Tetradentate Chelating Research Articles

Structural studies and physicochemical properties of indium(III) complexes with 2-formyl-8-hydroxyquinoline-derived hydrazones

The reaction of InCl3 with 2-formyl-8-hydroxyquinoline-4-nitroimidazole hydrazone (H2L1) in ethanol gave [In(H2L1)(HL1)Cl2], complex (1), as the product. Experimental data and theoretical DFT calculations suggested that complex (1) presents coordination number (CN) 8, with one neutral and one anionic ligand coordinated to the metal center through the ONpy-N tridentate chelating system together with two chloride ions. The reaction with 2-formyl-8-hydroxyquinoline-4-nitrobenzene hydrazone (H2L2) in methanol gave [In(HL2)Cl2(CH3OH)], complex (2), as the product while [In(HL2)Cl2]·CH3CH2OH, complex (3), was formed as the product using ethanol as solvent. Experimental data indicated that in complexes [In(HL2)Cl2(CH3OH)] (2) and [In(HL2)Cl2]·CH3CH2OH (3) one anionic ligand is attached to the indium(III) center through the ONpy-N-O tetradentate chelating system along with two chlorides. The crystal structure of the complex [In(HL2)Cl2(CH3OH)] (2) revealed that the indium(III) center presents CN 7. Calculated bond lengths in complex (2) were in accordance with the experimental values. The experimental and calculated electronic spectra of complexes (1) and (2) presented the same pattern and allowed the attribution of the absorption peaks to π - π* transitions.

Tetradentate Pt(II) Complexes Based on Xylenylamino Linked Dual Pyrazolate Chelates for Organic Light Emitting Diodes.

In this work, we report the syntheses of three Pt(II) emitters, namely, Pt4N1, Pt4N2, and Pt4N3, to which their tetradentate chelates were assembled by linking two pyrazolate chelates with a single xylenylamino entity. Functionalization of Pt4N1 was achieved upon the addition of electronegative CF3 substituent on pyridinyl groups and switching to more electron-deficient pyrazinyl groups in giving Pt4N2 and Pt4N3, respectively. The vertically arranged xylenylamino entity has effectively suppressed the inter-molecular π-π stacking and Pt⋅⋅⋅Pt interaction, as shown by the single crystal X-ray structural analyses. Upon fabrication of OLED devices, Pt4N2 and Pt4N3 based devices delivered efficient cyan and green emission, with an EQEmax of 15.2 % and 11.2 %, respectively, affirming the successfulness of the tetradentate chelating strategy.

Computational insights into the underlying mechanism of zinc ion-specificity of the fluorescent probe, BDA-1

Ion specificity is crucial for developing fluorescence probes. Using a recently reported optical sensor (BDA-1) of Zn2+ as a representative, we carried out extensive quantum chemical calculations on its photophysical properties using density function theory. According to the calculated optimized geometries, excitation energies and transition oscillator strengths, the weak fluorescence of BDA-1 observed in experiments is attributed to the suppression of fluorescence emission by efficient internal conversion, rather than the previously proposed photoinduced electron transfer (PET) mechanism. With the addition of Zn2+ or Cd2+ ions, the tetradentate chelates [M:BDA-1-H+]+ (M=Zn, Cd) are produced. According to frontier molecular orbital and interfragment charge transfer analyses of these complexes, PET is preferentially confirmed to occur upon photo-excitation. Notably, as one coordination bond in the excited [Cd:BDA-1-H+]+ complex is significantly weakened in comparison to that of [Zn:BDA-1-H+]+, their molecular orbital compositions in the S1 state are completely different. As a result, absorption and radiation transitions of [Zn:BDA-1-H+]+ both have considerable oscillator strength, while fluorescence radiation from the excited [Cd:BDA-1-H+]+ is doubly suppressed. This difference causes that the fluorescence intensity of BDA-1 is sensitive to the addition of metal ions, and exhibits the zinc ion-specificity.

