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Öğe A joint action of coordination, hydrogen and tetrel bonds toward a new 2D coordination polymer of lead(II) perchlorate and N'-isonicotinoylpyrazine-2-carbohydrazonamide(Elsevier b.v., 2025) Mahmoudi, Ghodrat; Garcia-Santos, Isabel; Safin, Damir A.; Fernández-Vazquez, Roi; Eftekhari-sis, Bagher; Gomila, Rosa M.; Frontera, AntonioA new 2D coordination polymer of lead(II) with N'-isonicotinoylpyrazine-2-carbohydrazonamide (HL) was readily produced by reacting with an equimolar amount of Pb(ClO4)2 in aqueous methanol solution. The resulting metallocomplex was isolated in the form of yellow prism-like crystals of {[PbL](ClO4)center dot 0.4H2O}n, suitable for a single crystal X-ray diffraction analysis, and was studied using FTIR and 1H NMR spectroscopy, and single crystal X-ray diffraction. The oxygen atoms of the ClO4- anion are disordered over two positions with an occupancy ratio of 60 % to 40 %. The minor occupancy is accompanied with the crystal water molecule, which, thus, yields 0.4 molecule per one [PbL](ClO4). Analysis of the crystal structure of the discussed complex allowed to reveal the formation of a dinuclear dimeric species [Pb2L2]2+ from the [PbL]+ cations through a pair of Pb center dot center dot center dot N tetrel bonds formed with the amide nitrogen atoms, which is further reinforced by a pair of pi center dot center dot center dot pi interactions formed between the pyrazine and pyridine rings. Three oxygen atoms from two perchlorate anions complete the coordination sphere (N4O4) of the metal cation, yielding an anionic {[PbL]2(ClO4)4}2- species, which is stabilized by a pair of N-H center dot center dot center dot O hydrogen bonds, formed by one of the NH2 hydrogen atoms and one of the oxygen atoms of the major occupancy of an adjacent perchlorate anion. In the crystal packing, the cations [PbL]+ are linked through the Pb-N coordination bonds formed with the pyridine nitrogen atom, yielding a 1D cationic coordination polymers {[PbL]n}n+ of a zig-zag structure, which, in turn, are linked into a 2D coordination network. The topology of this 2D network disclosed a uninodal 3-connected net of fes with the point symbol of (4 center dot 82). 2D layers are stacked with each other int a 3D supramolecular framework, which voids are filled by the perchlorate anions and crystal water molecules. DFT calculations have been performed to characterize the Pb center dot center dot center dot N/O tetrel bonding interactions along with more conventional hydrogen bonding that are crucial in the generation of the coordination polymer and its final 3D architecture.Öğe A lead(II)-N′-isonicotinoylpyrazine-2-carbohydrazonamide complex system as a converter of aerial carbon dioxide to carbonate under electrochemical conditions with the formation of a single-component white light-emitting phosphor(Royal society of chemistry, 2024) Mahmoudi, Ghodrat; Garcia-Santos, Isabel; Labisbal, Elena; Castineiras, Alfonso; Alizadeh, Vali; Gomila, Rosa M.; Frontera, Antonio; Safin, Damir A.In this contribution, a novel binuclear heteroleptic complex [Pb2L2(CO3)]2CH(3)CN2MeOH (12CH(3)CN2MeOH) is reported, which was fabricated by electrochemical oxidation of a lead anode under an ambient atmosphere in a CH3CN : MeOH solution of N '-isonicotinoylpyrazine-2-carbohydrazonamide (HL). The CO32- anion was produced from the conversion of aerial CO2 by the Pb2+-L complex system under electrochemical conditions. In the structure of 1, ligand L exhibits a tridentate pincer-like N,N ',O-coordination mode, while the CO32- anion exhibits a tetradentate bridging coordination mode with