Spectral, structural and theoretical study of the effects of thiocyanato and dicyanamido ligands on the geometry of PbIIcomplexes containing a triazinic ligand

2019 ◽  
Vol 75 (8) ◽  
pp. 1023-1030
Author(s):  
Farzin Marandi ◽  
Keyvan Moeini ◽  
Zahra Mardani ◽  
Harald Krautscheid
Keyword(s):  
Density Functional ◽  
Aromatic Rings ◽  
Functional Theory ◽  
One Dimensional ◽  
X Ray ◽  
H Nmr ◽  
1D Coordination Polymer ◽  
Binuclear Structure ◽  
Ft Ir ◽  
Structural Database

Two lead(II) complexes of 5,6-bis(furan-2-yl)-3-(pyridin-2-yl)-1,2,4-triazine (DFPT), namely one-dimensional (1D)catena-poly[[bis[5,6-bis(furan-2-yl)-3-(pyridin-2-yl-κN)-1,2,4-triazine-κN2]lead(II)]-di-μ-thiocyanato-κ2N:S;κ2S:N], [Pb(NCS)2(C16H10N4O2)2]n,1, and binuclear di-μ-dicyanamido-κ2N1:N5;κ2N5:N1-bis{[5,6-bis(furan-2-yl)-3-(pyridin-2-yl-κN)-1,2,4-triazine-κN2](nitrato-κ2O,O′)lead(II)}, [Pb2(C2N3)2(NO3)2(C16H10N4O2)4],2, as well as DFPT itself, were prepared and identified by elemental analysis, FT–IR,1H NMR spectroscopy and single-crystal X-ray structural analyses. In the double-chain 1D coordination polymer of1and the binuclear structure of2, the Pb atom has ahemidirected-PbN6S2and a rareholodirected-PbN6O2environment, respectively, with a distorted cubic geometry. All the coordination modes of dicyanamide ligands within lead complexes were studied using the Cambridge Structural Database (CSD) to compare them with the structures of1and2. In addition to hydrogen bonds, the crystal networks are stabilized by π–π stacking interactions between the triazine, furyl and pyridine aromatic rings. The most stable theoretical structures of the title compounds predicted by density functional theory (DFT) calculations were compared with the solid-state results.

scholarly journals A binuclear Cd(II) complex containing bridging pyrimidine-based ligands

2020 ◽  
Vol 75 (3) ◽  
pp. 287-293
Author(s):  
Samireh Hosseini ◽  
Zahra Mardani ◽  
Keyvan Moeini ◽  
Cameron Carpenter-Warren ◽  
Alexandra M.Z. Slawin ◽  
...  
Keyword(s):  
Density Functional ◽  
Natural Bond Orbital ◽  
Distribution Patterns ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
H Nmr ◽  
Crystal Network ◽  
Ft Ir ◽  
Orbital Analysis

AbstractIn this work, a pyrimidine-based ligand, N′-(amino(pyrimidin-2-yl)methylene)pyrimidine-2-carbohydrazonamide hydrate (APPH · H2O), and its binuclear complex of cadmium, [Cd(μ-APPH)Br]2, 1, were prepared and identified by elemental analysis, FT-IR, 1H NMR spectroscopy as well as single-crystal X-ray diffraction. X-ray structure analysis of 1 revealed octahedrally coordinated cadmium centers with a CdN4Br2 environment containing two bridging APPH ligands; each APPH ligand acts as an N4-donor (N2-donor toward each cadmium atom) and forms two five-membered chelate rings that are approximately perpendicular to each other. In the network of 1, the N–H · · · Br hydrogen bonds form motifs such as ${\rm{R}}_{\rm{2}}^{\rm{2}}(12,{\rm{ }}14),{\rm{ R}}_{\rm{6}}^{\rm{6}}(24,{\rm{ }}26,{\rm{ }} \ldots ,{\rm{ }}46).$ The crystal network is further stabilized by π-π stacking interactions between pyrimidine rings. The optimized structures of the ligand and complex were investigated along with their charge distribution patterns by density functional theory and natural bond orbital analysis, respectively.

