Anionic Ligands Research Articles

Synthesis and Characterization of Cobalt(II/II) and Cobalt(II/III) Macrocyclic Complexes and Their Application in the Copolymerization of Epoxides and CO2

The synthesis and characterization of six dinuclear cobalt complexes bearing a conjugated macrocyclic ligand are reported. The condensation of 2,6-diformylphenol and o-phenylenediamine led to semi-hydrogenated macrocycles A–C. The ligand precursor A reacted with Co(OAc)2·4H2O and generated the Co(II/II) complex 1, and a conjugated macrocyclic ligand was formed during the complexation. The partial oxidation of 1 with air resulted in mixed-valence Co(II/III) complexes 2 and 3 bearing different anionic ligands. Analogous Co(II/III) complexes 4–6 of Cl- and F-substituted ligand backbones were also synthesized. Structural characterization and charge determination of all complexes were achieved through X-ray diffraction analysis and X-ray photoelectron spectroscopy. These complexes were applied in the copolymerization of CO2 and cyclohexene oxide (CHO), and the mixed valence Co(II/III) complex 2 showed good reactivity and selectivity (>99% polycarbonate).

π Acceptor Abilities of Anionic Ligands: Comparisons Involving Anionic Ligands Incorporated into Linear d10 [(NH3)Pd(A)]-, Square Planar d8 [(NN2)Ru(A)]-, and Octahedral d6 [(AsN4)Tc(A)]- Complexes.

Extended transition state-natural orbitals for chemical valence (ETS-NOCV)] data were used to rank electron acceptor capacities for several potentially synergistic anionic ligands incorporated into linear d10 [(NH3)Pd(A)]-, square planar d8 [(NN2)Ru(A)]-, and octahedral d6 [(AsN4)Tc(A)]- complexes [A = anionic ligand, NN2 = HN(CH2CH2CH2NH2)2, and AsN4 = [As(CH2CH2CH2NH2)4]-]. It was possible to differentiate between the best acceptors, among them BI2- and B(CF3)2-, and the poorest ones. A sizable fraction of the anionic ligands studied exhibit similar acceptor capacities (backbonding), mostly regardless of d electron count. A number of trends were discerned, including the fact that acceptor capacity decreases down families and across rows but increases down families of the peripheral substituents. The latter appears tied to the ability of the peripheral ligands to compete with the metal in donating electrons to the ligand-binding atom.

Woven, Polycatenated, or Cage Structures: Effect of Modulation of Ligand Curvature in Heteroleptic Uranyl Ion Complexes

Combining the flexible zwitterionic dicarboxylate 4,4'-bis(2-carboxylatoethyl)-4,4'-bipyridinium (L) and the anionic dicarboxylate ligands isophthalate (ipht2-) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda2-), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO2)2(L)(ipht)2] (1) and [(UO2)2(L)(1,2-pda)2]·2H2O (2) have the same stoichiometry, and both crystallize as monoperiodic coordination polymers containing two uranyl-(anionic carboxylate) strands united by L linkers into a wide ribbon, all ligands being in the divergent conformation. Complex 3, [(UO2)2(L)(1,3-pda)2]·0.5CH3CN, with the same stoichiometry but ligands in a convergent conformation, is a discrete, binuclear species which is the first example of a heteroleptic uranyl carboxylate coordination cage. With all ligands in a divergent conformation, [(UO2)2(L)(1,4-pda)(1,4-pdaH)2] (4) crystallizes as a sinuous and thread-like monoperiodic polymer; two families of chains run along different directions and are woven into diperiodic layers. Modification of the synthetic conditions leads to [(UO2)4(LH)2(1,4-pda)5]·H2O·2CH3CN (5), a monoperiodic polymer based on tetranuclear (UO2)4(1,4-pda)4 rings; intrachain hydrogen bonding of the terminal LH+ ligands results in diperiodic network formation through parallel polycatenation involving the tetranuclear rings and the LH+ rods. Complexes 1-3 and 5 are emissive, with complex 2 having the highest photoluminescence quantum yield (19%), and their spectra show the maxima positions usual for tris-κ2O,O'-chelated uranyl cations.

