Ni Complexes Research Articles

Ni‐Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings

AbstractWe report the Ni‐catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.

High-Strength, Self-Healing Copolymers of Acrylamide and Acrylic Acid with Co(II), Ni(II), and Cu(II) Complexes of 4′-Phenyl-2,2′:6′,2″-terpyridine: Preparation, Structure, Properties, and Autonomous and pH-Triggered Healing

The utilization of self-healing polymers is a promising way of solving problems associated with the wear and tear of polymer products, such as those caused by mechanical stress or environmental factors. In this study, a series of novel self-healing, high-strength copolymers of acrylamide, acrylic acid, and novel acrylic complexes of 4′-phenyl-2,2′:6′,2″-terpyridine [Co(II), Ni(II), and Cu(II)] was prepared. A systematic study of the composition and properties of the obtained polymers was carried out using a variety of physicochemical techniques (elemental analysis, gel permeation chromatography (GPC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR), ultraviolet-visible spectroscopy (UV-vis), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), confocal laser scanning microscopy (CLSM), and tensile testing). All metallopolymer samples exhibit autonomous intrinsic healing along with maintaining high tensile strength values (for some samples, the initial tensile strength exceeded 100 MPa). The best values of healing efficiency are possessed by metallopolymers with a nickel complex (up to 83%), which is most likely due to the highest lability of the metal–heteroatom coordination bonds. The example of this system shows the ability to re-heal with negligible deterioration of the mechanical properties. The possibility of tuning the mechanical properties of self-healing films through the use of different metal ions has been demonstrated.

Recent achievements in nickel based electrochemical biorefinery of 5-hydroxymethylfurfural

The electrochemical conversion of biomass offers a sustainable approach for energy recycling and environmental protection. Specifically, the electro-oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid is notable for its potential to produce value-added products, including biodegradable plastics and other environmentally friendly materials. A critical factor in this process is the performance of the catalysts. Nickel-based catalysts have shown high efficiency and durability, primarily due to the formation of Ni-OOH active sites. This paper reviews recent advancements in the nickel-based electrocatalytic oxidation of HMF, including the use of Ni, Ni alloys, Ni oxides, Ni hydroxides, and other Ni complex, and discusses the underlying catalytic mechanisms. Additionally, it introduces the coupling reactions, various reactor designs and outlines future research directions, focusing on exploring reaction mechanisms, developing electrocatalysts, and practical applications of this technology.

Supramolecular architectures, Hirshfeld surfaces analysis, spectroscopic, computational and photovoltaic properties of nickel(II) binary and ternary complexes of N-phenethyl-iminodiacetate (2-) chelate

The bluish-green color nickel(II) binary and/or ternary compounds have been isolated from the solution of stoichiometric reaction between Ni(II) hydroxy-carbonate and N-phenethyl-iminodiacetic acid (H2pheida) chelating ligand in aqueous media with compound (2); [Ni(pheida)(Him)3]·4H2O and without imidazole compound (1); [Ni(pheida)(H2O)3]. The crystal pattern of binary compound [Ni(pheida)(H2O)3] (1) differs from the related tetra-hydrated ternary complex of [Ni(pheida)(Him)3]·4H2O (2) can be attributed to the presence of stronger N-(Him) spacer of imidazole ligand. The compounds reported herein, have been characterized by means of elemental analysis, FTIR, UV–vis, TGA and X-ray crystallography. Moreover, the distinctive inter-molecular forces particularly H-bonding interactions, 2D fingerprint plots and supramolecular architecture have been studied using Hirshfeld surface analysis. The nickel(II) binary and ternary complexes (1) and (2) show distorted octahedral geometry around the Ni(II) ion of the type 1 + 2 + 2 + 1 imposed by 3d8 electronic configuration with degenerate fully and half occupied t2g6 and eg2 orbitals respectively. The higher John-Teller distortion has been observed for complex (2) than that of complex (1). The IDA arm of chelate adopted fac-NO2 conformation in both complexes (1) and (2). Moreover, the photovoltaic properties as semiconducting nature for ligand and their corresponding Ni(II) complexes were estimated using Tauc’s equation, αhν = A(hν-Eg)r, where r = ½ for indirect and 2 for direct electronic transitions through UV–vis absorption data. The indirect and direct electronic transition bandgap (Eg) calculated for complex (1) is 2.0 and 3.07 eV respectively. Similarly, 2.55 and 4.39 eV respectively measured for complex (2).