Coordination of a triazine ligand with CuII and AgI investigated by spectral, structural, theoretical and docking studies

2019 ◽  
Vol 75 (10) ◽  
pp. 1389-1397
Author(s):  
Farzin Marandi ◽  
Keyvan Moeini ◽  
Harald Krautscheid
Keyword(s):  
Hydrogen Bonds ◽  
Density Functional ◽  
Docking Studies ◽  
Planar Geometry ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
X Ray ◽  
Square Planar ◽  
Binuclear Structure ◽  
Ft Ir

Two complexes of 5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine (PPTA), namely (ethanol-κO)bis(nitrato-κO)[5-phenyl-3-(pyridin-2-yl-κN)-1,2,4-triazine-κN 2]copper(II), [Cu(NO3)2(C14H10N4)(C2H6O)] or [Cu(NO3)2(PPTA)(EtOH)] (1), and bis[μ-5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine]-κ3 N 1:N 2,N 3;κ3 N 2,N 3:N 1-bis[(nitrato-κO)silver(I)], [Ag2(NO3)2(C14H10N4)2] or [Ag2(NO3)2(μ-PPTA)2] (2), were prepared and characterized by elemental analysis, FT–IR spectroscopy and single-crystal X-ray diffraction. The X-ray structure analysis of 1 revealed a copper complex with square-pyramdial geometry containing two O-donor nitrate ligands along with an N,N′-donor PPTA ligand and one O-donor ethanol ligand. In the binuclear structure of 2, formed by the bridging of two PPTA ligands, each Ag atom has an AgN3O environment and square-planar geometry. In addition to the four dative interactions, each Ag atom interacts with two O atoms of two nitrate ligands on adjacent complexes to complete a pseudo-octahedral geometry. Density functional theory (DFT) calculations revealed that the geometry around the Cu and Ag atoms in 1 opt and 2 opt (opt is optimized) for an isolated molecule is the same as the experimental results. In 1, O—H...O hydrogen bonds form R 1 2(4) motifs. In the crystal network of the complexes, in addition to the hydrogen bonds, there are π–π stacking interactions between the aromatic rings (phenyl, pyridine and triazine) of the ligands on adjacent complexes. The ability of the ligand and complexes 1 and 2 to interact with ten selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B-DNA) was investigated by docking studies. The results show that the studied compounds can interact with proteins better than doxorubicin (except for TrxR and Top II).

scholarly journals Structural study of the coordination behavior of a tetradentate NO3-donor amino alcohol ligand toward a CdII:HgII mixture

2017 ◽  
Vol 72 (5) ◽  
pp. 335-340
Author(s):  
Zahra Mardani ◽  
Vali Golsanamlou ◽  
Saba Khodavandegar ◽  
Keyvan Moeini ◽  
Alexandra M.Z. Slawin ◽  
...  
Keyword(s):  
Cadmium Atom ◽  
X Ray Diffraction ◽  
Cadmium Complexes ◽  
X Ray ◽  
H Nmr ◽  
Binuclear Structure ◽  
Coordination Behavior ◽  
Ft Ir ◽  
Structural Database ◽  
Minimum Distortion

AbstractIn this work, the reaction of 2,2′,2″-nitrilotriethanol (NTE) with a 1:1 mixture of CdI2and HgI2is investigated. The complex [Cd(NTE)2][Hg2(μ-I)2I4] was synthesized and identified by elemental analysis, FT-IR,1H NMR spectroscopy and single-crystal X-ray diffraction. The structure of the [HNTE]Cl salt is also presented. In the crystal structure of the complex, the cadmium atom has a CdN2O6environment in a slightly distorted cube geometry. This geometry is one of the rare cube geometries with a minimum distortion among the Cambridge Structural Database structures for cadmium complexes. The anionic moiety has a binuclear structure with the mercury atoms being in tetrahedral environments. In the network of the complex, in addition to O−H · · · I hydrogen bonds, there are I · · · I interactions which lead to ten-membered rings.

scholarly journals Anion–Cation Recognition Pattern, Thermal Stability and DFT-Calculations in the Crystal Structure of H2dap[Cd(HEDTA)(H2O)] Salt (H2dap = H2(N3,N7)-2,6-Diaminopurinium Cation)

