Pyrazole Complexes Research Articles

Substituents' Effect on the Photophysics of Trinuclear Copper(I) and Silver(I) Pyrazolate-Phosphine Cages.

A series of structurally similar trinuclear macrocyclic copper(I) and silver(I) pyrazolate complexes bearing various short-bite diphosphine R2PCH(R')PR2 ligands are reported. Upon diphosphine coordination, the planar geometry of the initial complexes undergoes bending along the line between two metal atoms coordinated to the phosphorus moieties. The complexes based on dcpm ligands (R = cyclohexyl, R' = H, Ph) do not exhibit dynamic behavior in solution at room temperature on the 31P NMR time scale as it was previously observed for similar trinuclear copper complexes bearing the dppm (R = Ph, R' = H) scaffold. All copper(I) complexes exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. Importantly, the use of aliphatic substituents on the phosphorus atoms instead of aromatic ones leads to an almost double increase in the quantum efficiency (ΦPL) of photoluminescence by eliminating nonradiative decay from the 3LCPh states of the dppm aromatic rings. The higher donating ability of the substituents in the pyrazolate ligand (CF3 vs CH3) lowers the energy of the metal-centered excited state, allowing for a significant metal impact on the T1 state. Finally, the Ag(I) complex displays an emission efficiency of approximately 14%, being the highest among known trinuclear silver(I) pyrazolate homometallic derivatives.

Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.

The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [TcII(NS)Cl3(PPh3)2] (3) and [TcII(NS)Cl3(PPh3)(OPPh3)] (4) and their reaction products with hydrotris(pyrazolyl)borates, {HB(pzR)3}-. Similar reactions were conducted with [TcI(NO)Cl2(PPh3)2(CH3CN)] and related rhenium thionitrosyls. Remarkably, most such reactions result in a rapid cleavage of the boron-nitrogen bonds of the ligands and the formation of pyrazole complexes of the two group 7 metals. Only one compound with an intact {HB(pzR)3}- ligand could be isolated: the technetium(I) complex [TcI(NO)Cl(PPh3){HB(pz)3}] (2). Other products show the coordination of one or four neutral pyrazole ligand(s) in the coordination spheres of technetium generated by thermal decomposition of the pyrazolylborates [TcI(NO)Cl2(PPh3)2(pzH)] (1) and [TcI(NS)Cl(pzHMe2)4]+ (5). Reactions with the corresponding thionitrosylrhenium complex [ReII(NS)Cl3(PPh3)2] require higher temperatures and only compounds with one pyrazole ligand, [ReI(NS)Cl2(PPh3)(pzHR)] (6a-6c), were isolated. The products were studied spectroscopically and by X-ray diffraction.

Facile Preparation of Gold Nanoparticles Silica Composite Film Embedded in Anodized Aluminium Oxide-Glass Substrate

Thin film based on gold nanoparticles or AuNPs is typically used as catalyst in the industrial processes due to their high stability and good reusability. In this work, a thin AuNPs-silica composite film was fabricated firstly from sol-gel method by mixing gold pyrazolate complex to a medium comprised of ethanol, deionized water, and hydrochloric acid followed by addition of tetrabutyl orthosilicate as silica source. Next, 70 microliters of the sol-gel solution were spin-coated on several type of substrates such as glass, anodized aluminium oxide or AAO, and combination of both to yield gold complex-silica composite film. It was found that gold complex-silica composite film fabricated on combination of both AAO-glass substrate gave the best quality based on its surface thickness, layer uniformity and film brittleness. Later, the film was selected and subjected to thermal hydrogen reduction at 210 degrees Celsius for 2 hours to facilitate the formation of gold nanoparticles to give AuNPs-silica in AAO-glass film. Before the heat treatment, the light-brownish colour of the original gold complex-silica in AAO-glass film in daylight will appear as a pinkish red film under UV light, suggesting the interaction between gold atoms and supported by its luminescence spectrum at 692 nm. Upon heat treatment, the resulting AuNPs-silica in AAO-glass film gave a deep-red colour indicating the successful formation of AuNPs. The presence of AuNPs in the film was further confirmed based on the absorption peak at 545 nm, X-ray diffraction pattern at 38.20 degrees for d111 plane in wide-angle region, transmission electron microscopy images showing a small and sphere shape particles as well as its elemental composition in energy dispersive X-ray analysis. Moreover, scanning electron microscope images also suggested that the AAO pores is fully filled with the composite and is in accordance with its surface roughness study via atomic force microscopy analysis.