Exploring supramolecular c-br … Br-C interactions as Organizing tools in a novel Ni(II)-tetrabromophthalate complex. Crystal structure and solvatochromism studies

The understanding of the non-covalent halogen…halogen interaction inside coordination complexes has special interest as design tools in crystal engineering and coordination chemistry. In this work, we show the use of the supramolecular C-Br…Br-C interactions as a tool in the crystalline organization of a Ni(II) complex and its solvatochromic properties. To do so, we selected the 3,4,5,6-tetrabromophthalate (TBrPh) ligand where the Br atoms pointing outside to favor their self-assembly through these interactions.Thus, a novel complex, [Ni(tmeda)(TBrPh)(H2O)3]•CH3OH was synthesized by the reaction between [Ni(tmeda)].(NO3)2 (tmeda = N, N, N’, N’-tetramethylethylenediamine) and K2TBrPh. The Ni(II)-complex was structurally analyzed by single-crystal X-ray diffraction, Hirshfeld surfaces, multiple analytical tools and DFT calculations.Structural analysis shows that Ni(II)-complex has 1D supramolecular chains based on the cooperativity of intra/inter-molecular charged-assisted hydrogen bonds of type Ni-OH2…O and Csp2-Br…Br-Csp2 interactions into 2D networks. These Br…Br interactions organize the crystal packing in the solid state as is evidenced by the molecular electrostatic potential studies and Plot of Hirsfeld surface.This Ni(II)-complex displays solvatochromism with a wide range of solvents (alcohols, DMF, CH3CN, chlorinated solvents), and solvent-dependent absorption maxima presents linear behavior as a function of their dielectric constant.

Bowl‐Shaped Anthracene‐Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion

The synthesis of bowl‐shaped antiaromatic molecules represents a formidable challenge, because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report the synthesis and properties of bowl‐shaped fused anthrylnorcorroles that exhibit near‐infrared (NIR) absorption reaching 1900 nm. The oxidation of meso‐anthryldibromodipyrrin provides fused anthryldibromodipyrrin, which was converted to the fused mono‐ and bisanthrylnorcorroles through Ni(0)‐mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single‐crystal X‐ray diffraction analyses revealed bowl‐shaped structures for the fused mono‐ and bisanthrylnorcorroles, which enables them to act as suitable receptors for C60 with bonding constants of 2.89 × 103 M–1 and 1.59 × 103 M–1, respectively. The formation of a 1:1 complex between the fused monoanthrylnorcorrole and C60 was confirmed by single‐crystal X‐ray diffraction analysis. The effective expansion of the π‐conjugation through the triple fusion of the norcorrole with the anthracene units substantially enhances the near‐infrared absorption bands, which endows these anthrylnorcorroles with effective photothermal conversion.

Synthesis, Characterization and Biological Studies of Gemifloxacin Mesylate with Nickel(II) and Copper(II)

Gemifloxacin mesylate, a fourth-generation fluoroquinolone-type antibiotic, is widely used for community treatment of acquired pneumonia and severe bacterial infections. The Cu(II) and Ni(II) complexes of gemifloxacin mesylate were synthesized by refluxing an aqueous solution of the ligand with the required amount of metal(II) salts in a round bottom flask with 2:1 (L:M) ratio in an oil bath at 90 ºC with a continuous stirring for 4 h. The mixture was kept overnight to obtain a coloured solid complex. The synthesized metal(II) complexes were characterized by physico-chemical parameters and spectral analyses, including UV-Vis, FT-IR and 1H NMR. The structures of the complexes were further confirmed by elemental (CHNS) and TG-DTA analyses. The spectral findings revealed that metal-ligand interaction has successfully occurred where the ligand acted as a bidentate chelate in the synthesized metal(II) complexes. The IR studies showed that upon complexation the characteristic carboxylic stretching frequency at 1714 cm-1 disappeared and the pyridone stretching frequency shifted to a lower frequency region. The 1H NMR data of the complexes confirm the effective interaction between the metal and the ligand via 3-carboxyl group and 4-oxo groups. The thermal and elemental analyses data were also in agreement with the proposed interaction. The ligand as well as its metal(II) complexes showed significant activity against all the studied 11 bacterial strains and one of the fungal strains, Candida sp.