one of the oxygen atoms exhibiting a bridging mu-coordination mode. The metal cations in the structure of 1 are in a five-membered N2O3 coordination environment, formed by covalent bonds. The molecular structure of 12CH(3)CN2MeOH is stabilized by a pair of intermolecular Pb & ctdot;N tetrel bonds formed with one of the NH2 nitrogen atoms of an adjacent complex molecule and with the acetonitrile nitrogen atom, and one Pb & ctdot;O tetrel bond formed with the carbonyl oxygen atom of the other adjacent complex molecule, yielding a 2D supramolecular sheet. This sheet is further stabilized by intermolecular N-H & ctdot;N-acetonitrile and N-H & ctdot;O-carbonate hydrogen bonds and pi(Pyrazine)& ctdot;pi(Pyridine) interactions. The optical properties of the complex were revealed by UV-vis spectroscopy and spectrofluorimetry in MeOH. It was established that the described complex is emissive upon excitation at 340 nm with a broad band from about 500 nm to 780 nm with a maximum at similar to 580 nm, accompanied by a shoulder at similar to 620 nm. The CIE-1931 chromaticity coordinates of (0.28, 0.36) fall within the white gamut of the chromaticity diagram. Thus, complex 1 is a single-component white light-emitting phosphor.Öğe A Nanosized Porous Supramolecular Lead(II)-N′-phenyl(pyridin-2-yl)methylene-N-phenylthiosemicarbazide Aggregate, Obtained Under Electrochemical Conditions(American Chemical Society, 2024) Mahmoudi, Ghodrat; Garcia Santos, Isabel; Labisbal, Elena; Castineiras, Alfonso; Alizadeh, Vali; Gomila, Rosa M.; Frontera, Antonio; Safin, Damir A.A novel nanosized porous supramolecular nonanuclear complex [Pb9(HL)12Cl2(ClO4)](ClO4)3·15H2O·a(solvent) (1·15H2O·a(solvent)) is reported that was synthesized by electrochemical oxidation of a Pb anode under the ambient conditions in a CH3CN:MeOH solution of N′-phenyl(pyridin-2-yl)methylene-N-phenylthiosemicarbazide (H2L), containing [N(CH3)4]ClO4 as a current carrier. The supramolecular aggregate of 1 is enforced by a myriad of Pb···S tetrel bonds (TtBs) established with the thiocarbonyl sulfur atoms of adjacent species, which have been also analyzed by DFT calculations via 2D maps of ELF, Laplacian and RDG properties. Moreover, Pb···Cl TtBs with the central Cl- anion, and Pb···O TtBs with the three oxygen atoms of the ClO4- anion, were revealed. Notably, the molecular structure of 1 differs significantly from that recently reported by us [Pb2(HL)2(CH3CN)(ClO4)2]·2H2O (2·2H2O), which was obtained using a conventional synthetic procedure by reacting Pb(ClO4)2 with H2L in the same CH3CN:MeOH solution, thus highlighting a crucial role of the electrochemical conditions. The optical characteristics of the complex were investigated using UV-vis spectroscopy and spectrofluorimetry in methanol. The complex was found to be emissive when excited at 304 nm, producing a broad emission band ranging from approximately 420 to 600 nm with multiple peaks. The CIE-1931 chromaticity coordinates, calculated as (0.33, 0.24), suggest that the emission lies in the white region of the chromaticity diagram. Further investigation is needed to fully characterize the origin of this emission. © 2024 The Authors. Published by American Chemical Society.