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    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, Antonio
    A 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.
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    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.
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    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.
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    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.
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    Anion driven tetrel bonding dictated supramolecular architectures of lead(ii) with a zwitterionic form of polydentate N′-(piperidine-1-carbonothioyl)picolinohydrazonamide
    (Royal society of chemistry, 2024) Mahmoudi, Ghodrat; Garcia-Santos, Isabel; Castineiras, Alfonso; Fernandez-Vazquez, Roi; Gargari, Masoumeh Servati; Gomila, Rosa M.; Frontera, Antonio
    Two novel supramolecular heteroleptic complexes [Pb2L2(NO3)(2)](n) (1) and {[Pb3L3](ClO4)(3)}(n)3.25nH(2)O (23.25nH(2)O), obtained from N '-(piperidine-1-carbonothioyl)picolinohydrazonamide (HL) and Pb(NO3)(2) or Pb(ClO4)(2) in aqueous methanol are reported. A crucial role of the auxiliary ligand (NO3- vs. ClO4-) was revealed as a driving force for the formation of the resulting architecture of complexes, which, in turn, are dictated by the formation of tetrel bonds. Complex 1 is constructed from heteroleptic dinuclear centrosymmetric species [Pb2L2(NO3)(2)], which, in turn, are formed from the heteroleptic mononuclear symmetry related [PbL(NO3)] units, linked through a pair of bonds formed between the metal cations and the thioamide nitrogen atoms. The metal cations form a weaker tetrel bond with the symmetry related nitrate atoms, yielding a 1D polymeric chain structure. These chains are interlinked through N-H & ctdot;O hydrogen bonds, formed between the covalently coordinated nitrate oxygen atom and the NH2 hydrogen atom, yielding a 2D supramolecular architecture. Complex 23.25nH(2)O is constructed from the trinuclear species [Pb3L3](ClO4)(3). The trinuclear cation is constructed from three [PbL](+) cations interlinked through two Pb-S and two Pb-N bonds, formed with the thiocarbonyl sulfur atoms and the amide nitrogen atoms. The cations [Pb3L3](3+) are interlinked through two Pb-N and two Pb-S bonds yielding a 1D supramolecular polymeric cationic chain {[Pb3L3](3+)}(n). The two metal cations corresponding to two [PbL](+) units, linked through a pair of the Pb-S bonds, are additionally bridged by two oxygen atoms of one of the perchlorate anions with the formation of two Pb & ctdot;O tetrel bonds. The coordination spheres of the metal cations are filled by one of the oxygen atoms of two different perchlorate anions with the formation of tetrel bonds. One of these perchlorates also forms the N-H & ctdot;O hydrogen bond within the trinuclear unit [Pb3L3](ClO4)(3). 1D supramolecular chains {[Pb3L3](3+)}(n) are interlinked through a myriad of hydrogen bonds formed by the perchlorate anions and crystallized water molecules. The tetrel bonds involving the counterions (Pb & ctdot;O) have been also analysed by DFT calculations via a MEP surface plot and 2D maps of electron localization function (ELF), Laplacian of electron density (del(2)rho) and reduced density gradient (RDG), confirming their noncovalent nature.
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    Exploring coinage bonding interactions in [Au(CN)4]− assemblies with silver and zinc complexes: a structural and theoretical study
    (Royal society of chemistry, 2025) Giordana, Alessia; Priola, Emanuele; Mahmoudi, Ghodrat; Doustkhah, Esmail; Gomila, Rosa M.; Zangrando, Ennio; Diana, Eliano; Operti, Lorenza; Frontera, Antonio
    This study investigates the non-covalent interactions between [Au(CN)4]- anions and silver and zinc complexes, with a particular focus on coinage bonding interactions. Four new complexes, [Ag2(pyNP)2][Au(CN)4]2 (1) [Zn(bipy)3][Au(CN)4]2 (2), [Zn(phen)3][Au(CN)4]2 (3) and [Zn(terpy)(H2O)3][Au(CN)4]2 (4), were synthesized and spectroscopically characterized, including their X-ray solid-state structures, where pyNP is (2-(2-pyridyl)-1,8-naphthyridine, bipy is 2,2 ' bipyridine, phen is 1,10 '-phenantroline and terpy is terpyridine. The [Au(CN)4]- anion exhibits unique anion & ctdot;anion interactions, despite the electrostatic repulsion, forming stable 1D supramolecular polymers in the solid state. Using a combination of X-ray crystallography and DFT calculations, this work characterizes the coordination and non-covalent bonding modes, including Au & ctdot;N coinage bonds. Energy decomposition analysis (EDA), QTAIM, and NCIplot methods were applied to understand the energetics and bonding nature. The study reveals that electrostatic and dispersion forces play critical roles in stabilizing these assemblies, especially in the formation of pi-stacking and T-shaped dimers. These findings offer insights into the design of new materials leveraging coinage bonding in molecular architectures.