Bowl-Shaped Anthracene-Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion.

The synthesis of bowl-shaped antiaromatic molecules represents a formidable challenge, because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report the synthesis and properties of bowl-shaped fused anthrylnorcorroles that exhibit near-infrared (NIR) absorption reaching 1900 nm. The oxidation of meso-anthryldibromodipyrrin provides fused anthryldibromodipyrrin, which was converted to the fused mono- and bisanthrylnorcorroles through Ni(0)-mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single-crystal X-ray diffraction analyses revealed bowl-shaped structures for the fused mono- and bisanthrylnorcorroles, which enables them to act as suitable receptors for C60 with bonding constants of 2.89 × 103 M-1 and 1.59 × 103 M-1, respectively. The formation of a 1:1 complex between the fused monoanthrylnorcorrole and C60 was confirmed by single-crystal X-ray diffraction analysis. The effective expansion of the π-conjugation through the triple fusion of the norcorrole with the anthracene units substantially enhances the near-infrared absorption bands, which endows these anthrylnorcorroles with effective photothermal conversion.

Precisely Prepared Hierarchical Micelles of Polyfluorene-block-Polythiophene-block-Poly(phenyl isocyanide) via Crystallization-Driven Self-Assembly.

The precise preparation of hierarchical micelles is a fundamental challenge in modern materials science and chemistry. Herein, poly(di-n-hexylfluorene)-block-poly(3-tetraethylene glycol thiophene) (poly(1m-b-2n)) diblock copolymers and polyfluorene-block-polythiophene-block-poly(phenyl isocyanide) triblock copolymers were synthesized using a one-pot process via the sequential addition of corresponding monomers using a Ni(II) complex as a single catalyst for living/controlled polymerization. The crystallization-driven self-assembly of amphiphilic conjugated poly(1m-b-2n) led to the formation of nanofibers with controlled lengths and narrow dispersity. The block copolymers exhibited white, yellow, and red emissions in different self-assembly states. By using uniform poly(1m-b-2n) nanofibers as seeds, introducing the polyfluorene-block-polythiophene-block-poly(phenyl isocyanide) triblock polymer as a unimer in the seed growth process, and adjusting the structure of the poly(phenyl isocyanide) block and the polarity of self-assembly solvent, A-B-A triblock micelles, multiarm branched micelles, and raft micelles were prepared.

Precisely Prepared Hierarchical Micelles of Polyfluorene‐block‐Polythiophene‐block‐Poly(phenyl isocyanide) via Crystallization‐Driven Self‐Assembly

The precise preparation of hierarchical micelles is a fundamental challenge in modern materials science and chemistry. Herein, poly(di‐n‐hexylfluorene)‐block‐poly(3‐tetraethylene glycol thiophene) (poly(1m‐b‐2n)) diblock copolymers and polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock copolymers were synthesized using a one‐pot process via the sequential addition of corresponding monomers using a Ni(II) complex as a single catalyst for living/controlled polymerization. The crystallization‐driven self‐assembly of amphiphilic conjugated poly(1m‐b‐2n) led to the formation of nanofibers with controlled lengths and narrow dispersity. The block copolymers exhibited white, yellow, and red emissions in different self‐assembly states. By using uniform poly(1m‐b‐2n) nanofibers as seeds, introducing the polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock polymer as a unimer in the seed growth process, and adjusting the structure of the poly(phenyl isocyanide) block and the polarity of self‐assembly solvent, A‐B‐A triblock micelles, multiarm branched micelles, and raft micelles were prepared.