Crystals ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 304 ◽  
Author(s):  
Jeannette Carolina Belmont-Sánchez ◽  
Noelia Ruiz-González ◽  
Antonio Frontera ◽  
Antonio Matilla-Hernández ◽  
Alfonso Castiñeiras ◽  
...  
Keyword(s):  
Density Functional ◽  
Amino Group ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Recognition Pattern ◽  
Ft Ir ◽  
Structural Database ◽  
Cation Recognition ◽  
Ft Ir Spectroscopy

The proton transfer between equimolar amounts of [Cd(H2EDTA)(H2O)] and 2,6-diaminopurine (Hdap) yielded crystals of the out-of-sphere metal complex H2(N3,N7)dap[Cd(HEDTA)(H2O)]·H2O (1) that was studied by single-crystal X-ray diffraction, thermogravimetry, FT-IR spectroscopy, density functional theory (DFT) and quantum theory of “atoms-in-molecules” (QTAIM) methods. The crystal was mainly dominated by H-bonds, favored by the observed tautomer of the 2,6-diaminopurinium(1+) cation. Each chelate anion was H-bonded to three neighboring cations; two of them were also connected by a symmetry-related anti-parallel π,π-staking interaction. Our results are in clear contrast with that previously reported for H2(N1,N9)ade [Cu(HEDTA)(H2O)]·2H2O (EGOWIG in Cambridge Structural Database (CSD), Hade = adenine), in which H-bonds and π,π-stacking played relevant roles in the anion–cation interaction and the recognition between two pairs of ions, respectively. Factors contributing in such remarkable differences are discussed on the basis of the additional presence of the exocyclic 2-amino group in 2,6-diaminopurinium(1+) ion.

A Density Functional Theory Study of 3,5-dichlorosalicyliden-p-iminoacetophenone oxime Complexes with Co, Ni, Cu and Zn Metals

2019 ◽  
Vol 41 (5) ◽  
pp. 770-770
Author(s):  
Ali apan Ali apan ◽  
Erdal Canpolat Erdal Canpolat ◽  
Henar Sleman and Niyazi Bulut Henar Sleman and Niyazi Bulut
Keyword(s):  
Metal Complexes ◽  
Density Functional ◽  
Azomethine Nitrogen ◽  
Carboxyl Oxygen Atom ◽  
Tetrahedral Geometry ◽  
Functional Theory ◽  
X Ray ◽  
Mechanical Methods ◽  
Elemental Analyses ◽  
Ft Ir

In this work, new Schiff baz ligand was synthesized by reaction of p-iminoacetophenone oxime with 3,5-dichlorosalicylaldehyde. Metal complexes of Co+2, Ni+2, Cu+2 and Zn+2 acetate metal salts were synthesized with this ligand. The ligand and complexes are characterized in experimental by their elemental analyses, X-ray, 1H-NMR, 13C-NMR, UV-Vis, FT-IR, magnetic susceptibility and thermogravimetric analyses (TGA) and also have been investigated by using quantum mechanical methods. The transition metals are coordinated to the schiff base through the azomethine nitrogen and the carboxyl oxygen atom. Obtained metal complexes were studied the magnetic properties and their geometries were determined. Co+2, Ni+2 and Zn+2 complexes have been found tetrahedral geometry and Cu+2 complex has been found four coordinated geometry.

Dicyclohexylammonium bromoacetate: a low molecular mass organogelator with a one-dimensional secondary ammonium monocarboxylate (SAM) synthon

2015 ◽  
Vol 71 (7) ◽  
pp. 593-597 ◽  
Author(s):  
Tomasz Rojek ◽  
Tadeusz Lis ◽  
Ewa Matczak-Jon
Keyword(s):  
Electron Microscopy ◽  
Scanning Electron Microscopy ◽  
Hydrogen Bond ◽  
Ion Pairs ◽  
Asymmetric Unit ◽  
One Dimensional ◽  
X Ray ◽  
H Nmr ◽  
Ft Ir ◽  
Scanning Electron

The asymmetric unit of the title salt, C12H24N+·C2H2BrO2−, contains a dicyclohexylammonium cation connected to a bromoacetate anion by means of an N—H...O hydrogen bond. In the crystal, the ion pairs assembleviaN—H...O interactions, forming zigzag infinite chains parallel to thecaxis with the (...H—N—H...O—C—O...)nmotif that is considered to be a prerequisite for ensuring gelation properties of secondary ammonium monocarboxylate salts. The title salt was characterized by FT–IR, X-ray powder diffraction (XRPD), TG–DTA and1H NMR spectroscopy in solution. Gelation experiments revealed that dicyclohexylammonium bromoacetate forms molecular gels with dimethylformamide and dimethyl sulfoxide. Scanning electron microscopy (SEM) was used to reveal morphological features of dried gels.