Öğe A novel tetrazole–1,8-naphthyridine–amide hybrid: First structurally characterized tetrazolo[1,5-a]-derivative of naphthyridines with a luminescence activity, potency against COVID-19, and anticancer activity(Elsevier B.V., 2025) Adhikari, Suman; Nath, Sourav; Sen, Tanushree; Raza, Rameez; Şahin, Onur; Eftekhari Sis, Bagher; Mahmoudi, Ghodrat; Borah, Pranab; Verma, Akalesh Kumar; Safin, Damir A.This contribution is devoted to a novel tetrazole–1,8-naphthyridine–amide hybrid N-(tetrazolo[1,5-a][1,8]naphthyridin-8-yl)butyramide (1), which was produced from N-(7‑chloro-1,8-naphthyridin-2-yl)butyramide by reacting with NaN3. In the crystalline state, molecules of 1 exhibited C–H···O intramolecular bonds and produced a 1D chain through N–H···N and C–H···N contacts. Chains produce a supramolecular 2D layer due to π···π interactions. In the UV–vis spectrum, 1 exhibits bands up to ∼360 nm and is emissive with a broad band from about 335 to 450 nm, with the maximum at 365 nm. Fine features of 1 were revealed using the density functional theory (DFT) calculations in water. The computed geometrical parameters are in accordance with the experimental values. The frontier electronic orbitals were found on the molecule except for the propyl fragment, and 1 was determined as a strong electrophile. The computed absorption, distribution, metabolism, elimination and toxicity (ADMET) features predicted positive gastrointestinal absorption (GA) activity and negative human blood-brain barrier (BBB) property of 1. Compound 1 in silico tested to inhibit some of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) proteins. Papain-like protease (PLpro) and Nonstructural protein 3 (Nsp3_range 207–379-MES) were established to interact with 1 more efficiently. The PLpro complex with 1 exhibits a ligand efficiency scores for a Hit. The present study also delved into elucidating the cytotoxic potential of compound 1 in Dalton's Lymphoma (DL) malignant cancer cell lines, aiming to explore its anticancer efficacy. Furthermore, this investigation extends its purview to scrutinize the cytotoxicity profile of the aforementioned compound on normal peripheral blood mononuclear cells (PBMCs), thus enabling a comprehensive comparative analysis of cellular responses under both neoplastic and non-neoplastic cell lines. © 2024 Elsevier B.V.Öğe Aerial carbon dioxide conversion to carbonate mediated by a lead(ii) complex with tridentate bipyridine containing a hydrazide ligand under electrochemical conditions yielding single-component white-light-emitting phosphors(Royal Society of Chemistry, 2024) Mahmoudi, Ghodrat; Garcia Santos, Isabel; Labisbal, Elena; Castiñeiras, Alfonso; Alizadeh, Vali; Gomila, Rosa M.; Frontera, Antonio; Safin, Damir A.A novel tetranuclear complex [Pb4L4(CO3)2]·4H2O (1·4H2O) is reported, which was obtained through the electrochemical oxidation of a lead anode under an ambient atmosphere in a CH3CN : MeOH solution of N’-isonicotinoylpicolinohydrazonamide (HL). CO32− anions were formed through the conversion of aerial CO2via the Pb2+-L complex system under electrochemical conditions. The ligand L links two Pb2+ cations through the carbonyl oxygen atom, while the CO32− anion links two Pb2+ cations through two monodentate and one bidentate oxygen atoms. The molecular structure of 1 is stabilized by a pair of Pb⋯O tetrel bonds formed with the bidentate oxygen atom of the CO32− anion, while molecules of 1 are interlinked through reciprocal π(chelate ring)⋯π(chelate ring), π(chelate ring)⋯π(noncovalent ring) and Pb⋯π(noncovalent ring) interactions, yielding a 1D supramolecular chain. The same reaction but under a nitrogen atmosphere yielded a novel mononuclear complex [PbL2]·MeOH·2H2O (2·MeOH·2H2O). In the structure of 2, each ligand L exhibits a tridentate coordination mode. Molecules of 2 are also interlinked through reciprocal π(chelate ring)⋯π(chelate ring), π(chelate ring)⋯π(noncovalent ring) and Pb⋯π(noncovalent ring) interactions, similar to 1, yielding a 1D supramolecular chain. The energetic features of these assemblies were studied using DFT