Fourth Coordination Site Research Articles

Fluorosolvatochromism of Platinum Supramolecular Coordination Complexes: Stepwise Synthesis and Photophysical Properties of Organometallic Tetranuclear Pt(II) Squares

The stepwise synthesis and characterization of three new mixed-ligand organometallic tetranuclear platinum squares were achieved. All of the complexes were constituted by the conjunction of two (2,2′-bpy)Pt-terph-Pt(2,2′-bpy) (terph = p-terphenyl) fragments linked by a variety of N^N ligands (4,4′-bipyridine (4,4′-bpy), 1,4-di(pyridin-4-yl)benzene (dpbz), and 4,4′-di(pyridin-4-yl)-1,1′-biphenyl (dpbph)), which occupied the fourth coordination site of each metal center, giving rise to square-shaped molecules of the general formula [Pt2(2,2′-bpy)2(terph)(N^N)]2. Consequently, the tetranuclear complexes, {[Pt(2,2′-bpy)]4(μ-terph)2(μ-4,4′-bpy)2}{PF6}4 (7), {[Pt(2,2′-bpy)]4(μ-terph)2(μ-dpbz)2}{PF6}4 (8), and {[Pt(2,2′-bpy)]4(μ-terph)2(μ-dpbph)2}{PF6}4 (9) were constructed. The photophysical properties of these complexes were studied both in the solid state and in various solvents, revealing fluorosolvatochromism.

Phase-Transition-Induced Surface Reconstruction of Rh1 Site in Intermetallic Alloy for Propane Dehydrogenation.

The fine-tuning of the geometric and electronic structures of active sites plays a crucial role in catalysis. However, the intricate entanglement between the two aspects results in a lack of interpretable design for active sites, posing a challenge in developing high-performance catalysts. Here, we find that surface reconstruction induced by phase transition in intermetallic alloys enables synergistic geometric and electronic structure modulation, creating a desired active site microenvironment for propane dehydrogenation. The resulting electron-rich four-coordinate Rh1 site in the RhGe0.5Ga0.5 intermetallic alloy can accelerate the desorption of propylene and suppress the side reaction and thus exhibits a propylene selectivity of ∼98% with a low deactivation constant of 0.002 h-1 under propane dehydrogenation at 550 °C. Furthermore, we design a computational workflow to validate the rationality of the microenvironment modulation induced by the phase transition in an intermetallic alloy.

Orbital Occupancy Modulation to Optimize Intermediate Absorption for Efficient Electrocatalysts in Water Electrolysis and Zinc-Ethanol-Air Battery.

Spin engineering is a promising way to modulate the interaction between the metal d-orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o-c-CoSe2 -Ni is prepared as pre-catalyst, then in situ electrochemical impedance spectroscopy (EIS)and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3 O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc-ethanol-air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co-existence of four-coordinated sites and six-coordination sites in o-c-CoSe2 -Ni. The dz2 + dx2 -y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6 -Oh field with CoSe6 -Oh /CoSe4 -Td . This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc-ethanol-air battery.

Development of a Fluctuating Charge Model for Zinc-Containing Metalloproteins.

Metalloproteins widely exist in biology and play important roles in various processes. To accurately simulate metalloprotein systems, modeling polarization and charge transfer effects is vital. The fluctuating charge (FQ) model can efficiently generate atomic charges and simulate the charge transfer effect; it has been developed for a wide range of applications, but few models have been specifically tailored for metalloproteins. In this study, we present a fluctuating charge model specifically for zinc-containing metalloproteins based on the extended charge equilibration (EQeq) scheme. Our model was parametrized to reproduce CM5 charges instead of RESP/CHELPG charges because the former is less dependent on the conformation or basis set, does not suffer from unphysical charges for buried atoms, and is still being able to well reproduce the molecular dipoles. During our study, we found that adding the Pauling-bond-order-like term (referred to as the "+C term" in a previous study) between the zinc ion and ligating atoms significantly improves the model's performance. Although our model was trained for four-coordinated zinc sites only, our results indicated it can well describe the atomic charges in diverse zinc sites. Morever, our model was used to generate partial charges for the metal sites in three different zinc-containing metalloproteins (with four-, five-, and six-coordinated metal sites, respectively). These charges exhibited performance comparable to that of the RESP charges in molecular dynamics (MD) simulations. Additional tests indicated our model could also well reproduce the CM5 charges when geometric changes were involved. Those results indicate that our model can efficiently calculate the atomic charges for metal sites and well simulate the charge transfer effect, which marks an important step toward developing versatile polarizable force fields for metalloproteins.