Synthesis, characterization, crystal structure, molecular docking, and biological studies of Cu, Ni and Co metal complexes of pyrazole

Utilizing ligands based on pyrazole synthesized some transition metal complexes. Selected salts such as Co(CH3COO)2·4H2O, Ni(CH3COO)2·4H2O (in the presence of triethylamine), Cu(CH3COO)2·H2O (in the presence of triethylamine) and CuCl2·2H2O reacted with the ligand (E)-1-(amino(1H-pyrazol-1-yl) methylene) guanidinium chloride in methanol as a solvent. Obtained novel metal complexes characterized using different analyses such as infrared spectroscopy, electrospray ionization mass spectrometry, single-crystal X-ray diffraction, and elemental analysis. Additionally, a novel series of complexes (2a-d) were investigated for their ability to inhibit enzymes. They exhibited highly potent inhibition effect on human carbonic anhydrase I and II (hCA I and II) and α-glycosidase (Ki values are in the range of 7.14 ± 1.97 to 29.34 ± 3.18 µM, 9.86 ± 2.46 to 32.47 ± 4.82 µM, and 2.08 ± 0.11 to 4.03 ± 0.30 µM for hCA I, hCA II, and α-glycosidase, respectively). Indeed, insulin and oral antidiabetic medications are the two mainstays of clinical diabetes treatment. To learn more about the potential of pyrazole-based metal complexes of Cu, Ni, and Co and how successfully they can inhibit hCA I, hCA II, and α-Gly enzymes, molecular docking applications were performed.

Photophysical properties of tris(benzoyltrifluoroacetonate)Eu(III) with pyrazole complex and its precursor

The precursor, [Eu(btfa)3(H2O)2] with yield of 84 % and its complex with monodentate pyrazole, [Eu(btfa)3(pz)2] were isolated successfully. To the best of our knowledge, no previous reports of such synthesis with a high yield of [Eu(btfa)3(H2O)2] exist in literature. Single crystal X-ray diffraction (SC-XRD) analysis demonstrates, octa-coordinate environment of Eu (III) in both the complexes. The geometry of these complexes was obtained from SHAPE v2.1 and found triangular dodecahedron (D2d) and square antiprism (D4d) for [Eu(btfa)3(H2O)2] and [Eu(btfa)3(pz)2], respectively. These complexes were further characterized by elemental, thermal analysis (TGA/DTA) and ATR-IR spectroscopy. The lifetime of [Eu(btfa)3(pz)2] (546 ± 0.35 μs) is much longer than that of its precursor [Eu(btfa)3(H2O)] (335 ± 0.11 μs). The overall quantum yield of [Eu(btfa)3(pz)2] complex (21 %) is seven times larger than its precursor (3 %). The Judd-Ofelt intensity parameters accredit that [Eu(btfa)3(pz)2] is more polarizable (Ω2 = 33.56 × 10-20 cm2) than its precursor, [Eu(btfa)3(H2O)2] (Ω2 = 13.95 × 10-20 cm2).

Ruthenium Pyrazole Complexes: A Family of Highly Active Metallodrugs for Photoactivated Chemotherapy.

Ruthenium complexes bearing bis pyrazole (pzH) ligands, cis-[Ru(bpy)2(R-pzH)2]2+ (bpy = 2,2'-bipyridine, R = -H, -Cl), were examined as photoactivated anticancer prodrugs. A dicationic pyrazole complex deprotonated to give monocationic pyrazole-pyrazolate complexes, cis-[Ru(bpy)2(R-pz-)(R-pzH)]+, in an aqueous solution with pKa values of 9.5 and 7.2 for R = H and R = Cl, respectively. Upon deprotonation, relative quantum yields of photosubstitution decreased while lipophilicity of the complexes increased according to the measurements of water-octanol coefficients. The ruthenium complex with 4-chloropyrazole ligands displayed high cytotoxicity upon light irradiation (IC50 = 0.060 ± 0.016 μM) toward lung cancer cells, which was 7 times higher than that in the dark (IC50 = 0.44 ± 0.07 μM). Additional experiments for the ruthenium R-pyrazole complexes indicated that (1) selective photodissociation of the 4-chloropyrazole ligand occurs from cis-[Ru(bpy)2(4-Clpz-)(4-ClpzH)]+, (2) photoinduced ligand dissociation is dominant rather than photoinduced generation of singlet oxygen (1O2), and (3) induction of cell death occurs via the intrinsic pathway of apoptosis.