calculations. Additionally, QTAIM analysis was employed to characterize noncovalent contacts, including intermolecular Pb⋯N tetrel bonds. These tetrel bonds were further analyzed using the ELF and Laplacian of electron density 2D maps, which confirmed their noncovalent nature. The optical properties of the complexes were revealed using UV-vis and diffuse reflectance spectroscopy and spectrofluorometry. Both complexes were found to be emissive in a solution of MeOH. CIE-1931 chromaticity coordinates of (0.38, 0.37) and (0.31, 0.32) for 1·4H2O and 2·MeOH·2H2O, respectively, fall within the white gamut of the chromaticity diagram. © 2024 The Royal Society of Chemistry.Öğe Discrete versus polymeric structures of coordination compounds of copper (II) with (pyridin-2-yl)methylenenicotinohydrazide and a library of dicarboxylic acids(ELSEVIER, 05.10.2024) Benito, Monica; Mahmoudi, Ghodrat; Molins, Elies; Zangrando, Ennio; Gargari, Masoumeh Servati; Frontera, Antonio; Safin, Damir A.A series of copper(II) discrete and polymeric coordination compounds, namely [{CuL(H2O)}(2)(fum)] (1), [{CuL(H2O)}(2)(mes)] (2), [Cu2L2(glu)](n)2n(H2O) (32n(H2O)) and [Cu3L2(adi)(2)](n) (4) were fabricated from (pyridin-2-yl)methylenenicotinohydrazide (HL) and a library of dicarboxylic acids, namely fumaric acid (H(2)fum), mesaconic acid (H(2)mes), glutaric acid (H(2)glu) and adipic acid (H(2)adi), using evaporative crystallization, grinding and slurry synthesis methods. The obtained coordination compounds have been fully characterized by single crystal X-ray diffraction revealing different types of complexes depending on the linker length, viz. from dinuclear complexes for the shorter linkers (fumaric and mesaconic acids) to 1D and 2D coordination polymers for longer glutaric and adipic acids. Thermal stability and spectroscopic features (FTIR and diffuse reflectance) of complexes were also studied. For the nonpolymeric compounds 1 and 2, the supramolecular assemblies driven by a combination of antiparallel pi-stacking and hydrogen bonding interactions have been studied and compared using DFT calculations, MEP surface analysis and a combination of QTAIM and NCIplot computational tools.Öğe Novel benzoyl and acetyl pyrazine-2-carbohydrazonamide hybrid derivatives: Experimental and theoretical insights(Elsevier B.V., 2024) Mahmoudi, Ghodrat; Garcia Santos, Isabel; Castiñeiras, Alfonso; Servati Gargari, Masoumeh; Frontera, Antonio; Safin, Damir A.A series of novel benzoyl and acetyl pyrazine-2-carbohydrazonamide hybrid derivatives, namely N’-benzoylpyrazine-2-carbohydrazonamide (1), N’-(4-methylbenzoyl)pyrazine-2-carbohydrazonamide (2), N’-(2-phenylacetyl)pyrazine-2-carbohydrazonamide (3) and N’-(2-(1H-indol-3-yl)acetyl)pyrazine-2-carbohydrazonamide (4), were readily obtained using a metallic Na-assisted interaction of 2-cyanopyrazine with benzohydrazide, 4-methylbenzohydrazide, 2-phenylacetohydrazide or 2-(1H-indol-3-yl)acetohydrazide in dry MeOH. Compounds 1–4 were studied by a set of physical measurements, including FTIR, 1H NMR and UV–vis spectroscopy, while their crystal structures were elucidated by single crystal X-ray diffraction and the corresponding crystal packing was further studied in detail using the Hirshfeld surface analysis. Compounds 3 and 4 were found to adopt both the E- and Z-isomeric forms in DMSO‑d6. Molecules of the title compounds are linked via N[sbnd]H⋯O and N[sbnd]H⋯N hydrogen bonds and π⋯π interactions, yielding supramolecular aggregates. As it was found by the Hirshfeld surface analysis, molecules of 1–4 mainly interact through the H⋯X (X = H, C, N and O) and C⋯X (X = C and N) contacts. The molecular interactions