Quasi-open Cu(I) sites for efficient CO separation with high O2/H2O tolerance.

Carbon monoxide (CO) separation relies on chemical adsorption but suffers from the difficulty of desorption and instability of open metal sites against O2, H2O and so on. Here we demonstrate quasi-open metal sites with hidden or shielded coordination sites as a promising solution. Possessing the trigonal coordination geometry (sp2), Cu(I) ions in porous frameworks show weak physical adsorption for non-target guests. Rational regulation of framework flexibility enables geometry transformation to tetrahedral geometry (sp3), generating a fourth coordination site for the chemical adsorption of CO. Quantitative breakthrough experiments at ambient conditions show CO uptakes up to 4.1 mmol g-1 and CO selectivity up to 347 against CO2, CH4, O2, N2 and H2. The adsorbents can be completely regenerated at 333-373 K to recover CO with a purity of >99.99%, and the separation performances are stable in high-concentration O2 and H2O. Although CO leakage concentration generally follows the structural transition pressure, large amounts (>3 mmol g-1) of ultrahigh-purity (99.9999999%, 9N; CO concentration < 1 part per billion) gases can be produced in a single adsorption process, demonstrating the usefulness of this approach for separation applications.

Highly efficient and stable near-infrared broadband luminescence in SrGa4O7:Cr3+, Yb3+ phosphor

Developing novel broadband near-infrared (NIR) phosphors is crucial to promote NIR phosphor-converted light emitting diodes (pc-LEDs) development. In this paper, a novel multifunctional near-infrared phosphor, SrGa4O7:Cr3+, Yb3+, was synthesized by the conventional high-temperature solid-state method. The emission band of the material spans from 650 nm to 1100 nm. Despite the predominance of four-coordinate and five-coordinate sites within the SrGa4O7 (SGO) lattice, the incorporation of Cr3+ ions induces distortion in the Ga–O tetrahedra, resulting in an octahedral environment for Cr3+. Under blue light excitation, the Cr3+ ions exhibit an ultra-wide emission band (650–900 nm) with a Full Width at Half Maximum (FWHM) of 131 nm. Furthermore, energy transfer from Cr3+ to Yb3+ was achieved in SrGa4O7:Cr3+, Yb3+, and the incorporation of an optimal quantity of Yb3+ co-dopant yielded a significantly enhanced and extraordinarily broad spectrum from 600 to 1100 nm. Moreover, Yb3+-codoping improves the thermal stability due to the energy transfer from Cr3+ to more thermally stable Yb3+ emitters, and the integrated intensity of SrGa4O7:Cr3+, Yb3+ at 300 K was 74% of that at room temperature. Based on these findings, a blue-light-excited NIR pc-LED was encapsulated. The forward voltage and intensity of the LED remained almost constant after 500 h of thermal aging at high temperatures, indicating its particular reliability in NIR pc-LED applications. The results show that SrGa4O7:Cr3+, Yb3+ phosphors have great potential in ultra-wideband NIR pc-LED applications.

Cyclopalladated complexes with pincer-like ONC-donor N-(4-R-benzoyl)-N′-(9-phenanthrylidene)hydrazines: Regioselective peri‑palladation of the 9-phenanthryl group

Two series of cyclopalladates [Pd(HL1–5)Cl] (1–5) and [Pd(L1–5)(PPh3)] (6–10) with the Schiff bases N-(4-R-benzoyl)-N′-(9-phenanthrylidene)hydrazines (H2Ln, where n = 1–5 for R = H, Cl, OMe, NO2 and NMe2, respectively and 2 Hs represent the amide and the ortho or peri H-atom of the 9-phenanthryl group) are reported. All the complexes were characterized by mass spectrometric and spectroscopic (IR, UV–Vis and fluorescence) measurements. Molecular structures of two Schiff bases (H2L1 and H2L4) and three representative complexes from each series [Pd(HL1,3,5)Cl] (1, 3 and 5) and [Pd(L1,2,4)(PPh3)] (6, 7 and 9) were confirmed by single crystal X-ray crystallographic studies. In each of the two types of complexes (HLn)– or (Ln)2– acts as ONC-donor pincer-like ligand. In [Pd(HL1,3,5)Cl], the metal center is in square-planar ONCCl environment assembled by amide-O, azomethine-N and 9-phenanthryl peri‑C coordinating (HL1,3,5)– and the Cl-atom. On the other hand, in [Pd(L1,2,4)(PPh3)], (L1,2,4)2– coordinate through amidate-O, azomethine-N and 9-phenanthryl peri‑C and the P-atom of PPh3 satisfies the fourth coordination site to form a square-planar ONCP coordination geometry around the metal center. The mass spectrometric and infrared and electronic spectroscopic characteristics of all the complexes are complementary to their molecular structures. All the Schiff bases and the complexes are emissive in solution. Theoretical calculations were carried out with a representative complex to comprehend the regioselective peri‑palladation of the 9-phenanthryl fragment of the tridentate ligand.