Iron-Catalyzed Selective Hydroboration of CO2 by Cooperative B–H Bond Activation

We report a novel iron(II) complex supported by an anionic phosphanyl-iminopyridinate ligand, Cp*Fe(Cy2PN═C5H4N) (1), which shows remarkable catalytic activity in the selective hydroboration of CO2 with HBpin, producing boryl formate with a turnover frequency (TOF) of ∼1176 h–1 at room temperature. This catalysis involves cooperative metal–ligand reactivity for H–B bond activation, affording a key Fe(II)–H intermediate, Cp*FeH(Cy2PN(Bpin)C5H4N) (2), that binds the Bpin moiety at the non-coordinated amino site. The very fast and selective formoxy production can be conveniently coupled to the N-formylation of amines, which delivers a variety of formamides. In addition, the reduction of boryl formate to the CH3OBpin stage was also achieved by 1 with HBpin under N2.

Developing terpyridine-based metal complexes for non-aqueous redox flow batteries

This paper describes the design and synthesis of a series of terpyridine-based complexes of the first-row transition metals Cr, Mn, Fe, and Co for non-aqueous redox flow batteries (NARFBs). Electrochemical studies reveal that these complexes can undergo multi-electron transfer redox reactions. In particular, the Mn and Fe-based complexes exhibit both low negative redox potentials and high positive redox potential, permitting them to serve as a bipolar electrolyte for symmetric RFBs with a cell voltage of more than 2 V. The solubility of these complexes can be effectively improved by incorporating a polyether substituent on the terpyridine ligand and counter anion optimization. The iron complex [Fe(tpy-O(CH2CH2O)3CH3)2][TFSI]2 shows a high solubility of 0.76 M in MeCN. The fabricated iron-based symmetric NARFB demonstrates a superior battery performance with a high cell voltage of 2.3 V, columbic efficiency of 97%, energy efficiency as high as 88%, and stable charge-discharge capacity retention of 60% after 160 cycles, corresponding to 99.75 % capacity retention per cycle. The post-cycling cyclic voltammetry (CV), UV-Vis, and 1H-NMR characterizations indicate only minor chemical decomposition of the cycled complex, confirming its good charging-discharging stability.

Heteroleptic Metal-Organic Frameworks of Lanthanides (Lа, Ce, and Ho) Based on Ligands of the Anilate Type and Dicarboxylic Acids

New heteroleptic metal-organic frameworks of lanthanides, units of which contain anionic organic ligands of two types, are prepared by the solvothermal synthesis in N,N-dimethylformamide (DMF). The cross-linked coordination polymer [Ho2(CA)2(Bdc)·4DMF] (I) and two scaffold derivatives [La2(pQ)2(Bpdc)·4DMF] (II) and [Ce2(CA)(Bdc)2·4DMF]·2DMF (III·2DMF), where CA is chloranilic acid dianion, pQ is 2,5-dihydroxy-3,6-di-tert-butyl-para-benzoquinone dianion, Bdc is terephthalic acid dianion, and Bpdc is 4,4'-biphenyldicarboxylic acid dianion, are synthesized. The structures of compounds I, II, and III·2DMF are studied by X-ray diffraction (XRD) (CIF file CCDC nos. 2212230, 2212231, and 2212232, respectively).

Divalent Europium, NIR and Variable Emission of Trivalent Tm, Ho, Pr, Er, Nd, and Ce in 3D Frameworks and 2D Networks of Ln–Pyridylpyrazolates

The redox reactions of various lanthanide metals with 3-(4-pyridyl)pyrazole (4-PyPzH) or 3-(3-pyridyl)pyrazole (3-PyPzH) ligands yield the 2D network ∞2[Eu(4-PyPz)2(Py)2] containing divalent europium, the 3D frameworks ∞3[Ln(4-PyPz)3] and ∞3[Ln(3-PyPz)3] for trivalent cerium, praseodymium, neodymium, holmium, erbium, and thulium as well as ∞3[La(4-PyPz)3], and the 2D networks ∞2[Ln(4-PyPz)3(Py)] for trivalent cerium and thulium and ∞2[Ln2(4-PyPz)6]·Py for trivalent ytterbium and lutetium. The 18 lanthanide coordination polymers were synthesized under solvothermal conditions in pyridine (Py), partly acting as a co-ligand for some networks. The compounds exhibit a variety of luminescence properties, including metal-centered 4f–4f/5d–4f emission in the visible and near-infrared spectral range, metal-to-ligand energy transfer, and ligand-centered fluorescence and phosphorescence. The anionic ligands 3-PyPz− and 4-PyPz− serve as suitable antennas for lanthanide-based luminescence in the visible and near-infrared range through effective sensitization followed by emission through intra–4f transitions of the trivalent thulium, holmium, praseodymium, erbium, and neodymium. ∞2[Ce(4-PyPz)3(Py)], ∞3[Ce(4-PyPz)3], and ∞3[Ce(3-PyPz)3] exhibit strong degrees of reduction in the 5d excited states that differ in intensity compared to the ligand-based emission, resulting in a distinct emission ranging from pink to orange. The direct current magnetic studies show magnetic isolation of the lanthanide centers in the crystal lattice of ∞3[Ln(3-PyPz)3], Ln = Dy, Ho, and Er.