A Neutral Pyridine-Pyrazole-Based N^N*N^N Ligand as a Tetradentate Chromophore for Diverse Transition Metal Cations

Herein, the synthesis and the structural as well as the photophysical characterization of five transition metal complexes bearing a neutral pyridine-pyrazole-based N^N*N^N ligand (L) acting as a tetradentate chelator are reported. The luminophore can be synthesized via two different pathways. An alkyl chain with a terminal tert-butyl moiety was inserted on the bridging nitrogen atom to enhance the solubility of the complexes in organic solvents. Due to the neutral character of L, metal ions with different charges and electronic configurations can be chelated. Thus, complexes with Pt(II) (C1), Ag(I) (C2), Zn(II) (C3), Co(II) (C4) and Fe(II) (C5) were synthesized. Single-crystal X-ray diffraction experiments showed that complex C2 exhibits a completely different structure in the crystalline state if compared with C3 and C5, i.e., depending on the chelated cation. The UV-vis absorption and the NMR spectra showed that the complexes dissociate in liquid solutions, except for the Pt(II)-based coordination compound. Therefore, the photophysical properties of the complexes and of the ligand were studied in the solid state. For the Pt(II)-based species, a characteristic metal-perturbed ligand-centered phosphorescence was traceable, both in dilute solutions as well as in the solid state.

Copper selective 8-aminoquinoline based tetradentate chelators as anticancer agents.

Cancer cell proliferation and metastasis are known to be dependent on angiogenesis which is regulated by several parameters including copper availability. Tetradentate monoquinoline (TDMQ) ligands constitute a series of chelators tailored to regulate copper homeostasis due to their specificity for copper(ii) with respect to Cu(i) or other biometals like iron or zinc. One of these chelators, TDMQ20 efficiently inhibits both proliferation and migration of several human cancer cell lines, better than the reference drug 5-fluorouracil, and with higher selectivity indexes with respect to non-cancer human cells. The biological activity of TDMQ20 may be driven by the coordination chemistry of copper, and the ability of this chelator to restore copper homeostasis and its subsequent redox properties. The anticancer mechanism of action of TDMQ20 involves intracellular production of reactive oxygen species, drastic mitochondrial damages and induction of tumor cell apoptosis. These data support the selection of TDMQ20 as drug-candidate against several human cancers.

A nickel(II) complex with an unsymmetrical tetra-dentate chelating ligand derived from pyridine-2,6-dicarbaldehyde and 2-amino-thio-phenol.

[(2-{[6-(1,3-Benzo-thia-zol-2-yl)pyridin-2-yl]carbonyl-aza-nid-yl}phen-yl)sulf-anido]nickel(II), [Ni(C19H11N3OS2)], crystallizes in the centrosymmetric monoclinic space group P21/n with one mol-ecule in the asymmetric unit. The expected ligand, a bis-Schiff base derived from pyridine-2,6-dicarbaldehyde and 2-amino-thio-phenol, had modified in situ in a both unexpected and unsymmetrical fashion. One arm had cyclized to form a benzo[d]thia-zol-2-yl functionality, while the imine linkage of the second arm had oxidized to an amide group. The geometry about the central NiII atom is distorted square-planar N3S. The mol-ecules form supra-molecular face-to-face dimers via rather strong π-π stacking inter-actions, with these dimers then linked into chains via pairwise C-H⋯O inter-actions.

New homo‐bimetallic complexes of dihydrazone‐oxime ligand incorporating isatinic moiety: Preparation, characterization, theoretical, microbicidal, and anticancer investigation

A new series of dihydrazone‐oxime ligand's homo‐bimetallic complexes of formulas [M2LCl5(H2O)3].nH2O (M=Fe3+, n=0; Ru3+, n=2), [M2L((O)CH3COO)3(H2O)5].nH2O (M=Co2+, Mn2+, Zn2+ or UO22+, n=4, 6, or 1) and [Cu2L(NO3)3(H2O)3] is designated from the reaction of 3‐((3‐(hydroxyimino)butan‐2‐ylidene)hydrazono)indolin‐2‐one (HL,1) with the salts of Fe3+, Ru3+, Co2+, Cu2+, Mn2+, Zn2+, and UO22+. The newly prepared compounds' structure was elucidated based on traditional techniques such as molar conductance, magnetic measurements, elemental, thermogravimetric (TGA) analyses, and mass spectrometry, as well as spectroscopic tools such as electronic absorption, infrared, nuclear magnetic resonance, mass, and electron spin resonance spectra. The values of complexes molar conductance in DMSO indicated that they were non‐electrolytes. The elemental analysis, in conjunction with other data obtained, confirmed that the ligand performed as a uni‐negative tetradentate chelator that bound two metal cations via the indoline carbonyl; deprotonated oximatic and azomethine groups adopt distorted octahedral or square pyramidal geometries. The chemical formula of these complexes was corroborated by TG analysis, which verified that the homo‐bimetallic complexes were degraded in three or four decaying steps in temperature range 50–596°C ended with the formation of metallic oxide. The prepared compounds' structural characterization was verified by DFT calculations utilizing DFT‐B3LYP technique with a basis set (6–311++G[d,p]). Theoretical calculations' results demonstrated that the homo‐bimetallic complexes' reactivity is higher than un‐complexed ligand's reactivity. The anticancer activity was determined versus three cell lines, namely, SKOV3, PC‐3, and HeLa cell lines. The assignment data revealed that the Zn2+ complex has a stronger inhibitory effect against the three cell lines. Additionally, the synthesized substances' in vitro microbicidal activity was performed versus a variety of bacterial and fungal species.