Primary amines as ligands and linkers in complexes of tripyrrindione radicals

Biopyrrin pigments, which result from the degradation of heme in biological settings, feature three or two pyrrole rings and characteristic pyrrolin-2-one termini. These scaffolds serve as redox-active ligands and electron reservoirs in coordination compounds. Tripyrrin-1,14-dione coordinates divalent transition metals as a dianionic ligand hosting a delocalized radical. Herein, we report the synthesis and characterization of palladium(II) and platinum(II) tripyrrindione complexes featuring a primary amine (i.e., aniline, tert-butylamine, 1,2-ethylenediamine) at the fourth coordination site within square planar geometries. Interligand hydrogen-bonding interactions are observed between the coordinated amine and the carbonyl groups on the tripyrrindione scaffold. Notably, 1,2-ethylenediamine is employed to link two Pt(II) tripyrrindione complexes. As revealed by optical absorption and electron paramagnetic resonance (EPR) spectroscopy, all resulting complexes present ligand-based radicals that are stable at room temperature and when exposed to air. Spin pairing through multicenter interactions leads to [Formula: see text]-dimerization of the tripyrrindione radicals and a decrease in the EPR signal at low temperatures. Electrochemical measurements indicate that the ligand system undergoes quasi-reversible one-electron oxidation and reduction, thus confirming the ability of tripyrrindione to form square planar complexes in three different redox states.

Ein neuartiger T-förmiger 14-Elektronen-Iridium(I)-Komplex stabilisiert durch eine agostische Ir–H-Wechselwirkung

AbstractThe reaction of [{Ir(µ-Cl)(coe)2}2] (1, coe =cis-cyclooctene) with the bulky tertiary phosphane P(o-tolyl)3in dichloromethane at room temperature was investigated. It afforded in good yield the tri-coordinate iridium(I) complex [IrCl{P(o-tolyl)3}2] (2) which was characterized in the solid state by a single-crystal X-ray diffraction study revealing a molecular structure of a rare tri-coordinate complex. The iridium(I) complex is stabilized by an agostic interaction of a hydrogen atom from the methyl group of the bulky phosphane ligand to fill the fourth unsaturated coordination site. The title compound crystallized from dichloromethane/diethyl ether as orange crystals in a mixture of two modifications (monoclinicP21/c,2a, and orthorhombicPbca,2b). The co-existence of the two components as a nearly 1:1 mixture in the crystalline bulk material was supported by solid-state31P{1H} NMR measurements.

Reversible Transformation and Distribution Determination of Diverse Pt Single-Atom Species.

In single-atom catalysts (SACs), the complexity of the support anchoring sites creates a vast diversity of single-atom species with varied coordination environments. To date, the quantitative distribution of these diverse single-atom species in a given SAC has remained elusive. Recently, CeO2-supported metal SACs have been extensively studied by modulating their local environments via numerous synthetic strategies. However, owing to the absence of a quantitative description, unraveling the site-specific reactivity and regulating their transformation remain challenging. Here, we show that two distinct Pt/CeO2 SACs can be reversibly generated by oxidative and nonoxidative dispersions, which contain varied Pt1On-Ceδ+ single-atom species despite similar Pt charge states and coordination numbers. By means of Raman spectroscopy and computational studies, we semiquantitatively reveal the distribution of diverse Pt1On-Ceδ+ species in each specific SACs. Remarkably, the minority species of Pt1O4-Ce3+-Ov accounting for only 14.2% affords the highest site-specific reactivity for low-temperature CO oxidation among the other abundant counterparts, i.e., Pt1O4-Ce4+ and Pt1O6-Ce4+. The second nearest oxygen vacancy (Ov) not only acts synergistically with the nearby active metal sites to lower the reaction barrier but also facilitates the dynamic transformation from six-coordinated to four-coordinated sites during cyclic nonoxidative and oxidative dispersions. This work elucidates the quantitative distribution and dynamic transformation of varied single-atom species in a given SAC, offering a more intrinsic descriptor and quantitative measure to depict the inhomogeneity of SACs.