Mono-, Bis-, and Tris-Chelate Zn(II) Complexes with Imidazo[1,5-a]pyridine: Luminescence and Structural Dependence.

New mono-, bis-, and tris-chelate Zn(II) complexes have been synthesized starting from different Zn(II) salts and employing a fluorescent 1,3-substituted-imidazo[1,5-a]pyridine as a chelating ligand. The products have been characterized by single-crystal X-ray diffraction; mass spectrometry; and vibrational spectroscopy. The optical properties have been investigated to compare the performances of mono-, bis-, and tris-chelate forms. The collected data (in the solid state and in solution) elucidate an important modification of the ligand conformation upon metal coordination; which is responsible for a notable increase in the optical performance. An intense modification of the emission quantum yield along the series in the solid state is observed comparing mono-, bis-, and tris-chelate adducts; independently from the anionic ligand introduced by ionic exchange.

Synthesis, crystal structure and thermal decomposition pathway of bis-(iso-seleno-cyanato-κN)tetra-kis-(pyridine-κN)manganese(II).

The reaction of MnCl2·2H2O with KSeCN and pyridine in water leads to the formation of the title complex, [Mn(NCSe)2(C5H5N)4], which is isotypic to its Fe, Co, Ni, Zn and Cd analogues. In its crystal structure, discrete complexes are observed that are located on centres of inversion. The Mn cations are octa-hedrally coordinated by four pyridine coligands and two seleno-cyanate anions that coordinate via the N atom to the metal centres to generate trans-MnN(s)2N(p)4 octa-hedra (s= seleno-cyanate and p= pyridine). In the extended structure, weak C-H⋯Se contacts are observed. Powder X-ray diffraction (PXRD) investigations prove that a pure sample was obtained and in the IR and Raman spectra, the C-N stretching vibrations are observed at 2058 and 2060 cm-1, respectively, in agreement with the terminal coordination of the seleno-cyanate anions. Thermogravimetric investigations reveal that the pyridine coligands are removed in two separate steps. In the first mass loss, a compound with the composition Mn(NCSe)2(C5H5N)2 is formed, whereas in the second mass loss, the remaining pyridine ligands are removed, which is superimposed with the decomposition of Mn(NCSe)2 formed after ligand removal. In the inter-mediate compound Mn(NCSe)2(C5H5N)2, the CN stretching vibration is observed at 2090 cm-1 in the Raman and at 2099 cm-1 in the IR spectra, indicating that the Mn cations are linked by μ-1,3-bridging anionic ligands. PXRD measurements show that a compound has formed that is of poor crystallinity. A comparison of the powder pattern with that calculated for the previously reported Cd(NCSe)2(C5H5N)2 indicates that these compounds are isotypic, which was proven by a Pawley fit.

Regulating the Solvation Structure of Li+ Enables Chemical Prelithiation of Silicon-Based Anodes Toward High-Energy Lithium-Ion Batteries

HighlightsBy selecting 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized SiO/C anode can achieve an initial Coulombic efficiency of ~100%.Molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li+.The positive effect of pre-lithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film.

The Role of Anionic Ligands on Photoreactivity in Mo(VI) Dioxo Complexes of the Form MoO2 X2 (NN).