Evaluation of Antimicrobial, Antitumor, Antioxidant Activities, and Molecular Docking Studies of Some Co(II), Cu(II), Mn(II), Ni(II), Pd(II), and Pt(II) Complexes With a Schiff Base Derived From 2‐Chloro‐5‐(trifluoromethyl)aniline

ABSTRACTThe antimicrobial, antitumor and antioxidant potential of Co(II), Cu(II), Mn(II), Ni(II), Pd(II), and Pt(II) complexes with 2‐(((2‐chloro‐5‐(trifluoromethyl)phenyl)imino)methyl)phenol HL ligand was investigated. A molecular docking study was carried out to estimate the predicted binding affinity of the compounds to protein targets involved in proliferative and bacterial activities. Fluorescence quenching studies and synchronous spectra were used to examine the metal complexes interactions with CT‐DNA and BSA protein. The DNA binding study have revealed that the complexes are capable of binding with DNA via intercalative mode. The antimicrobial activity of the ligand and metal complexes was studied against three Gram‐positive bacteria, two Gram‐negative bacteria, and three strains of fungi. The best antibacterial effect was demonstrated by the Pt(II) complex on the Staphylococcus aureus strain, and as for the inhibitory effect on fungi, it was stronger on the Candida albicans strain after treatment with the Co(II) complex. The in vitro antiproliferative activity of ligand and complexes was analyzed using MTT, Annexin V/PI, and cell cycle assays. The in vitro results showed that, except for Pd(II) complex, where slight effects were observed, the MCF‐7 line was resistant to the activity of the complexes. In the case of A549 cells, Cu(II) and Pd(II) complexes showed a dose‐dependent antitumor activity, confirmed by both the Alamar blue and the Annexin V/PI analysis. Finally, the antioxidant activity of the compounds was examined by ABTS and DPPH methods. Antioxidant investigation showed that the Ni(II) complex possesses a remarkable ability to trap the cation of the ABTS+ radical (IC50 value 9.35 μM).

Synthesis, characterization, antimicrobial activity of 2-amino-5-picoline and dipicolinic acid of Ni(II) and Cu(II) metal complexes

Synthesis, characterization, antimicrobial activity of 2-amino-5-picoline and dipicolinic acid of Ni(II) and Cu(II) metal complexes

Co(II), Ni(II), and Cu(II) Ternary Complexes With 2,6‐Pyridinedicarboxylic Acid and 2,2′‐Bipyridyl: Synthesis, Characterization, DNA Binding, Photo‐Cleavage, and Antimicrobial Studies

ABSTRACTThe interaction of 2,6‐pyridinedicarboxylicacid (PDA) and 2,2′‐bipyridyl (Bipy) with Co(II), Ni(II), and Cu(II) ions produced new ternary complexes [M (PDA)(Bipy)(H2O)] (M = Co(II), Ni(II), and Cu(II)), which were studied by elemental, spectral (FT‐IR, Mass, UV–Vis), and thermal analysis, and their interaction with Ct‐DNA was thoroughly studied using various methods, including absorption spectroscopy, fluorescence spectroscopy, and viscosity measurements. Spectrophotometric titration and viscosity measurements indicated that all the complexes bind to DNA via the groove mode of binding. The salt‐dependent binding of ternary metal complexes to Ct‐DNA has been studied by a UV–Vis spectrophotometric titration experiment. Furthermore, photocleavage studies were used to examine how the metal complexes interacted with the pBR322 DNA, and the results proved that these compounds have obvious photo cleavage properties. The biological effects were studied by antibacterial activity.