Modification of the Bridging Unit in Luminescent Pt(II) Complexes Bearing C^N*N and C^N*N^C Ligands

In this work, we explored the synthesis and characterization of Pt(II) complexes bearing different tri- and tetradentate luminophores acting as C^N*N- and C^N*N^C-chelators. Thus, we investigated diverse substitution patterns in order to improve their processability and assessed the effects of structural variations on their excited state properties. Hence, a detailed analysis of the different synthetic pathways is presented; the photophysical properties were studied by using steady-state and time-resolved photoluminescence spectroscopy. We determined the absorption and emission spectra, the photoluminescence efficiencies, and the excited state lifetimes of the complexes in fluid solutions at room temperature and frozen glassy matrices at 77 K. Finally, a structure–property relationship was established, showing that the decoration of the bridging unit on the tridentate luminophores only marginally affects the excited state properties, whereas the double cyclometallation related to the tetradentate chelator prolongs the excited state lifetime and increases the photoluminescence quantum yield.

6,6′-Di-(8″-quinoline)-2,2′-bipyridine Cobalt(II) Complex

This short note describes the synthesis of a novel compound, 6,6′-di-(8″-quinoline)-2,2′-bypyridine (2), that bears a bipyridyl backbone and quinoline donors. Compound 2 coordinates with a cobalt(II) ion in a tetradentate manner and affords the complex [CoII(2)(TfO)2], whose molecular structure has been identified by single crystal X-ray diffraction crystallographic analysis. The coordination features of 2 were compared with those of 2,2′:6′,2″:6″,2‴-quaterpyridine (qtpy, 1), a well-studied tetradentate polypyridine ligand. Compound 2 presents a new example of tetradentate chelators for 3d metal ions.

Structural variety of Cu (II), Ni (II), and Co (II) complexes of a hydrazone based on 5‐acetyl‐4‐hydroxy‐2H‐1,3‐thiazine‐2,6(3H)‐dione: Synthesis, spectroscopic, density functional theory, antitumor, and docking studies

New nickel (II), cobalt (II), and several copper (II) complexes have been synthesized from the hydrazone ligand (AHTDSH; H2L); which obtained from 5‐acetyl‐4‐hydroxy‐2H‐1,3‐thiazine‐2,6(3H)‐dione with salicylaldehyde hydrazone. The structures of H2L ligand and the prepared complexes were confirmed by spectroscopic and analytical techniques. The ligand behaves as bis (monobasic bidentate) and dibasic tetradentate chelating agent via azomethine nitrogen and phenolic oxygen atoms. Octahedral geometries have been assigned for the prepared complexes. The Coats–Redfern equations were used to estimate the kinetic parameters (Ea, A, H, S, and G) of the thermal decomposition stages. The molecular structural characteristics of the ligand and its metal complexes were estimated based on density functional theory (DFT) level implemented in the Gaussian 09 software at B3LYP/6‐311G(d,p) level and the theoretical data were connected with the results of the experimental work. The anticancer activity of AHTDSH ligand and its complexes was demonstrated toward HepG2 cell lines. The interaction between the chemical and the active site of the CDK2 kinase was examined using a docking study of the hydrazone ligand and its complexes.

Synergetic spin singlet-quintet switching and luminescence in mononuclear Fe(II) 1,3,4-oxadiazole tetradentate chelates with NCBH3 co-ligand.

