-metallic catalysts containing Fe, Co, and Ni exhibit remarkable OER activity, while the specific contributions of each component and the synergistic effects in the ternary metal catalyst has remained elusive. In this work, we synthesized a series of S and N-doped mono-metallic, bi-metallic, and tri-metallic hollow carbon sphere electrocatalysts (M−SNC) with the goal of enhancing the catalysts OER activity and shedding light on the unique roles and synergistic effects of the various metals in the FeCoNi ternary metal catalyst. Our systematic analyses demonstrated the introduction of Fe effectively reduces the overpotential, Co accelerates the kinetics of OER, and the addition of Ni further improves the OER performance. Benefiting from the synergistic effects, the FeCoNi-SNC exhibits a low overpotential of 270 mV, with no morphological or structural changes after reaction, maintaining high activity for 72 h at 10 mA cm−2. Moreover, the assembled FeCoNi-SNC || Pt/C water electrolysis device operates for 65,000 s with minimal degradation, demonstrating its potential for practical application. This work presents a synergy strategy for the preparation of low-cost and highly efficient OER catalysts and further provides insights into the rational design and preparation of multicomponent catalysts.

NiFe pyrophosphate enables long-term alkaline seawater oxidation at an ampere-level current density

Seawater electrolysis has potential for scalable hydrogen (H₂) production, yet anode corrosion by chloride ions (Cl⁻) remains a critical challenge. Herein, we present an amorphous NiFe pyrophosphate (P2O74−) on Ni foam (NiFe-PPi/NF) for long-term alkaline seawater oxidation (ASO). Ex situ and in situ characterizations demonstrate that the in situ released P2O74− can act as an anion protective layer, effectively repelling Cl⁻ and safeguarding high-valence active metal sites during ASO. Through surface-anticorrosion design, NiFe-PPi/NF demonstrates stable operation at 1000 mA cm⁻2 for over 1000 hours with no loss in activity and requires a low overpotential of just 370 mV to achieve this industrial current density in alkaline seawater. This study offers a valuable strategy for developing corrosion-resistant anodes for ASO.

Modulating electronic density of active metal site via MXene intercalated by alkali ions for superior hydrogen production

Modulating electronic density of active metal site via MXene intercalated by alkali ions for superior hydrogen production

Highly Active Photoreduction of Atmospheric‐Concentration CO2 into CH3COOH over Palladium Particles on Nb2O5 Nanosheets

AbstractThe endeavor to drive CO2 photoreduction towards the synthesis of C2 products is largely thwarted by the colossal energy hurdle inherent in C−C coupling. Herein, we load active metal particles on metal oxide nanosheets to build the dual metal pair sites for steering C−C coupling to form C2 products. Taking Pd particles anchored on the Nb2O5 nanosheets as an example, the high‐angle annular dark‐field image and X‐ray photoelectron spectroscopy demonstrate the presence of Pd−Nb metal pair sites on the Pd‐Nb2O5 nanosheets. Density functional theory calculations reveal these sites exhibit a low reaction energy barrier of only 1.02 eV for C−C coupling, implying that the introduction of Pd particles effectively tailors the reaction step to form C2 products. Therefore, the Pd‐Nb2O5 nanosheets achieve a CH3COOH evolution rate of 13.5 μmol g−1 h−1 in photoreduction of atmospheric‐concentration CO2, outshining all other single photocatalysts reported to date under analogous conditions.

Loading Lewis Acid/Base Pair on Metal Nanocluster for Catalytic Ugi Reaction

AbstractConstructing structurally robust and catalytically active metal nanoclusters for catalyzing multi‐component reactions is an interesting while challenging task. Inspired by Lewis acid and Lewis base catalysis, we realized the combination of both Lewis acid and Lewis base sites on the surface of a stable gold nanocluster Au35Cd2. The catalytic potential of Au35Cd2 in four‐component Ugi reaction was explored, demonstrating high activity and exceptional recyclability. In‐depth mechanism studies indicate that the catalytic synergy of the Lewis acid/base pair is crucial for the high efficiency of Au35Cd2‐catalyzed Ugi reaction. Bearing the stable structure, multiple activation sites and hierarchical chirality, Au35Cd2 is expected to display further interesting catalytic performance such as asymmetric catalysis.

Synthesis and characterization of new organometallic lanthanides metal complexes for photodynamic therapy

New Schiff base ligand: 4-methoxy salicaldhyde-2-2-phenyl-hydrazono acetaldehíyde prepared by facile method. The molecular structures characterized by elemental analysis and proton magnetic resonance spectra (1H-NMR spectra). This spectra at the chemical shifts (3.5–10.39 ppm) confirmed the types and the numbers of protons. The sharp melting point at the range 110–112 °C confirmed purity. New optically active metal (samarium, terbium and gadolinium) complexes of the Schiff base synthesized in a one pot reaction. Vibrational IR spectra confirmed functional groups. Scanning electron microscopy micrographs confirmed that the modified microstructure of the metal complexes differed in morphology than the ligand. Powder X-ray diffraction patterns confirmed good crystalline structure. The optically activity of the solid metal complexes confirmed from electronic absorption spectra. The UV absorbance band at the wavelength range 280–390 nm and the intense phosphorescence bands up to 830 nm enabled application in photo dynamic therapy for apoptosis cancer cells by conversion triplet oxygen in the tissues into reactive singlet oxygen. Low charge transfer energy: 2.59–2.61 eV, high molar extinction coefficients (ε) at the order of magnitude \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\:{10}^{6}$$\\end{document} M− 1 cm− 1 and the intense phosphorescence bands reflected good photodynamic activity. The metal complexes are thermally stable.