Synthesis, characterization, DFT computational studies and biological activity of transition metal complexes derived from 4-(((6-nitrobenzo[d]thiazol-2-yl)imino)methyl)benzene-1,3-diol

A series of Co(II), Ni(II), Cu(II), Zn(II) complexes have been synthesized with a benzothiazole azo dye containing tridentate (NNO) donor ligand 4-(((6-nitrobenzo[d]thiazol-2-yl)imino)methyl)benzene-1,3-diol derived from 2-amino-6-nitrobenzothiazole and 2,4-dihydroxybenzaldehyde. The structures of the novel ligand and metal complexes were identified and confirmed via various spectroscopic techniques (FT-IR,1H NMR,13C NMR, UV-Vis, mass spectrometry), TGA-DTA, powder X-ray diffraction, and DFT calculations. The optimal structural parameters and chemical reactivity of the ligand and metal complexes have been investigated using Density Functional Theory calculations (DFT/B3LYP,6-31G** and LanL2DZ basis sets) to provide insight about their frontier molecular orbitals (FMO) and molecular electrostatic potential (MESP). In vitro DPPH radical scavenging techniques have been used to assess the antioxidant activity of the ligand and complexes, indicating good antioxidant activity. The Ni(II) complex was the most potent with the lowest IC50 values. The in vitro antibacterial activities have been explored by screening against bacteria (Bacillus subtilis) and bacteria (E. coli) exhibiting significant activity against the tested strains of bacteria with Zn(II) complex as most potent with the lowest MIC value against E. coli and B. subtilis) and highest zone of inhibition against E. coli and B. subtilis at 1000 μg/mL concentration). The antifungal activity of complexes against Aspergillus niger and Candida albicans indicate that the Co(II) complex is most active for C. albicans and Zn(II) complex for A. niger .

Synthesis and EMI shielding study of Ni (II) semicarbazone driven nickel nanoparticles

Herein, we report the synthesis of nickel nanoparticles (Ni-NPs) from Ni (II) complexes of cyclic semicarbazone derivatives and their electromagnetic interference (EMI) shielding behaviour. Ni (II) complexes of cyclic semicarbazones were synthesized and characterized by various spectroscopic tools. It was observed that such complexes are excellent precursors for the synthesis of Ni-NPs when reduced by hydrazine hydrate. It is expected that the reaction kinetics will be ably normalized by the presence of semicarbazone ligand and that upon dissociation and partial consumption during nano-particle formation, will provide an added advantage of mild functionality around the particles. Overall various nickel complexes obtained from cyclic semicarbazones were tested as an effective precursor for the synthesis of Ni-NPs which were characterized by XRD, TEM, SEM, and AFM, and their magnetic behaviour was studied by VSM. EMI shielding efficiency of flexible Ni/PVA composite films showed shielding efficiency of about minus (−) 30 dB in X-band (8–12 GHz) for about 25 % loading in the PVA matrix.

Electrochemical, photocatalytic and biological investigation of carbaldehyde derived azo dye ligand and its Co(II), Ni(II), Cu(II) complexes

2-[(E)-(3-hydroxypyridin-2-yl)diazenyl]-1H-indole-3-carbaldehyde (HDC) a novel azo dye ligand and its Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) complexes have been prepared. The newly synthesized compounds were characterized by physiochemical techniques. The modified electrode, [Co(HDC)2Cl2]/GCE has been prepared by using the synthesized Co(Ⅱ) complex to check the electrocatalytic properties by cyclic Voltammetric (CV) studies. The biologically important molecule, folic acid present in the solution at different concentration has been detected by CV technique. The sensitivity of [Co(HDC)2Cl2]/GCE was 8.366 μAμM−1cm−2 and the limit of detection (LOD) 6.666 μM/L in the linear range 20–140 μM/L. The oxidation current of folic acid increased potentially with scan rate and the regression found was 0.9961, which indicates surface diffusion-controlled nature of process. The synthesized compounds were also screened for antimicrobial, antioxidant and anticancer activities. All the synthesized compounds gave promising results towards biological activities. The photodegradation of Methylene Blue dye was studied under visible light and in the presence of metal complexes to determine the catalytic efficiency of the synthesized metal complexes. The results indicated that the [Co(HDC)2Cl2] exhibited excellent results when compared to [Ni(HDC)2Cl2] and [Cu(HDC)2Cl2] complexes.

Ancillary Ligand-Promoted Charge Transfer in Bis-indole Pyridine Ligand-Based Nickel Complexes.