Structural modifications to platinum(II) pincer complexes resulting in changes in their vapochromic and solvatochromic properties.

There is a need to develop rapidly responsive chemical sensors for the detection of low concentrations of volatile organic solvents (VOCs). Platinum pincer complexes have shown promise as sensors because of their colours and vapochromic and solvatochromic properties, that may be related to the non-covalent interactions between the pincer complexes and the guest VOCs. Here we report an investigation into a series of Pt(II) complexes based on the 1,3-di(pyridine)benzene tridentate (N⁁C⁁N) skeleton with the formula [Pt(N⁁C(R)⁁N)(CN)] (R = C(O)Me 2, C(O)OEt 3, C(O)OPh 4) with the fourth coordination site occupied by a cyanide ligand. Solid-state samples of the complexes have been tested with a range of volatiles including methanol, ethanol, acetone, dichloromethane and water, and while 2 displays thermochromism, 3 and 4 display rapidly reversible vapochromism and solvatochromism. These results are correlated with X-ray powder and single crystal X-ray structural data including an assessment of the crystal packing and the void space in the crystalline space. The cyanide ligand and the R substituents are involved in hydrogen bonding that creates the voids within the structures and interact with the solvent molecules that influence the Pt⋯Pt separation in the crystalline state.

Site-selective occupation of Cr3+ ions toward ultra-broadband near-infrared emission stannate phosphors

Cr3+-activated near-infrared (NIR) luminescent materials with broadband emission have attracted extensive attentions for multipurpose NIR phosphor-converted light-emitting diodes (LED). It is widely believed that broadband NIR-emitting from optical center Cr3+ could merely made in crystal-filed caused six-coordinated sites or four-coordinated sites. Herein, taking La3Ga5SnO14 compound with six-coordinated Sn and four-coordinated Ga sites as host, we design and synthesize a new ultra-broad NIR-emitting La3Ga5Sn1-xO14:xCr3+ (LGSn1-x:xCr3+) phosphor ranging from 700 to 1500 nm via solid-state reaction. Structural analysis, low-temperature spectra investigations, and density functional theory calculations demonstrate that, in La3Ga5SnO14 (LGSn) host lattice, six-coordinated Sn sites and four-coordinated Ga sites can be successfully occupied by Cr3+ ions, leading to two distinct Cr3+ centers and an impressive broadband with full width at half maximum of up to 275 nm. At 373 K, emission intensity of LGSn0.97:3%Cr3+ phosphor maintains 43% of that at room temperature. We fabricate a NIR phosphor-converted LED device by using as-prepared LGSn0.97:3%Cr3+ phosphor and a blue LED chip and demonstrate its potential applications in night vision and food analysis. These findings provide not only an in-deep insight on site-occupation of Cr3+ residing in compounds with six-coordinated sites and four-coordinated sites but also feasible method of designing ultra-broadband NIR phosphors.

Multilevel Computational Studies Reveal the Importance of Axial Ligand for Oxygen Reduction Reaction on Fe-N-C Materials.

The systematic improvement of Fe-N-C materials for fuel cell applications has proven challenging, due in part to an incomplete atomistic understanding of the oxygen reduction reaction (ORR) under electrochemical conditions. Herein, a multilevel computational approach, which combines ab initio molecular dynamics simulations and constant potential density functional theory calculations, is used to assess proton-coupled electron transfer (PCET) processes and adsorption thermodynamics of key ORR intermediates. These calculations indicate that the potential-limiting step for ORR on Fe-N-C materials is the formation of the FeIII-OOH intermediate. They also show that an active site model with a water molecule axially ligated to the iron center throughout the catalytic cycle produces results that are consistent with the experimental measurements. In particular, reliable prediction of the ORR onset potential and the Fe(III/II) redox potential associated with the conversion of FeIII-OH to FeII and desorbed H2O requires an axial H2O co-adsorbed to the iron center. The observation of a five-coordinate rather than four-coordinate active site has significant implications for the thermodynamics and mechanism of ORR. These findings highlight the importance of solvent-substrate interactions and surface charge effects for understanding the PCET reaction mechanisms and transition-metal redox couples under realistic electrochemical conditions.