were quantified and compared using DFT calculations, molecular electrostatic potential (MEP) analysis and quantum theory of atoms in molecules (QTAIM) analysis, highlighting the dominant role of hydrogen bonding interactions in governing the crystal packing. © 2024 The Author(s)Öğe Versatile copper(ii) discrete and polymeric coordination compounds with (pyridine-2-yl)methylenenicotinohydrazide and azelaic acid(Royal society of chemistry, 2024) Benito, Mónica; Mahmoudi, Ghodrat; Molins, Elies; Zangrando, Ennio; Servati Gargari, Masoumeh; Gomila, Rosa M.; Frontera, Antonio; Safin, Damir A.In this contribution, a series of copper(ii) discrete and polymeric coordination compounds, namely [Cu3L2(aze)2]nnH2O (1nH2O), [CuL2]H2O (2H2O) and [CuL(H2O)(Haze)]H2O (3H2O) were fabricated from (pyridin-2-yl)methylenenicotinohydrazide (HL) and azelaic acid (H2aze), using evaporative crystallization, grinding and slurry synthesis methods. The solvent crystallization method produced a crystalline precipitate of complex 1nH2O. The filtrate allowed the production of crystals of complex 3H2O. The grinding synthetic method gave rise to a mixture of complexes 1nH2O, 2H2O and an undetermined phase. Results of the slurry synthetic approach highly depend on the stirring time. The obtained coordination compounds have been fully characterized by single crystal X-ray diffraction revealing different structures of complexes, viz. from mononuclear homo- and heteroleptic complexes (2 and 3) to a 1D heteroleptic coordination polymer (1). DFT calculations on non-polymeric complexes were conducted to evaluate the hydrogen-bonding and pi-stacking interactions that play a critical role in the solid-state structures of complexes 2 and 3. Additionally, the impact of co-crystallized water molecules, which enhance the pi-stacking interactions, was analyzed using energy decomposition analysis.Öğe Zinc(II) coordination compound with N ′-(pyridin-2-ylmethylene) nicotinohydrazide: Synthesis, crystal structure, computational and cytotoxicity studies(Elsevier science INC, 2024) Adhikari, Suman; Nath, Sourav; Kansız, Sevgi; Balidya, Nabajyoti; Paul, Anirban Kumar; Dege, Necmi; Şahin, Onur; Mahmoudi, Ghodrat; Verma, Akalesh Kumar; Safin, Damir A.In this work, we report on the synthesis of a novel zinc(II) coordination compound [ZnL 2 ] ( 1 ), which was readily obtained from the reaction of Zn(OAc) & sdot; 2H 2 O and N ' -(pyridin-2-ylmethylene)nicotinohydrazide ( HL ) in methanol. Recrystallization of 1 from dimethylformamide under ambient conditions allowed to produce yellow blocklike crystals of 1 & sdot; H 2 O. Complex 1 & sdot; H 2 O was characterized by FT-IR and 1 H NMR spectroscopy, while its optical properties were studied by UV - vis and spectrofluorimetry in methanol. The crystal structure of the title complex was revealed by single crystal X-ray diffraction and further explored in detail by the Hirshfeld surface analysis. Theoretical investigations based on the DFT calculations have also been applied to show the electronic properties of complex 1 . The antitumor activities of the parent ligand HL and complex 1 were studied using Dalton ' s lymphoma malignant cancer model. Both compounds were found to induce concentration -dependent cytotoxicity and apoptotic cell death, leading to a decrease in cell viability, body weight, and tumor volume in mice with the superior activity of complex 1 over HL . Mice treated with complex 1 demonstrated an increase in life span with a survival period of 23 days. Finally, using a molecular docking approach, we have probed complex 1 to inhibit the recombinant mouse tumor -necrosis factor alpha (mTNF).