Vinyl-pyrazole as a biomimetic acetaldehyde surrogate.

Inspired by the enzyme acetylene hydratase, we investigated the reactivity of acetylene with tungsten(II) pyrazole complexes. Our research revealed that the complex [WBr2(pz-NHCCH3)(CO)3] (pz = 3,5-dimethyl-pyrazolate) facilitates the stochiometric reaction between pzH and acetylene to give N-vinyl-pz. This vinyl compound readily hydrolyzes to acetaldehyde, mirroring the product of acetylene hydration in the enzymatic process. The formation of the vinyl compound likely involves a reactive intermediate complex where acetylene acts as a two-electron donor, in contrast to isolable acetylene complexes that are inert to nucleophilic attack by water. Results suggest an alternative mechanism for the enzyme, including vinylation of a neighboring amino acid by acetylene in the active site prior to hydration.

The nature of π-hole spodium bonds in the HgLCl2(L = pyrrole, pyrazole, imidazole, pyridine, pyridazine, and pyrimidine) complexes: from noncovalent to covalent interactions

Computational investigations reveal the electrophilicity of the π-hole and the nature of spodium bonds in the HgLCl2⋯ZH3/CH2Y complexes.

Synthesis, Spectroscopy and Structural Elucidation of Two new CoII and NiII Complexes of Pyrazole Derived Heterocyclic Schiff base ligand as Potential Anticancer and Photocatalytic Agents

Synthesis, Spectroscopy and Structural Elucidation of Two new CoII and NiII Complexes of Pyrazole Derived Heterocyclic Schiff base ligand as Potential Anticancer and Photocatalytic Agents

An efficient one-pot synthesis of pyrazole complexes formed in situ: synthesis, crystal structure, Hirshfeld surface analysis and in vitro biological properties.

The molecular crystals of monomeric and dimeric pyrazole complexes were prepared via one-pot syntheses. These are dichloridobis(3,5-dimethyl-1H-pyrazole-κN1)cobalt/zinc(0.2/0.8), [Co0.20Zn0.80Cl2(C5H8N2)2] or [Co0.2Zn0.8Cl2(3,5-dmp)2] (1), and bis(μ-3,5-dimethyl-1H-pyrazole)-κ2N1:N2;κ2N2:N1-bis[bromido/chlorido(0.7/0.3)bis(3,5-dimethyl-1H-pyrazole-κN1)cobalt/zinc(0.1/0.9)], [Co0.20Zn1.80Br1.40Cl0.60(C5H7N2)2(C5H8N2)2] or [Co0.1Zn0.9Br0.7Cl0.3(μ-3,5-dmp)(3,5-dmp)]2 (2). The isolated complexes contain 3,5-dimethylpyrazole (3,5-dmp) ligands formed in situ from the decomposition of 1-hydroxymethyl-3,5-dimethylpyrazole. In both isolated complexes, some positional disorder is observed at the metal ions and halogen ligands. The molecular crystals of 1 and 2 are centrosymmetric, with the space groups C2/c and P-1, respectively. Additionally, in the dinuclear complex, the pyrazole ring has a bridging coordination function with respect to the metal ions. Both complexes have good biological activities against cancer cells. The results of an in vitro cytotoxicity study indicated that compounds 1 and 2 showed significant cytotoxicity for cancer cell lines, including hepatic (HepG2 cells), lung (A549 cells) and colon cancer cells (SW 480 and SW 620). Based on the calculated IC50 values against human cancer cell lines, it was found that both complexes demonstrated potent antiproliferative activity combined with great selectivity towards cancer cells. Complex 2 was a more effective cytotoxic agent which, at the same time, exhibited high cytocompatibility. The obtained data are very encouraging and could be useful for anticancer drug discovery.