Tunable “In-Chain” and “At the End of the Branches” Methyl Acrylate Incorporation in the Polyolefin Skeleton through Pd(II) Catalysis

The synthesis of functionalized polyolefins through coordination–insertion polymerization is a highly challenging reaction. The ideal catalyst, in addition to showing a high productivity, has to be able to control the copolymer microstructure and, in particular, the way of the polar vinyl monomer incorporation. In this contribution, we modified the typical Brookhart’s catalyst by introducing in the fourth coordination site of palladium a hemilabile, potentially bidentate ligand, such as a thiophenimine (N–S). The obtained cationic Pd(II) complexes, [Pd(Me)(N–N)(N–S)][PF6], generated active catalysts for the ethylene/methyl acrylate (MA) copolymerization leading to the desired copolymer with a different incorporation of the polar monomer depending on both the reaction medium and the N–S ligand. Surprisingly enough, the produced copolymers have the inserted acrylate both at the end of the branches (T(MA)) and in the main chain (M(MA)) in a ratio M(MA)/T(MA) that goes from 9:91 to 45:55 moving from dichloromethane to trifluoroethanol (TFE) as a solvent for the catalysis and varying the N–S ligand. The catalytic behavior of the new complexes was compared to that of the parent compound [Pd(Me)(N–N)(MeCN)][PF6], highlighting the fact that when the copolymerization is carried out in trifluoroethanol, this complex is also able to produce the E/MA copolymer with MA inserted both in the main chain and at the end of the branches. Accurate NMR studies on the reactivity of the precatalyst [Pd(Me)(N–N)(MeCN)][PF6] with the two comonomers allowed us to discover that in the fluorinated solvent, the catalyst resting state is an open-chain intermediate having both the organic fragment, originated from the migratory insertion of MA into the Pd–Me bond, and the acetonitrile coordinated to palladium and not the six-membered palladacycle typically observed for the Pd-α-diimine catalysts. This discovery is also supported by both DFT calculations and in situ NMR studies carried out on [Pd(Me)(N–N)(N–S)][PF6] complexes that point out that N–S remains in the palladium coordination sphere during catalysis. The open-chain intermediate is responsible for the growth of the copolymer chain with the polar monomer inserted into the main chain.

New Pd(II) complexes of the bisthiocarbohydrazones derived from isatin and disubstituted salicylaldehydes: Synthesis, characterization, crystal structures and inhibitory properties against some metabolic enzymes.

Pd(II) complexes (Pd1, Pd2, and Pd3) were synthesized for the first time using asymmetric isatin bisthiocarbohydrazone ligands and PdCl2(PPh3)2. All complexes were characterized by a range of spectroscopic and analytical techniques. The molecular structures of Pd1 and Pd3 have been determined by single-crystal X-ray diffraction analysis. The complexes are diamagnetic and exhibit square planar geometry. The asymmetric isatin bisthiocarbohydrazone ligands coordinate to Pd(II) ion in a tridentate manner, through the phenolic oxygen, imine nitrogen and thiol sulfur, forming five- and six-membered chelate rings within their structures. The fourth coordination site in these complexes is occupied by PPh3 (triphenylphosphine). The free ligands and their Pd(II) complexes were evaluated for their carbonic anhydrase I, II (hCAs) and acetylcholinesterase (AChE) inhibitor activities. They showed a highly potent inhibition effect on AChE and hCAs. Ki values are in the range of 9 ± 0.6-30 ± 5.4nM for AChE, 7 ± 0.5-16 ± 2.2nM for hCA I and 3 ± 0.3-24 ± 1.9nM for hCA II isoenzyme. The results clearly demonstrated that the ligands and their Pd(II) complexes effectively inhibited the used enzymes.

1-Chloroalumole

A representative of the stable alumoles with a chlorine substituent at the aluminum atom was synthesized by the coupling of a cyclobutadiene dianion derivative and aluminum trichloride. The structure of alumole was established by X-ray crystallography, which showed that alumole exists as a monomer. The aluminum atom is tetracoordinated with the fourth coordination site occupied by a thf molecule, which reduces the intrinsically high Lewis acidity of the aluminum center, thus stabilizing the alumole molecule.

