Synthesis, crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa=hexafluoroacetylacetonate, Phen=o-phenanthroline)

Rogachev, Andrey Yu.; Миначева, Л. Х.; Сергиенко, В. С.; Малкерова, И. П.; Alikhanyan, A. S.; Stryapan, V.V.; Kuzmina, Natalia

doi:10.1016/j.poly.2004.06.006

Cited by 30 publications

(9 citation statements)

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“…The Ln(dik) 3 -Phen bonding energy obtained at the DFT/B3PW91 level agrees well with the experimental mass-spectrometry data [36,37].…”

Section: Discussionsupporting

confidence: 81%

“…These values can be used to estimate the thermodynamic stability of compounds of such type, which turns out to be fairly low. The findings are consistent with a tendency of mixed-ligand molecules to dissociate to parent species in the gas phase [36,37]. Low bonding energies are in agreement with the experimentally determined energies of the gas-phase dissociation of complexes studied in mass-spectrometry experiments [36,37].…”

Section: ␤-Diketonate-based Lanthanidesupporting

confidence: 86%

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QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

Nemukhin¹,

Rogachev²,

Konyukhov³

et al. 2005

Int J of Quantum Chemistry

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ABSTRACT:The structure and properties of the lanthanum and lutetium ␤-diketonates and mixed Ln(dik) 3 ligand complexes with o-phenantroline, Ln(dik) 3 Phen, are modeled by using the quantum mechanical/molecular mechanical (QM/MM) technique with the universal force fields (UFF) in the MM part. The set of parameters for UFF was adjusted to obtain the adequate modeling of the structures. The LnOO and Ln(dik) 3 OPhen bond energies were estimated by using the single-point calculations with Becke's three-parameter functional with Perdew-Wang correlational functional density functional theory. It is shown that the LnOO and Ln(dik) 3 OPhen bond energies are decreasing in the series from nonbulky ␤-diketonate ligands to their branched analogs. The introduction of the fluorinated substituents leads to substantial increase in bond energy. The natural bond orbital analysis was used for characterization of electronic structure of the complexes.

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“…The Ln(dik) 3 -Phen bonding energy obtained at the DFT/B3PW91 level agrees well with the experimental mass-spectrometry data [36,37].…”

Section: Discussionsupporting

confidence: 81%

Section: ␤-Diketonate-based Lanthanidesupporting

confidence: 86%

QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

Nemukhin¹,

Rogachev²,

Konyukhov³

et al. 2005

Int J of Quantum Chemistry

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“…The mean average of all La-O bond lengths is 2.476 Å . The La-N distances are with 2.699 (3) and 2.700 (3) Å (mean value 2.693 Å ) shorter than those previously obtained for a 1,10-phenanthrolinate lanthanum (III) complex with hexafluoroacetylacetonate (2.747-2.782 Å ; Rogachev et al, 2005) and longer than La-N bonds in a carbacylamidophosphate ligand complex (2.601-2.635 Å ; Litsis et al, 2015;Sokolnicki et al, 1999).…”

Section: Structural Commentarymentioning

confidence: 53%

Tris(N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)lanthanum(III)

et al. 2017

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2 )] is created by one La III ion, three deprotonated N-{bis[methyl(phenyl)amino]phosphoryl}benzene-sulfonamidate (L À ) ligands and one 1,10-phenanthroline (Phen) molecule. Each La III ion is eight-coordinated (6O+2N) by three phosphoryl O atoms, three sulfonyl O atoms of three L À ligands and two N atoms of the chelating Phen ligand, leading to the formation of six-and five-membered metallacycles, respectively. The lanthanum coordination polyhedron has a bicapped trigonalprismatic geometry. 'Sandwich-like' intramolecular -stacking interactions are observed between the 1,10-phenanthroline ligand and two benzene rings of two different L À ligands. The phenyl rings of L À that are not involved in the stacking interactions show minor positional disorder. Molecules form layers parallel to the (010) plane due to weak C-HÁ Á ÁO intermolecular hydrogen bonds. Unidentified highly disordered solvate molecules that occupy ca 400 Å 3 large voids have been omitted from the refinement model. Chemical context-Diketone derivatives have been the topic of investigations in many different branches of the chemical science, such as organic, coordination, bio-and theoretical chemistry. Of special interest have been carbacylamidophosphates (CAPh), containing the functional fragment C(O)NHP(O), because of their properties as extractants (Morgalyuk et al., 2005;Safiulina et al., 2015), urease inhibitors (Jaroslav & Swerdloff, 1985), enzyme inhibitors (Grimes et al., 2008;Adams et al., 2002), their antibacterial properties (Oroujzadeh et al., 2017) and anticancer activity (Kovalchyk et al., 1991;Amirkhanov et al., 1995). The presence of the phosphoryl group gives them a high affinity towards highly charged metal ions, and these types of compounds are used in the coordination chemistry of lanthanides and actinides (Litsis et al., 2010(Litsis et al., , 2017Kariaka et al., 2013). Many efforts have been devoted to the synthesis of another type of structural analogs of -diketones -sulfonylamidophosphates (SAPh) with the structural fragment S(O) 2 NHP(O). These types of compounds were first synthesized by Kirsanov (Kirsanov & Shevchenko, 1954) and some have since been used as bactericidal agents in medicine and toxicology (Xu & Angell, 2000), while others have found use as pesticides (Kishino & Saito, 1979). In addition, these compounds are potentially bidentate O,O-donor chelating ISSN 2056-9890 ligands for metal ions, similar to other deprotonated phosphorylic ligand derivatives (Znovjyak et al., 2015;Amirkhanov et al., 2014;Litsis et al., 2016;Shatrava et al., 2016a). For details of the coordination chemistry of phosphorylic ligands in molecular form, see Gholivand et al. (2012Gholivand et al. ( , 2014, Yizhak et al. (2013) and Shatrava et al. (2016b).Recently, we reported the preparation and study of the coordination properties of several representatives of sulfonylamidophosphates:methyl ( Knowledge of the crystal structure is an essential part of understanding the luminescent properties of these types of lanthanide complexes. In this...