Pyrazole and Benzimidazole Derivatives: Chelating Properties Towards Metals Ions and their Applications

Abstract: Due mainly to their structural diversities, pharmacological, electrochemical, and photophysical properties, the metal synthesis pyrazole and benzimidazole complexes were extensively designed and developed. The nitrogen-containing ligands playing an important role in coordination chemistry contain a wide variety of heterocyclic systems possessing one or more nitrogen atoms as electron donors, such as pyridine, isoxazole, pyrazole, 1,2,4-triazole, 1,3,5-triazine, quinoline, quinoxaline and benzothiazole. The structure of all ligands and the corresponding metal complexes are established using elemental analysis, infrared spectroscopy, NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, thermogravimetric differential thermal analysis, static, magnetic susceptibility measurements, electron paramagnetic resonance spectroscopy (EPR), UV-Vis spectroscopy, and conductivity measurements.In this review, we report the synthesis and the chelating reactions of several heterocyclic ligands with various metals such as transition metals and lanthanides. The photophysical and photochemical properties of the metal complexes will also be presented and discussed.

Recent Developments in Reactions and Catalysis of Protic Pyrazole Complexes.

Protic pyrazoles (N-unsubstituted pyrazoles) have been versatile ligands in various fields, such as materials chemistry and homogeneous catalysis, owing to their proton-responsive nature. This review provides an overview of the reactivities of protic pyrazole complexes. The coordination chemistry of pincer-type 2,6-bis(1H-pyrazol-3-yl)pyridines is first surveyed as a class of compounds for which significant advances have made in the last decade. The stoichiometric reactivities of protic pyrazole complexes with inorganic nitrogenous compounds are then described, which possibly relates to the inorganic nitrogen cycle in nature. The last part of this article is devoted to outlining the catalytic application of protic pyrazole complexes, emphasizing the mechanistic aspect. The role of the NH group in the protic pyrazole ligand and resulting metal-ligand cooperation in these transformations are discussed.

Tetranuclear Copper(I) and Silver(I) Pyrazolate Adducts with 1,1'-Dimethyl-2,2'-bibenzimidazole: Influence of Structure on Photophysics.

A reaction of a cyclic trinuclear copper(I) or silver(I) pyrazolate complex ([MPz]3, M = Cu, Ag) with 1,1'-dimethyl-2,2'-bibenzimidazole (L) leads to the formation of tetranuclear adducts decorated by one or two molecules of a diimine ligand, depending on the amount of the ligand added (0.75 or 1.5 equivalents). The coordination of two L molecules stabilizes the formation of a practically idealized tetrahedral four-metal core in the case of a copper-containing complex and a distorted tetrahedron in the case of a Ag analog. In contrast, complexes containing one molecule of diimine possess two types of metals, two- and three-coordinated, forming the significantly distorted central M4 cores. The diimine ligands are twisted in these complexes with dihedral angles of ca. 50-60°. A TD-DFT analysis demonstrated the preference of a triplet state for the twisted 1,1'-dimethyl-2,2'-bibenzimidazole and a singlet state for the planar geometry. All obtained complexes demonstrated, in a solution, the blue fluorescence of the ligand-centered (LC) nature typical for free diimine. In contrast, a temperature decrease to 77 K stabilized the structure close to that observed in the solid state and activated the triplet states, leading to green phosphorescence at ca. 500 nm. The silver-containing complex Ag4Pz4L exhibited dual emission from both the singlet and triplet states, even at room temperature.

Synthesis, Characterization, DFT, and Thermogravimetric Analysis of Neutral Co(II)/Pyrazole Complex, Catalytic Activity toward Catecholase and Phenoxazinone Oxidation

The pyrazole-pyridin-2-amine, as a tridentate pyrazole ligand, and its neutral Co(II)/pyrazole complex were prepared using a direct method with a high yield. The desired pyrazole ligand and its complex were subjected to several physicochemical and thermal analyses; moreover, the DFT-like optimization of MEP, HOMO/LUMO, and TD-DFT correlated well with their experimental relatives. Additionally, the oxidation catalytic activities of the Co(II)/pyrazole complex, such as the catecholase of catechol to o-quinone and the phenoxazinone of 2-aminophenol to 2-aminophenoxazinone, were also evaluated under mild RT conditions and atmospheric oxygen.