The photoreactivity of d0 metal dioxo complexes in activating C-H bonds has been recently studied.[1-3] We have previously reported that MoO2 Cl2 (bpy-t Bu) is an effective platform for light initiated C-H activation with unique product selectivity for the overall functionalization.[1] Herein we expand on these studies and report the synthesis and photoreactivity of several new Mo(VI) dioxo complexes with the general formula MoO2 (X)2 (NN); where X=F- , Cl- , Br- , CH3 - , PhO- , t BuO- and NN=2,2'-bipyridine (bpy) or 4,4'-tert-butyl-2,2'bipyridine (bpy-t Bu). Among these compounds, MoO2 Cl2 (bpy-t Bu) and MoO2 Br2 (bpy-t Bu) are able to participate in bimolecular photoreactivity with several substrates containing C-H bonds of various types such as allyls, benzyls, aldehydes (RCHO) and alkanes. MoO2 (CH3 )2 bpy and MoO2 (PhO)2 bpy do not participate in bimolecular photoreactions and instead they undergo photodecompositions. Computational studies indicate that the nature of the HOMO and LUMO is critical in supporting photoreactivity, with access to an LMCT (bpy→Mo) being necessary for tractable hydrocarbon functionalization.

Cationic Molecular Metal Chalcogenide Ligand‐Passivated Colloidal Quantum Dots and Their Application to Suppressed Dark‐Current Near‐Infrared Photodetectors

AbstractThe surface of colloidal‐type quantum dots (QDs) is protected with surfactants to maintain their nanoscale size and dispersion in various solvents. Such protection is advantageous to the processability of the dots, but the surfactants also act as insulators, thereby adversely affecting the electrical properties of the resulting devices. Anion‐type molecular metal chalcogenide complexes (MCCs) have been developed as an alternative to these surfactants. However, anionic ligands limit the charges of the resulting QDs to negative values; thus, additional processes are required to compensate for these charges. Herein, this work prepares cationic‐type dimetal diselenium perchlorate MCCs (M2Se2(ClO4)2, M = Mn, Zn, and Sn) and applies them to stabilize colloidal QDs. The resulting M2Se2‐PbS QDs are then used to fabricate near‐infrared photodetectors (NIR‐PDs). The devices exhibit remarkably suppressed dark current densities (JD) of as low as 4.92 × 10−10 A cm−2 when compared with PDs based on 1,2 ethandithiol‐PbS (EDT‐PbS) (JD = 1.41 × 10−8 A cm−2). In addition, the devices exhibit a high responsivity of 0.07 A W−1 in response to 950 nm NIR light signals, as well as an excellent specific detectivity of 5.66 × 1012 Jones at 950 nm. Finally, this work fabricates hybrid‐type QD films using cationic and anionic MCC‐PbS QDs and obtains a high external quantum efficiency (EQE) of 13.1%.

Neutral, Heteroleptic [Cu(I)(PPh3 )2 (4H-imidazolato)] Complexes: Ligand Exchange Reactivity, Redox Properties, Excited-State Dynamics.

Cu(I) 4H-imidazolate complexes are rare examples of Cu(I) complexes with chelating anionic ligands and are potent photosensitizers with unique absorption and photoredox properties. In this contribution, five novel heteroleptic Cu(I) complexes with monodentate triphenylphosphine co-ligands are investigated. As a consequence of the anionic 4H-imidazolate ligand and in contrast to comparable complexes with neutral ligands, these complexes are more stable than their homoleptic bis(4H-imidazolato)Cu(I) congeners. Here, the ligand exchange reactivity was studied by 31 P-,19 F-, and variable temperature NMR and the ground state structural and electronic properties by X-ray diffraction, absorption spectroscopy, and cyclic voltammetry. The excited-state dynamics were investigated by femto- and nanosecond transient absorption spectroscopy. The observed differences, with respect to chelating bisphosphine bearing congeners, are often due to the increased geometric flexibility of the triphenylphosphines. These observations render the investigated complexes interesting candidates for photo(redox)reactions not accessible with chelating bisphosphine ligands.

Synthesis and characterization of a new complex based on antibiotic: Zirconium complex