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“…Due to their high charge transfer mobility, bright light emission and good electro and photo active properties they provide potential for various technological applications (Brechin et al, 2000;Rogachev et al, 2005). They also play important roles in supramolecular assemblies, metallo-dendrimers and formation of stable complexes (Sigman, 1990;Lehn et al, 1995;Binnemans et al, 2004;Lenaerts et al, 2005).…”

Section: Introductionmentioning

confidence: 99%

Syntheses, spectral characterization, thermal properties and DNA cleavage studies of a series of Co(II), Ni(II) and Cu(II) polypyridine complexes with some new imidazole derivatives of 1,10-phenanthroline

Ahmed

Khaled

2019

Arabian Journal of Chemistry

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Please cite this article as: S.K. Ahmed, S. Khaled, Syntheses, spectral characterization, thermal properties and DNA cleavage studies of a series of Co(II), Ni(II) and Cu(II) polypyridine complexes with some new imidazole derivatives of 1,10-phenanthroline, Arabian Journal of Chemistry (2015), doi: http://dx. AbstractIn the present study three new imidazole derivatives of phen, 2-(4-hydroxy-3,5-diiodophenyl) imidazo[4,5-f][1,10]phenathroline L 1 , 2-(2-hydroxy-3,5-diiodophenyl)imidazo[4,5-f][1,10]phenanthroline L 2 , 2-(4-hydroxy-5-iodo-3-methoxyphenyl)imidazo[4,5-f][1,10]phenanthroline L 3 and their nine new polypyridine complexes[M(N-N) 2 (L 1-3 )](OAc) 2 .(nH 2 O) where M is Ni(II), Co(II) and Cu(II) and where (N-N) 2 is 2,2'-bipyridine (bpy) 2 or 1,10-phenanthroline (phen) 2 have been synthesized from the reaction of the metal precursor complexes [M(phen) 2 (OAc) 2 ].(nH 2 O) and [M(bpy) 2 (OAc) 2 ].(nH 2 O) with the respective ligands in ethanol and water. The structures of the compounds were determined with the aid of elemental analysis and FT-IR, UV-Vis., 1 H NMR, ESR spectroscopic methods, magnetic measurements and conductance measurements, further analyzed by powder XRD and thermal studies. Elemental analysis data suggested that the complexes have a 1:2:1 molar ratio among the metal and phen or bpy and L 1 / L 2 or L 3 ligands. The spectral data show that all the complexes were six coordinated and possess octahedral geometry around the metal ions. The X-band ESR spectrum of the Cu(II) in DMSO solution at room temperature were recorded and observed anisotropic g values indicate the presence of metal ion in an octahedral environment. The powder XRD patterns of complexes recorded in the range (2θ = 0-80°) and average crystallite size (d XRD ) was calculated using Scherrer's formula. Thermal decomposition profiles of complexes show high decompound temperatures indicating a good thermal stability. Binding of the complexes with calf thymus DNA (CT DNA) has been investigated by gel electrophoresis. The experimental results indicate that the complexes bind to DNA by intercalation mode and found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation.

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Synthesis, crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa=hexafluoroacetylacetonate, Phen=o-phenanthroline)

Cited by 30 publications

References 12 publications

QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

Tris(N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)lanthanum(III)

Syntheses, spectral characterization, thermal properties and DNA cleavage studies of a series of Co(II), Ni(II) and Cu(II) polypyridine complexes with some new imidazole derivatives of 1,10-phenanthroline

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Synthesis, crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa=hexafluoroacetylacetonate, Phen=o-phenanthroline)

Cited by 30 publications

References 12 publications

QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

QM/MM modeling of the structures and properties of the β‐diketonate–based lanthanide complexes

Tris(N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidato-κ2O,O′)(1,10-phenanthroline-κ2N,N′)lanthanum(III)

Syntheses, spectral characterization, thermal properties and DNA cleavage studies of a series of Co(II), Ni(II) and Cu(II) polypyridine complexes with some new imidazole derivatives of 1,10-phenanthroline

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Tris(N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)lanthanum(III)