Filling the gap with a bulky diaryl boron group: fluorinated and non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety on the backbone.

Successful synthesis has been reported of 4-Mes2B-3,5-(CF3)2PzH and 4-Mes2B-3,5-(CF3)2PzH bearing sterically demanding diarylboron moieties at the pyrazole ring 4-position, and their corresponding copper(I) pyrazolate complexes. They show visible blue photoluminescence in solution. The X-ray crystal structures revealed that the fluorinated {[4-BMes2-3,5-(CF3)2Pz]Cu}3 crystallizes as discrete trinuclear molecules whereas as the non-fluorinated {[4-BMes2-3,5-(CH3)2Pz]Cu}3 forms dimers of trimers with two close inter-trimer Cu⋯Cu separations. The solid {[4-BMes2-3,5-(CF3)2Pz]Cu}3 featuring a sterically confined Cu3N6 core displays bright blue phosphorescence while {[4-BMes2-3,5-(CH3)2Pz]Cu}3, which is a dimer of a trimer, is a red phosphor at room temperature. This work illustrates the modulation of photo-physical properties of metal pyrazolates by adjusting the supporting ligand steric features and introducing secondary diarylboron luminophores. Computational analysis of the structures and photophysical properties of copper complexes are also presented.

Synthesis, Structure, and Hydrolytic Activation of Ruthenium (III)-Pyrazole Complex

We report here the synthesis of water-soluble mer-[RuCl3(DMSO-S) (pyz)2] 2 prepared by the reaction of mer-RuCl3(DMSO-S)31 with pyrazole in anhydrous CH2Cl2. Compound 2 was characterized by IR and UV-visible spectroscopy, X-ray diffraction, cyclic voltammetry, and DFT calculations. The X-ray diffraction analysis disclosed that compound 2 has two independent molecules present in the asymmetric unit with different conformations for one of the pyrazoles and different hydrogen bonding. The DFT calculations suggest the structure-activity relationship and hydrolytic activity of these complexes.

Polyoxometalate-Supported Copper(I)-Pyrazole Complex: Unusual Stability, Geometrical Isomers, Organic Transformation, and Computation.

We have described the synthesis and characterization of a polyoxometalate (POM)-supported copper(I)–pyrazole complex, [CuI(C15H12N2)2] [PW12O40{CuI(C15H12N2)2}2]·CH3OH (1). There are three Cu(I)–pyrazole coordination complexes in compound 1, out of which two are supported by the {PW12O40}3– Keggin POM by coordinate covalent bonds from the POM surface through oxygen donors to the Cu(I) centers of two Cu(I) complexes and one remains uncoordinated to the POM surface, acting as a cationic complex species in the crystals of 1. The POM-coordinated Cu(I) complexes have a T-shaped geometry, and the uncoordinated Cu(I) complex is a linear one. During the solvothermal synthesis of compound 1, remarkably, the associated 1,5-diphenylpyrazole ligand is formed from cinnamaldehyde phenylhydrazone through oxidative cyclization at the cost of Cu(II) reduction to Cu(I), and then, these two (copper(I) and pyrazole ligand) form the coordination complex. Compound 1 undergoes desolvation on heating the single crystals of compound 1 at 55 °C in the aerial atmosphere with the formation of the desolvated compound [CuI(C15H12N2)2][PW12O40{CuI(C15H12N2)2}2] (2). Interestingly, when an aqueous suspension of compound 1 is bubbled with O2 gas at room temperature, it undergoes solid-to-solid transformation, resulting in the formation of the compound [CuI(C15H12N2)2]3[PW12O40] (3). Compounds 1, 2, and 3 have been characterized by routine spectral analyses (including cyclic voltammetry and X-ray photoelectron spectroscopy (XPS) studies) and unambiguously by single-crystal X-ray crystallography. We have performed density functional theory (DFT) calculations on compound 1 to understand the rationale of its unusual stability toward oxidation.