We report the multi-step synthesis of the tetradentate 2-(naphthalen-2-yl)-5-[N,N-bis(2-pyridylmethyl)aminomethyl]-1,3,4-oxadiazole ligand (LTetra-ODA) along with its corresponding [FeII(LTetra-ODA)(NCBH3)2]·1.5CH3OH (C1) complex, which is the first mononuclear 1,3,4-oxadiazole based Fe(II) spin crossover (SCO) complex, and its zinc analogue [ZnII(LTetra-ODA)(NCBH3)2]·0.5H2O (C2). The spin transition is followed by variable temperature (VT-) X-ray crystallography of [Fe(LTetra-ODA)(NCBH3)2]·1.5CH3OH (C1) at 120 and 220 K. The magnetic susceptibility measurements on the bulk sample recorded from 2 to 300 K show that the complex exhibits a complete abrupt reversible spin transition with a T1/2 of 207 K. The loss of the lattice solvent methanol shifts the T1/2 slightly to around 210 K. The spin transition in solution for [Fe(LTetra-ODA)(NCBH3)2]·1.5CH3OH (C1) was followed using the VT-1H-NMR Evans method in CD3CN, with a T1/2 of 357 K. Solid state VT luminescence studies provide some preliminary evidence of interplay of luminescence and spin transition in the [Fe(LTetra-ODA)(NCBH3)2]·1.5CH3OH (C1) complex.

Oxygenation of copper(I) complexes containing fluorine tagged tripodal tetradentate chelates: significant ligand electronic effects

Copper-dioxygen (O2) interactions are of great importance in biological and chemical transformations involving reversible dioxygen binding, activation, or reduction. In this report, we describe O2-reactions with the mononuclear copper(I) complexes containing two new analogues of the known nitrogen-containing tetradentate tripodal chelate, tris[(2-pyridyl)methyl]amine (TMPA). In both derivatives, one electron-rich and one electron-deficient, fluorine atoms are attached to the ligand framework, allowing for the use of 19F-NMR spectroscopy to probe the oxygenation process. Variations of ligand electronic properties are manifested in the electrochemical behavior of copper complexes and their reactivities toward O2. Our NMR spectroscopic studies, along with variable-temperature electronic absorption measurements, revealed that the copper(I) complexes reversibly react with O2 to form the corresponding 1:1 copper-O2 (i.e., end-on superoxo) intermediates which can further react reversibly with second equivalents of copper(I) complexes to form the related dinuclear 2:1 copper-O2 (i.e., trans-peroxo) adducts. However, considerable differences exist in detail at various temperatures, depending on the chelate. All three end-on superoxo and trans-peroxo species described here possess similar spectroscopic features, although small but significant shifts in the energy of their signature bands were observed, suggesting that the variation in the chelates directly affects the electronic properties of the copper-O2 cores.

Targeted synthesis of two iron(III) tetradentate dibasic chelating Schiff base complexes toward inhibition of acidic induced steel corrosion: Empirical and DFT insights

Two new azomethine chelates for Fe3+ ions were prepared from two dibasic tetradentate chelating imine ligands. The studied Schiff base ligands were 2,2′‐((1E,1′E)‐((4‐nitro‐1,2‐phenylene)bis(azanylylidene))bis(methanylylidene))bis(4‐bromophenol) (NABS) and 2,2′‐((1E,1′E)‐((4,5‐dimethyl‐1,2‐phenylene)bis(azanylylidene))bis(methanylylidene))bis(4‐bromophenol) (MABS). Alternative spectral and physicochemical tools such as Fourier transform infrared spectroscopy (FTIR), C13 NMR, 1H NMR, and CHN analyses, thermogravimetric analysis (TGA), molecular electronic spectra, and magnetic susceptibility measurements were applied to inspect the structural composition of the compounds under investigation. In addition, the DFT approach was used to optimize the geometry of all compounds in order to get ideal structures and important characteristics. The synthesized compounds examined as an anticorrosive films of C‐steel in acidic chloride medium utilizing theoretical and electrochemical studies such electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), and potentiodynamic anodic polarization curve (PAP) approaches. The inhibition efficiency augmented with the increasing of the inhibitor dose. The prepared Schiff bases and their iron complexes exhibited protection capacity around 96.8% in the presence of 0.5 mmol L−1. PDP outcomes approve the additive molecules act as mixed inhibitors. The Langmuir model is followed by Schiff bases and their iron complexes as it is contains both chemical and physical adsorption on the metal interface. The surface morphology of the substrate (in blank and inhibited systems) was scanned using field‐emission scanning electron microscopy (FESEM). A good agreement among experimental techniques and corresponding density functional theory (DFT) results was found, which confirmed the purity of the studied compounds and suggested octahedral geometry around Fe(III) ions in both MABSFe and NABSFe complexes.

