DFT studies for three Cu(II) coordination polymers: Geometrical and electronic structures, g factors and UV–visible spectra

Ding, Chang‐Chun; Wu, Shao-Yi; Xu, Ya‐Qiong; Wu, Luyi; Zhang, Lijuan

doi:10.1016/j.chemphys.2018.04.016

Cited by 13 publications

(3 citation statements)

References 26 publications

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“…EPR has been shown to be an efficient and reliable tool to reveal the local structures of transition metals in their paramagnetic compounds. The EPR spectra of triplet Cp 3 Co 3 (CO) n ( n = 3, 2, 1, 0) and doublet and quartet Cp 3 Ni 3 (CO) n ( n = 3, 2, 1, 0) have been simulated by ORCA , and EasySpin programs based on the optimized structures (Figure ). The shapes of the simulated EPR spectra and the positions of resonant magnetic fields are quite close to each other except for Ni3-1D .…”

Section: Resultsmentioning

confidence: 99%

Unraveling the Major Differences between the Trinuclear Cyclopentadienylmetal Carbonyl Chemistry of Cobalt and That of Nickel─A Theoretical Study

2023

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The geometries and energetics of the trinuclear cyclopentadienylmetal carbonyls Cp 3 M 3 (CO) n (Cp = η 5 -C 5 H 5 ); M = Co, Ni; n = 3, 2, 1, 0) have been investigated by density functional theory. The cobalt and nickel systems are found to be rather different owing to the different electronic configurations of the metal atoms. For cobalt, the small calculated energy separation of 5.0 kcal/mol between the two lowest-energy singlet Cp 3 Co 3 (μ 3 -CO)(μ-CO) 2 and Cp 3 Co 3 (μ-CO) 3 tricarbonyl structures accounts for the experimental results of both isomers as stable species that can be isolated and structurally characterized by X-ray crystallography. The corresponding Cp 3 Ni 3 (CO) 3 species in the nickel system are predicted not to be viable owing to exothermic CO dissociation to give the experimentally observed very stable Cp 3 Ni 3 (μ-CO) 2 , which is found to be the lowest-energy isomer by a substantial margin of ∼25 kcal/mol. In all of the low-energy Cp 3 M 3 (CO) n (n = 2, 1) structures, including that of the experimentally known triplet spin state Cp 3 Co 3 (μ 3 -CO) 2 , all of the carbonyl groups are face-bridging or face-semi-bridging μ 3 -CO groups bonded to all three metal atoms of the M 3 triangle. In the lowest-energy carbonyl-free Cp 3 M 3 (M = Co, Ni) structures, agostic C−H−M interactions are found using hydrogens of the Cp rings. In addition, the lowest-energy Cp 3 Ni 3 is the only structure among all of the low-energy Cp 3 M 3 (CO) n (M = Co, Ni; n = 3, 2, 1, 0) structures in which each Cp ring is a bridging rather than terminal ligand.

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Section: Resultsmentioning

confidence: 99%

Unraveling the Major Differences between the Trinuclear Cyclopentadienylmetal Carbonyl Chemistry of Cobalt and That of Nickel─A Theoretical Study

2023

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“…The DFT/B3LYP technique was used. The standard basis sets were 6311G and LANL2DZ concerning the synthesized H 2 L and its metal complexes, respectively ( Ammar et al, 2014 ; Maurya et al, 2015 ; Ding et al, 2018 ; Abdalrazaq et al, 2022 ; Aly et al, 2022b ; Mahani and Mohammadi, 2022 ; Ugurlu and Harmankaya, 2022 ). The topoisomerase IIa was simulated using MOE 2009 (Molecular Operating Environment) software.…”

Section: Experimental Methodsmentioning

confidence: 99%

Synthesis, characterization, PXRD studies, and theoretical calculation of the effect of gamma irradiation and antimicrobial studies on novel Pd(II), Cu(II), and Cu(I) complexes

Hassan,

Aly,

Al-Sulami

et al. 2024

Front. Chem.

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The main objective of this study is to synthesize and characterize of a new three complexes of Pd (II), Cu (II), and Cu (I) metal ions with novel ligand ((Z)-2-(phenylamino)-N'-(thiophen-2-ylmethylene)acetohydrazide) H2LB. The structural composition of new compounds was assessed using several analytical techniques including FT-IR, 1H-NMR, electronic spectra, powder X-ray diffraction, and thermal behavior analysis. The Gaussian09 program employed the Density Functional Theory (DFT) approach to optimize the geometry of all synthesized compounds, therefore obtaining the most favorable structures and crucial parameters. An investigation was conducted to examine the impact of γ-irradiation on ligands and complexes. Before and after γ-irradiation, the antimicrobial efficiency was investigated for the activity of ligands and their chelates. The Cu(I) complex demonstrated enhanced antibacterial activity after irradiation, as well as other standard medications such as ampicillin and gentamicin. Similarly, the Cu(I) complex exhibited superior activity against antifungal species relative to the standard drug Nystatin. The docking investigation utilized the target location of the topoisomerase enzyme (2xct) chain A.

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“…3). From the adsorption energies ÁH (' À185.7, À180.2, 449.2 and 513.9 kcal mol À1 ; 1 kcal mol À1 = 4.184 kJ mol À1 ) for PCN-224Co 2+ interacting with molecular CO (N = 12) at 12, 75, 150 and 195 K, the increasing ÁH, which even has an opposite (positive) sign, reveals the unfavorable adsorption at relatively higher temperatures (Supronowicz et al, 2013;Ding et al, 2018).…”

Section: Adsorption Energymentioning

confidence: 99%

Investigations of the temperature-dependent electron paramagnetic resonance spectra and local structures for a cobalt(II) porphyrin complex within a metal–organic framework

Ding

Fan

2019

Acta Crystallogr Sect B

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The interaction between an adsorbed CO molecule and the unsaturated coordinated Co 2+ center in the metal-organic framework (MOF) PCN-224 is investigated by analyzing the electron paramagnetic resonance (EPR) parameters (g factors and hyperfine structure constants) and the adsorption energies at various temperatures. Six-and five-coordinated octahedral models (four planar N with two and one axial CO molecules, respectively) are constructed to simulate the local structures of the Co 2+ centers at different temperatures. Because of the Jahn-Teller effect of the Co 2+ centers, the C 2 -Co-N 4 and C-Co-N 4 combinations undergo different tetragonal elongation distortions along the C 4 axis, characterized by the relative elongation ÁZ and displacement ÁZ 0 of Co 2+ at different temperatures. Given the agreement between the calculated and experimental EPR parameters, as well as the adsorption properties, the six-and five-coordinated models are regarded as suitable for low-and high-temperature systems, respectively. These studies may be helpful to understand the properties of similar MOFs with adsorbed molecules under the effect of ambient temperature.

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DFT studies for three Cu(II) coordination polymers: Geometrical and electronic structures, g factors and UV–visible spectra

Cited by 13 publications

References 26 publications

Unraveling the Major Differences between the Trinuclear Cyclopentadienylmetal Carbonyl Chemistry of Cobalt and That of Nickel─A Theoretical Study

Unraveling the Major Differences between the Trinuclear Cyclopentadienylmetal Carbonyl Chemistry of Cobalt and That of Nickel─A Theoretical Study

Synthesis, characterization, PXRD studies, and theoretical calculation of the effect of gamma irradiation and antimicrobial studies on novel Pd(II), Cu(II), and Cu(I) complexes

Investigations of the temperature-dependent electron paramagnetic resonance spectra and local structures for a cobalt(II) porphyrin complex within a metal–organic framework

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