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    Exploring coinage bonding interactions in [Au(CN)4]− assemblies with silver and zinc complexes: a structural and theoretical study
    (Royal society of chemistry, 2025) Giordana, Alessia; Priola, Emanuele; Mahmoudi, Ghodrat; Doustkhah, Esmail; Gomila, Rosa M.; Zangrando, Ennio; Diana, Eliano; Operti, Lorenza; Frontera, Antonio
    This study investigates the non-covalent interactions between [Au(CN)4]− anions and silver and zinc complexes, with a particular focus on coinage bonding interactions. Four new complexes, [Ag2(pyNP)2][Au(CN)4]2 (1) [Zn(bipy)3][Au(CN)4]2 (2), [Zn(phen)3][Au(CN)4]2 (3) and [Zn(terpy)(H2O)3][Au(CN)4]2 (4), were synthesized and spectroscopically characterized, including their X-ray solid-state structures, where pyNP is (2-(2-pyridyl)-1,8-naphthyridine, bipy is 2,2′ bipyridine, phen is 1,10′-phenantroline and terpy is terpyridine. The [Au(CN)4]− anion exhibits unique anion⋯anion interactions, despite the electrostatic repulsion, forming stable 1D supramolecular polymers in the solid state. Using a combination of X-ray crystallography and DFT calculations, this work characterizes the coordination and non-covalent bonding modes, including Au⋯N coinage bonds. Energy decomposition analysis (EDA), QTAIM, and NCIplot methods were applied to understand the energetics and bonding nature. The study reveals that electrostatic and dispersion forces play critical roles in stabilizing these assemblies, especially in the formation of π-stacking and T-shaped dimers. These findings offer insights into the design of new materials leveraging coinage bonding in molecular architectures.
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    Structural diversity and tetrel bonding significance in lead(ii) complexes with pyrazoylisonicotinoylhydrazone and varied anionic co-ligands
    (Royal Soc Chemistry, 2024) Mahmoudi, Ghodrat; Garcia-Santos, Isabel; Fernandez-Vazquez, Roi; Gomila, Rosa M.; Castineiras, Alfonso; Doustkhah, Esmail; Zangrando, Ennio
    Four lead(ii) complexes featuring pyrazoylisonicotinoylhydrazone ligand paired with various anionic co-ligands (azido, thiocyanato, nitrito, and nitrato) were synthesized and thoroughly examined using structural, analytical, and spectroscopic techniques. These ligands, in their mono-deprotonated state, bind to the lead(ii) ion in a tridentate manner through two nitrogen atoms and one oxygen atom. Single-crystal X-ray crystallography revealed the capacity of these molecular complexes to form larger aggregates influenced by the nature of the anion attached to the metal center. In every complex, the lead atom adopts a hemidirectional coordination environment, making it geometrically suited for tetrel bond formation. The crystal structures demonstrate that lead atoms engage in notably short interactions with nitrogen atoms, distances that are shorter than the sum of their van der Waals radii yet exceed the sum of their covalent radii. These tetrel bonds play a pivotal role in weaving the monomeric into self-assembled dimers or extended supramolecular 1D polymers. The formation and characteristics of these intriguing supramolecular structures observed in the solid state of each complex were further explored and validated through density functional theory (DFT) calculations and several computational tools like MEP, NCIPlot, QTAIM, and ELF methods.
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    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.