6,6′-Di-(2″-thiophenol)-2,2′-bipyridine

This short note describes the synthesis of compound 6,6′-di-(2″-thiophenol)-2,2′-bipyridine from its methyl phenyl sulfane precursor via deprotection of the methyl groups. The product as well as the intermediate in the synthetic route have been characterized by UV-Vis spectroscopy, 1H- and 13C-NMR spectroscopy, FT-IR spectroscopy, and HR-MS analysis. This work presents a rare example of tetradentate chelators that bears pyridyl backbones and thiophenol donors for the coordination with 3d-transition metal cations.

Preparation of immobilized lipase on Co2+-chelated carboxymethyl cellulose based MnFe2O4 magnetic nanocomposite particles

Lipase immobilization was performed via physical adsorption on a novel metal-chelating nanostructure consisted of (S)-N-(5-Amino-1-carboxypentyl) iminodiacetic acid (NTA), as a tetra-dentate chelating agent, grafted onto MnFe2O4 nanoparticles coated with carboxymethyl cellulose (CMC) for Co2+-chelated affinity lipase adsorption. The influential immobilization parameters for enzyme adsorption were investigated. The maximum amount of immobilized lipase (8.5 mg/g adsorbent) was obtained at modified conditions with initial enzyme concentration of 2 mg/mL and adsorbent dosage of 1 mg/mL after 90 min incubation at 50 mM buffer citrate at pH 5. The Fourier transform infrared spectroscopy (FTIR), energy dispersive spectroscopy (EDS), and elemental mapping provided evidence of successful immobilization of lipase. The results of kinetic study revealed that the adsorption of lipase followed pseudo second order kinetic model. Investigation on the enzymatic properties demonstrated that the immobilized lipase possesses remarkable thermal stability at 60 °C for 120 min, as the catalytic activity of immobilized lipase was 75% higher than that of free lipase at the same temperature. Beside, the immobilized lipase still retained 70% of its initial activity after 7 successive recycles, suggesting the new designed Co2+-chelated magnetic nanostructure as a great matrix for the non-covalent enzyme immobilization.

Structural and theoretical studies of iron(III) and copper(II) complexes of dianion N1,N4-bis(salicylidene)-S-alkyl-thiosemicarbazide

Iron(III) and copper(II) complexes with an allyl N'-(1-(2-hydroxyphenyl)ethylidene)carbamohydrazonothioate·hydrobromide (H2L) and ethyl N'-5‑bromo-2-hydroxybenzylidenecarbamohydrazonothioate·hydrobromide (H2L') ligands were synthesized and characterized by elemental analysis, FT-IR spectroscopy and molar conductivity. Single crystal X-ray crystallography reveals that the iron and copper complexes have square pyramidal and square planar geometries, respectively. The ligands act as a binegative tetradentate chelating agent and they are bonded to the metal center through the phenolic oxygen, isothioamide nitrogen, and azomethine nitrogen atoms. The fifth site of the Fe(III) coordination sphere in both Fe complexes is occupied by chloride ion. Density functional theory method was used to complement the structural and spectroscopic data obtained experimentally. We also performed docking calculations of the complexes with human serum albumin and the copper complex binds preferentially.

Highly phosphorescent dinuclear Cu(I) complexes with iminephosphine tetradentate chelating ligand (PNNP): Structures and luminescence properties

Two dinuclear copper(I) iodide complexes [Cu(μ-I)]2L (1) and [CuIPPh3]2L (2), based on a new iminephosphine tetradentate chelating ligand (PNNP), have been synthesized and characterized. The crystal structures of the complexes display distorted tetrahedron configurations around Cu(I) centers. In powder at 298 K, these complexes exhibit bright orange-red and yellow emissions with excellent photo-luminescent quantum yields of 54.6% (1) and 66.8% (2), and short lifetimes of 2.26 μs (1) and 2.32 μs (2), respectively. The reversible mechanochromic luminescent (MCL) properties of complex 2 have been confirmed by monitoring the changes in emission spectra and X-ray diffraction patterns. X-ray crystallography analysis reveals that the unique pore structure filled with CHCl3 molecule is considered to be the origin of MCL properties of 2.

Synthesis, Characterization, and Reaction Studies of Pd(II) Tripeptide Complexes.