Abstract It is well known that sulfonamide derivatives, through exchange of different functional groups without modification of the –S(O)2N(H)– function, can exhibit a wide variety of pharmacological activities. In addition, some metal complexes of these ligands have been prepared to promote rapid healing of burns in humans and animals, for example, the complex of Zn(ii) sulfadiazine. Their effectiveness does not depend solely on the slow release of the metal ion, but rather strongly on the nature of the material to which the metal is bound. Given the ability of sulfonamide derivatives to coordinate with metal atoms in different ways, considerable interest in the synthesis and structural aspects of new complexes has arisen. These results confirm that the significant chemical capacity of sulfonamides to act as ligands is based on the acidity of its –S(O)2N(H)– function, which gives a donor anionic ligand, allied to the presence of atoms vicinal to nitrogen, sulfur or oxygen of the heterocyclic ring, which provide the stereochemical requirements for the realization of complexes with monodentate ligand, chelating agent or bridging ligand, providing monomeric structures, dimeric arrangements and polymers. In addition, the aromatic amino group is responsible for the chemical versatility of the sulfonamides, since it can act as a coordination site, as well as a reactive site for chemical modifications of sulfonamide complexes with very interesting biological purposes. In the present work, the synthesis and structure of a novel sulfanilamide complex: nitro (4-aminobenzenesulfonamide) zirconium was presented. Characterization of the complex was performed by infrared spectroscopic, thermogravimetric and X-ray diffraction analysis.

Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines.

Chiral amines are commonly used in the pharmaceutical and agrochemical industries1. The strong demand for unnatural chiral amines has driven the development of catalytic asymmetric methods1,2. Although the N-alkylation of aliphatic amines with alkyl halides has been widely adopted for over 100 years, catalyst poisoning and unfettered reactivity have been preventing the development of a catalyst-controlled enantioselective version3-5. Here we report the use of chiral tridentate anionic ligands to enable the copper-catalysed chemoselective and enantioconvergent N-alkylation of aliphatic amines with α-carbonyl alkyl chlorides. This method can directly convert feedstock chemicals, including ammonia and pharmaceutically relevant amines, into unnatural chiral α-amino amides under mild and robust conditions. Excellent enantioselectivity and functional-group tolerance were observed. The power of the method is demonstrated in a number of complex settings, including late-stage functionalization and in the expedited synthesis of diverse amine drug molecules. The current method indicates that multidentate anionic ligands are a general solution for overcoming transition-metal-catalyst poisoning.

Room-Temperature Cu-Catalyzed Amination of Aryl Bromides Enabled by DFT-Guided Ligand Design.

Ullmann-type C-N coupling reactions represent an important alternative to well-established Pd-catalyzed approaches due to the differing reactivity and the lower cost of Cu. While the design of anionic Cu ligands, particularly those by Ma, has enabled the coupling of various classes of aryl halides and alkyl amines, most methods require conditions that can limit their utility on complex substrates. Herein, we disclose the development of anionic N1,N2-diarylbenzene-1,2-diamine ligands that promote the Cu-catalyzed amination of aryl bromides under mild conditions. Guided by DFT calculations, these ligands were designed to (1) increase the electron density on Cu, thereby increasing the rate of oxidative addition of aryl bromides, and (2) stabilize the active anionic CuI complex via a π-interaction. Under optimized conditions, structurally diverse aryl and heteroaryl bromides and a broad range of alkyl amine nucleophiles, including pharmaceuticals bearing multiple functional groups, were efficiently coupled at room temperature. Combined computational and experimental studies support a mechanism of C-N bond formation that follows a catalytic cycle akin to the well-explored Pd-catalyzed variants. Modification of the ligand structure to include a naphthyl residue resulted in a lower energy barrier to oxidative addition, providing a 30-fold rate increase relative to what is seen with other ligands. Collectively, these results establish a new class of anionic ligands for Cu-catalyzed C-N couplings, which we anticipate may be extended to other Cu-catalyzed C-heteroatom and C-C bond-forming reactions.

Searching for Systems with Planar Hexacoordinate Carbons

Here, we present evidence that the D2h M2C50/2+ (M = Li-K, Be-Ca, Al-In, and Zn) species comprises planar hexacoordinate carbon (phC) structures that exhibit four covalent and two electrostatic interactions. These findings have been made possible using evolutionary methods for exploring the potential energy surface (AUTOMATON program) and the Interacting Quantum Atoms (IQA) methodology, which support the observed bonding interactions. It is worth noting, however, that these structures are not the global minimum. Nonetheless, incorporating two cyclopentadienyl anion ligands (Cp) into the CaC52+ system has enhanced the relative stability of the phC isomer. Moreover, cycloparaphenylene ([8]CPP) provides system protection and kinetic stability. These results indicate that using appropriate ligands presents a promising approach for expanding the chemistry of phC species.