There is growing demand for the utilization of first-row transition metal complexes in light-driven processes instead of their conventional noble metal counterparts due to the greater sustainability of first-row transition metal complexes. However, their major drawback is the ultrafast lifetime of the electronic excited states of these first-row transition metal complexes, particularly those of d8 square-planar systems such as Ni(II) complexes, wherein low-lying metal-centered (MC) states provide the deactivation pathway. To increase the excited-state lifetime and broaden their applications, it is important to develop sterically bulky, strong field ligands with low-lying π* orbitals and a highly σ-donating nature to augment the energy of MC states. The current strategy relies on synthetically carbene-based ligands, which are substitutionally cumbersome and act as σ-donors only. In this work, we introduce a bis-indole pyridine (H2BIP) ligand framework, whose dianionic congener (BIP) demonstrates the ability to form stronger covalent bonds with a Ni(II) center compared to neutral donors like carbene and its effect on the complex to produce a less distorted excited-state structure. When conjoined with ancillary ligands such as pyridine or lutidine, the BIP ligand orchestrates the formation of low-energy 3CT states, which decay in ∼40 ps.

A tale of two old drugs tetracycline and salicylic acid with new perspectives—Coordination chemistry of their Co(II) and Ni(II) complexes, redox activity of Cu(II) complex, and molecular interactions

Extensive use of the broad-spectrum tetracycline antibiotics (TCs) has resulted their wide spread in the environment and drive new microecological balances, including the infamous antibiotic resistance. TCs require metal ions for their antibiotic activity and resistance via interactions with ribosome and tetracycline repressor TetR, respectively, at specific metal-binding sites. Moreover, the Lewis-acidic metal center(s) in metallo-TCs can interact with Lewis-basic moieties of many bioactive secondary metabolites, which in turn may alter their associated chemical equilibria and biological activities. Thus, it is ultimately important to reveal detailed coordination chemistry of metallo-TC complexes. Herein, we report (a) conclusive specific Co2+, Ni2+, and Cu2+-binding of TC revealed by paramagnetic 1H NMR, showing different conformations of the coordination and different metal-binding sites in solution and solid state, (b) significant metal-mediated activity of Cu-TC toward catechol oxidation with different mechanisms by air and H2O2 (i.e., mono- and di-nuclear pathways, respectively), (c) interactions of metallo-TCs with bioactive salicylic acid and its precursor benzoic acid, and (d) noticeable change of TC antibiotic activity by metal and salicylic acid. The results imply that TCs may play broad and versatile roles in maintaining certain equilibria in microecological environments in addition to their well-established antibiotic activity. We hope the results may foster further exploration of previously unknown metal-mediated activities of metallo-TC complexes and other metalloantibiotics.

Terpyridine Ni(II) Complex Grafted CdS Nanorods for Cooperative Selective Benzyl Alcohol Oxidation and Hydrogen Production.

Efficient utilization of photogenerated charge carriers to realize photocatalytic solar fuel production and oxidative chemical synthesis is a challenging task. Herein, a conventional amidation reaction route is adopted to successfully construct a novel composite photocatalyst composed of a Ni(II)-terpyridine complex with carboxyl groups grafted on CdS nanorods (labeled as CdS@Ni(terpyC)2). Experimental results have unequivocally revealed that the as-fabricated composite catalyst exhibited a remarkable enhancement in photocatalytic activity for the dehydrogenation of benzyl alcohol under visible light, demonstrating superior hydrogen evolution efficiency and benzaldehyde selectivity, surpassing both pristine CdS and the blend of CdS and Ni(terpyC)2. The carrier dynamics study demonstrated that the Ni(terpyC)2 on the surface of CdS could quickly extract the photogenerated electrons of CdS, which reduced the carrier recombination efficiency, further improving the photocatalytic activity of the catalyst. This work illustrates the effect of surface active site engineering on photocatalysis and is expected to shed substantial inspiration on future surface modulation and design of semiconductor photocatalysts.

Metal-Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering.

Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal-ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt)2]n- and [Ni(mnt)2]n- anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core-valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal-ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal "ligand field" or "d-d" states that typically dominate the photophysics of 3d metal complexes but with significant metal-ligand charge transfer character dictated by their covalency. These results suggest that strong metal-ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.