The aqueous synthesis of Pd(II) complexes with alkylated tripeptides led to the hydrolysis of the peptides at low pH values and mixtures of complexed peptides were formed. A non-aqueous synthetic route allowed the formation and isolation of single products and their characterization. Pd(II) complexes with α-Asp(OR)AlaGly(OR), β-Asp(OR)AlaGly(OR), and TrpAlaGly(OR) (R = H or alkyl) as tri and tetradentate chelates were characterized. The tridentate coordination mode was accompanied by a fourth monodentate ligand that was shown to participate in both ligand exchange reactions and a direct removal to form the tetradentate coordination mode. The tetradentate coordination revealed a rare a hemi labile carbonyl goup coordination mode to Pd(II). Reactivity with small molecules such as ethylene, acids, formate, and episulfide was investigated. Under acidic conditions and in the presence of ethylene; acetaldehyde was formed. The Pd(II) is a soft Lewis acid and thiophilic and the complexes abstract sulfur from episulfide at apparent modest catalytic rates. The complexes adopt a square planar geometry according to a spectroscopic analysis and DFT calculations that were employed to evaluate the most energetically favorable coordination geometry and compared with the observed infrared and NMR data.

Structure investigation, density functional theory, and biostudy of synthesized dihydrazone incorporating isatin moiety and its homo‐bimetallic complexes

AbstractSeven homo‐bimetallic complexes derived from 3‐(‐(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)methylene)hydrazono)indolin‐2‐one with Fe3+, Co2+, Cu2+, and UO22+have been prepared and structurally investigated using elemental and thermo‐gravimetric analyses and spectral, magnetic, and molar conductivity measurements. This structural investigation leads us to conclude that the bis‐hydrazone has behaved as neutral tetradentate chelator chelated to the Fe3+, Co2+, Cu2+, and UO22+ions via the carbonyl and azomethine groups adopting distorted octahedral structure for Fe3+, Co2+, and Cu2+complexes (2–5), whereas the Cu2+complexes (6–7) have square planar structures. The structural characterization of bis‐hydrazone and its chelated compounds has been supported by density functional theory calculations. The optimized geometry, global reactivity descriptors, and lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the molecules have been calculated in accordance with the density functional theory (DFT)‐Beckee3eLeeeYangeParr (B3LYP) technique and 6e311G(d,p) basis set. The molecular electrostatic potential image was also drawn by the DFT‐B3LYP technique and 6e311G(d,p) basis set to envision the charge distribution and chemical reactivity on the molecules. The bioeffect of bis‐hydrazone and its chelated compounds was assessed against bacterial strainsBacillus subtilis,Escherichia coli, as well as fungal strainsCanadian albicansandAspergillus niger. The observed data imply encouraging bioeffect of some of these complexes in comparing with the free bis‐hydrazone or amphotericin B (AmB) against all fungalC. albicansandA. niger.

Synthesis, structural characterization, and density functional theory calculations of the two new Zn (II) complexes as antibacterial and anticancer agents with a neutral flexible tetradentate pyrazole‐based ligand

Two new mono‐ and dinuclear zinc (II) complexes with a formula of [Zn (LN)OMeCl] (1) and [Zn2(LN)(N3)2Cl2] (2) [where LN = 1,1,3,3‐tetrakis(3,5‐dimethyl‐1‐pyrazolyl)propane)] have been synthesized in methanol as a solvent and fully characterized by the single crystal X‐ray diffraction, elemental analysis, FT‐IR, UV–Vis, density functional theory (DFT) calculations, antibacterial, and anticancer properties. In both of them, zinc ion is tetrahedrally coordinated to two nitrogen atoms from one of the chelating bidentate bis(3,5‐dimethylpyrazolyl)methane units of the LN ligand and one terminal chlorine. The forth coordination site was occupied by methoxy group in 1 and azide co‐ligand in complex 2. In contrast to 1, in the structure of 2 two metal centers are bridged by the tetradentate chelating LN ligand to form a dinuclear complex. Interestingly, the environment around the central atom in these complexes are mimicked with the core structure of the zinc metalloproteinases, Thermolysin {[NNO]ZnX} and Carbonic anhydrase {[NNN]ZnX} for complexes 1 and 2, respectively. Data analysis of the antibacterial activities demonstrated that the gram positive species showed more sensitivity toward the target title agents. Although, both complexes exhibit antibacterial activities and kill bacteria at low concentration, but complex 1 has higher DNA cleavage activity than 2. Additionally, the cytotoxicity of the free ligand and its complexes was evaluated against the human carcinoma cell line (Caco‐2) by the MTT method and the IC50 values were calculated for all of them. Due to the presence of pyrazole rings in the structure of the ligand and its complexes, these materials have a substantial potential to inhibit cancer cell metastasis. The energetic stabilization due to donor‐acceptor interactions in terms of the natural bond orbital (NBO) analyses and nonlinear optical properties were also examined by using the DFT calculations.