Nickel(II) complexes containing tridentate ONCi ligands (i = abnormal N-heterocyclic carbene donors) and their catalytic application in Suzuki-Miyaura coupling reaction.

New nickel complexes with tridentate phenoxy-amidate-aNHC donor groups were synthesized from the reactions between nickel acetate and imidazolium ligand precursors in net pyridine. An unusual degradation pathway was observed, leading to imidazole derivatives occupying the fourth coordination sites in these square planar complexes. A new imidazole-coordinated nickel complex was found to be efficient in catalyzing Suzuki-Miyaura cross-coupling with aryl chlorides under 3 mol% of catalyst loading. The catalytic activities were superior to those of its reported normal NHC counterpart. Instead of the common procedure of using additional phosphine, the addition of IMes·HCl significantly enhances the product yields of the catalytic reaction.

Stereochemistry and chiroptical properties of bimetallic single helicates of hexapyrrole-α,ω-dicarbaldimines with high diastereoselectivity

Bimetallic complexes of hexapyrrole-[Formula: see text],[Formula: see text]-dicarbaldimines consisting of a pair of four-coordinate metal sites adopt a helical closed [Formula: see text]-symmetric form or sigmoidal open forms depending on whether the 2,2[Formula: see text]-bipyrrole subunit at the center of the hexapyrrole chain takes cis- or trans-conformation. X-ray crystallography of a bisNi complex having N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units at both ends of the hexapyrrole chain revealed a non-symmetric heterohelical open form where the metal coordination sites of opposite helical sense sit on opposite sides of the central 2,2[Formula: see text]-bipyrrole subunit. BisPd complexes preferred a closed [Formula: see text] form and a steric bulk at the 3,3[Formula: see text]-position of the 2,2[Formula: see text]-bipyrrole subunit improved the helical sense bias. A bisPd complex with N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units adopts a helical closed [Formula: see text] form exclusively with full bias for a [Formula: see text]-helical sense. These bimetallic single stranded helicates were reversibly oxidized to [Formula: see text]-cation radicals at 0.1∼0.3 V vs. a ferrocene/ferrocenium couple and spectroelectrochemistry revealed remarkable absorption and CD spectral changes in the Vis-NIR region.

Synthesis of Unsupported Primary Phosphido Complexes of Aluminum(III)

AbstractPrimary phosphido complexes of aluminum(III) are rare, particularly those that are not supported by interactions with Lewis bases or stabilizing cations. Here we report two new examples of unsupported primary phosphido complexes of Al(III). The ancillary ligand on Al is a pincer ligand, diiminopyridine (denoted as I2P). Solid‐state structures show distorted tetrahedral geometry about Al and single bond character in the Al−P bond. Near infra‐red spectra display low energy absorption bands near 1050 nm that are consistent with pincer ligand – Al charge transfer transitions and metalloaromatic character in the “(I2P2−)Al” fragment of the molecules. The phosphido ligands lie out of the I2P ligand plane by up to 15° and this is consistent with our previous reports where π‐donor halide ligands occupy the fourth coordination site on Al.

New asymmetric bisthiocarbohydrazones and their mixed ligand nickel(II) complexes: Synthesis, characterization, crystal structure, electrochemical-spectroelectrochemical property, antimicrobial and antioxidant activity

New asymmetric isatin bisthiocarbohydrazone ligands were synthesized by the condensation of 3,5-dibromosalicylaldehyde, 3,5-dichlorosalicylaldehyde and 3-bromo-5-chlorosalicylaldehyde with isatin monothiocarbohydrazone. New mixed ligand Ni(II) complexes were synthesized from these ligands using triphenylphosphine (PPh3) as a secondary ligand. The synthesized ligands and complexes were characterized by elemental analysis, FT-IR, 1H NMR, UV–Vis spectroscopy and mass spectrometry techniques, along with conductivity measurements. The ligands bind to the Ni(II) ion as ONS donors. The fourth coordination site is completed by the secondary ligand PPh3. The single crystal structures of one ligand and one complex were also resolved by X-ray crystallography. The electrochemical responses of the ligands and their complexes were determined and the results were evaluated to illustrate the influence of the substitution of different groups on the ligands. While the free ligands only give one oxidation peak, two oxidation peaks are observed for the Ni(II) complexes. Complexation of the ligands with the Ni(II) ion considerably affected the in-situ spectroelectrochemical responses of the ligands. Finally, the in vitro antioxidant and antimicrobial activities of the synthesized compounds were determined.