Environmental Factors Controlling the Electronic Properties and Oxidative Activities of Birnessite Minerals

Recent studies of birnessite-type lattices show that they have an unusually low-lying band structure with an electron affinity value of 6.0 eV, which is the highest among all common oxides and sulfides in an aqueous solution. This study reports on the underlying mechanism through which environmental factors, such as organic and inorganic ligands, exert a strong influence on the band structure and oxidative reactivity of various synthetic and natural birnessite phases. Specifically, the study evaluated the effect of (i) disorder/crystallinity, (ii) common aqueous cations, and (iii) Mn(II) and Mn(III) complexing anionic ligands on Cr(III) to Cr(VI) oxidation activity, Mn dissolution, and the band structure of birnessite mineral with the aim of finding correlations between them. The results show that the high oxidative activity of various birnessites is coupled with their high electron affinity, which, in turn, is modulated by various aqueous anions and cations through their dynamic influence on the dissolution-controlled structural Mn(III)/Mn(II) content. Inorganic cations of different ionic radii and hydration strengths control the interlayer spacing of the basal sheets, while inorganic and organic aqueous anions control the extent of Mn(II) and Mn(III) complexation. Their combined effects are seen to govern the efficiency of Mn dissolution from the crystal, which modulates the birnessite activity and band structure.

Cobalt(II), nickel(II), palladium(II) and zinc(II) metallothiosemicarbazones: Synthesis, characterization, X-ray structures and biological activity

Metal(II) complexes of the type [Co(S-HL)2Cl2] and [Ni(N,S-L)2], [Pd(N,S-L)2], [Zn(N,S-L)2], were synthesized from the reaction of HL with metal(II) chlorides. All complexes were characterized by spectroscopic methods, such as elemental analysis, FT-IR, 1H NMR, and single crystal X-ray diffraction. In the [Co(S-HL)2Cl2] complex, the cobalt atom adopts a distorted tetrahedral geometry around the cobalt(II) ion, with two neutral monodentate S-thiosemicarbazone ligands coordinating via one of the thiocarbonyl sulfur atom and two chlorides. In the [Ni(N,S-L)2] and [Pd(N,S-L)2] complexes, HL ligand is coordinated with the metal center, as a mono anionic bidentate N,S donors which are in trans position and that metal(II) ions adopt square planar coordination. [Zn(N,S-L)2] indicates that the anionic thiosemicarbazone ligands bind to the metal in a distorted tetrahedral arrangement with N,S donor atoms. The antimicrobial activity of the ligand and metal(II) complexes were studied against bacterial strains and fungal stain. It was observed that the ligand showed weaker activity than the metal complexes. The Zn(II) complex had the best antibacterial activity against E. faecalis, while the Co(II) complex showed the best activity against S. aureus bacteria. Co(II) and Pd(II) complexes were relatively more effective against Gram-negative bacteria. It was determined that metal complexes were less effective against gram negative bacteria compared to gram positive bacteria. A little antifungal activity was observed in Zn(II) and Co(II) complexes.

Synthesis, characterization, crystal structure, Hirshfeld surface analysis and DFT of 1,2-benzothiazine metal (II) complexes

In the present study, the mononuclear complexes of oxicam precursor with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions have been prepared. The UV/Vis, FT-IR, 1H NMR spectroscopies, elemental analysis and magnetic susceptibility measurements were used to confirm successful synthesis of transition metal complexes. The square planar coordination geometry of the Cu(II) complex 5 was confirmed by XRD analysis. The spectroscopic data indicated that two mono anionic bidentate ligands act as chelating agents and attached with metal center via enolate oxygen and carbonyl oxygen of the ester group present in 1,2-benzothiazine. The molar conductance indicated the non-ionic nature of the Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes. The octahedral geometry is proposed for the Mn(II), Co(II) and Zn(II) complexes, respectively and square planar geometry for Ni(II) and Cu(II) complexes is proposed on the basis of obtained data. The reported basis sets with ligand and its Cu(II) complex were used to conduct DFT studies. The synthesis of the targeted compounds was also confirmed by energy gap calculations between HOMO and LUMO. The Hirshfeld surface analysis of the copper complex was carried and 2D contacts were drawn. Furthermore, COX-I and COX-II inhibition studies for the targeted compounds were carried out by applying molecular docking study. The docking results revealed that these molecules have potential to inhibit the cyclooxygenases and may reduce the inflammation in the body.