Copper(I)–Pyrazolate Complexes as Solid-State Phosphors: Deep-Blue Emission through a Remote Steric Effect

We describe a novel manifestation of rigidochromic behavior in a series of tetranuclear Cu(I)-pyrazolate (Cu4pz4) macrocycles, with implications for solid-state luminescence at deep-blue wavelengths (<460 nm). The Cu4pz4 emissions are remarkably sensitive to structural effects far from the luminescent core: when 3,5-di-tert-butylpyrazoles are used as bridging ligands, adding a C4 substituent can induce a blue shift of more than 100 nm. X-ray crystal and computational analyses reveal that C4 units influence the conformational behavior of adjacent tert-butyl groups, with a subsequent impact on the global conformation of the Cu4pz4 complex. Emissions are mediated primarily through a cluster-centered triplet (3CC) state; compression of the Cu4 cluster into a nearly close-packed geometry prevents the reorganization of its excited-state structure and preserves the 3CC energy at a high level. The remote steric effect may thus offer alternative strategies toward the design of phosphors with rigid excited-state geometries.

Design and Development of Ruthenium-Based Catalysts for Enabling Hydrogen Storage

For past decades, hydrocarbon-based fuels have been the primary source of energy as a necessity for modern machines and automotive vehicles. Despite use in combustion engines and power plants, fossil fuels reserves are unpredictable and the associated CO2 emissions are now causing terrible effects on the environment and human health. Researchers have realized H2 as a potentially safe and efficient energy source, with an energy density of 33.3 kWh per kg. Moreover, H2 is significantly more environmentally friendly as H2O is the only by-product. Currently, the development of on-board storage technology is progress for use in the transportation industry. The chemical storage of hydrogen, in which H2 is bound to a carrier molecule, provides a more practical and safer method to store and release immense amounts of H2. Ammonia Borane (H3N-BH3, AB) is a useful material for storing up to 19.6 wt% of and 0.145kg L-1 of H2 with the ability to release H2 under mild ambient conditions through exposure to a suitable catalyst. This project investigates the use of pyrazole-based compounds as ligands for η6-arene Ru-complexes in order to formulate efficient catalysts for AB dehydrogenation. Pyrazoles are interesting diaza-five member heterocycles and have strong electron-donating properties. Mono- and di-coordinating substituted pyrazole complexes and an unusual Cl-bridging dimeric Ru complex were successfully synthesized and characterized (NMR, ESI-MS and X-ray diffraction crystallography) before undergoing evaluation for AB dehydrogenation studies in a high-pressure stainless steel reactor. The dimeric Ru Cl-bridging catalyst released the largest H2 equivalent per mol of AB with 1.45 with a total of 7.82 bar of H2 pressure, proving to be the most successful catalyst in the series. However, from the H2 release profiles, it appears that catalysts undergo slow transformation where it is possible that the pyrazole ligands are lost. Further mechanistic studies are required to determine the decomposition process.

Phosphorescent Vapochromic Responses of Copper(I) Complex Bearing Pyrazole Ligands for Detection of Alcohol Derivatives

The methodical study of trinuclear copper(I) metal complexes phosphorescent vapochromic chemosensor via metal-metal interactions for sensing various volatile organic compounds has piqued the interest of many researchers. Herein, we highlighted the performance of chemosensors trinuclear copper(I) pyrazolate complexes (2Pz1‒2Pz5) with different molecular design short alkyl side chains from the respective pyrazole ligands. The synthesized complexes had demonstrated a high phosphorescent sensing capacity of various alcohol derivatives. Due to weak metal-metal interactions, the complexes give emission bands centered around 553-644 nm at an excitation of 280 nm. We found that the only 2Pz3 chemosensors showed quenching phenomena with a significant decrease in its emission intensity of 100% for exposure in 5 minutes with irreversible performance. Interestingly, we also found that the shifting of the emission center due to the disruption of metal-metal interaction performed by chemosensor 2Pz5 resulting in the best detection performance of methanol and ethanol (∆λ= 60 nm) and propanol (∆λ = 22 nm) showing autonomous recovery within 15 minutes. Based on the findings, the specific balance, such as rigidity and amphiphilicity in the molecular design of chemosensors, is important for the detection of vapors via supramolecular interactions.