Nontemplate synthesis, characterization and theoretical study of tetraazamacrocycles

2012 ◽  
Vol 23 (1) ◽  
pp. 121-127
Author(s):  
İbrahim Șen ◽  
Cem Burak Yildiz ◽  
Akın Azizoğlu
Keyword(s):  
Density Functional ◽  
Basis Sets ◽  
Frontier Molecular Orbital ◽  
Spectroscopic Techniques ◽  
Functional Theory ◽  
Hartree Fock ◽  
H Nmr ◽  
Ft Ir ◽  
Molecular Electrostatic Potential Maps ◽  
C Nmr

Abstract The syntheses of new tetraaza macrocyclic compounds of variable ring sizes by non-template methods and their characterization with the help of elemental analysis and spectroscopic techniques (FT-IR, 1H-NMR, and 13C-NMR) have been reported in detail. The vibrational frequencies determined experimentally are compared with those obtained theoretically from density functional theory (DFT) and Hartree-Fock (HF) calculations. The comparisons between the experimental and theoretical results indicate that B3LYP level with both the 3-21G(d) and 6-31G+(d,p) basis sets is able to provide satisfactory results for predicting IR properties. The frontier molecular orbital diagrams and molecular electrostatic potential maps of title compounds have been also calculated and visualized at the B3LYP/6-31G+(d,p) level of theory.

Organometallic pyrene-containing porphyrins: Synthesis, characterization, and non-covalent interactions with C60 fullerenes

2016 ◽  
Vol 20 (08n11) ◽  
pp. 1098-1113 ◽  
Author(s):  
Yang Li ◽  
Hannah M. Rhoda ◽  
Anthony M. Wertish ◽  
Victor N. Nemykin
Keyword(s):  
Excited States ◽  
Electronic Structures ◽  
Density Functional ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
C60 Fullerenes

A reaction between 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and 1-bromopyrene resulted in the formation of 5,10,15,20-tetra[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (1), while cross-condensation between 4-(4-(pyrenyl-1)butoxy)benzaldehyde, ferrocenecaboxaldehyde, and pyrrole resulted in the formation of 5-ferrocenyl-10,15,20-tri[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (2), 5,10-diferrocenyl-15,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (3), and 5,15-diferrocenyl-10,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (4). All pyrene-containing porphyrins were characterized by 1H NMR, UV-vis, MCD, and high-resolution ESI methods, while their electronic structures and the nature of the excited states were elucidated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The molecular structure of 1 and its fluorescence quenching upon the addition of C[Formula: see text] fullerene was also investigated using X-ray crystallography and steady-state fluorescence approaches.

scholarly journals Electrochromic 2,5-Dihydroxyterephthalic Acid Linker in Metal-Organic Frameworks

2021 ◽  
Author(s):  
Hidetsugu Shiozawa ◽  
Zuzana Melnikova ◽  
Zdeněk Bastl ◽  
Herwig Peterlik ◽  
Martin Kalbac ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Cations ◽  
Density Functional Theory Calculations ◽  
Photoemission Spectroscopy ◽  
Electrochromic Devices ◽  
Functional Theory ◽  
One Dimensional ◽  
X Ray ◽  
Metal Organic ◽  
Excellent Adhesion

We report electrochromism of M-MOF-74 (M=Mg, Mn, Co or Zn), a honeycomb nano-framework in which hexagonally packed one-dimensional<br>arrays of metal cations are coordinated with 2,5-Dihydroxyterephthalic acid linker. Raman spectroscopy upon electrochemical doping combined with density functional theory calculations reveals redox reactions of the linker while the metal cations stay divalent as<br>probed by X-ray photoemission spectroscopy. Excellent adhesion of the MOFs to glass allows synthesis of quality thin films to be implemented into electrochromic devices that exhibit promising colour contrast and durability.

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