Application of periodic density functional theory calculations for exploring copper(II) coordination effects on the mesophase behavior of p-n-alkoxybenzoic acids

Copper(II) benzoates ([Formula: see text]OBA-Cu) with various terminal alkoxy carbon numbers, [Formula: see text]–12, were prepared from [Formula: see text]-[Formula: see text]-alkoxy benzoic acids (nOBAs). Fourier transform infrared (IR) experiments suggested that dimerization through copper(II) chelating bidentate coordination created [Formula: see text]OBA-Cu with a linear rod-like structure, similar to the hydrogen-bonded structure of its parent [Formula: see text]OBA. However, the coordination structure of [Formula: see text]OBA-Cu changed during heating. Periodic density functional theory calculations provided valuable insight into the possible arrangement of the parent and copper(II)-coordinated [Formula: see text]OBAs. The formation of binuclear complexes between two adjacent [Formula: see text]OBA-Cu dimers forced [Formula: see text]OBA-Cu to arrange itself in a layer and exhibit smectic A mesophase. Accordingly, four types of IR stretching absorption of benzoyl carbonyl were observed in binuclear [Formula: see text]OBA-Cu complexes, replacing the original symmetric and asymmetric vibrations of benzoyl carboxylate in chelating bidentate coordination. The lateral association by [Formula: see text]–[Formula: see text] interactions between adjacent parent [Formula: see text]OBA dimers preferred a progressive smectic C arrangement. The origin of the odd–even effect was understood from the consideration of the molecular structure.

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Behavior of Si Interstitials and Boron-Interstitial Pairs at the Si/SiO2 Interface

MRS Proceedings ◽

10.1557/proc-810-c8.5 ◽

2004 ◽

Vol 810 ◽

Author(s):

Taras A. Kirichenko ◽

Decai Yu ◽

Sanjay K. Banerjee ◽

Gyeong S. Hwang

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Valuable Insight ◽

Generalized Gradient ◽

Functional Theory ◽

Diffusion Behavior ◽

Generalized Gradient Approximation ◽

And Diffusion ◽

Insight Into

ABSTRACTUsing density functional theory calculations within the generalized gradient approximation, we have investigated the structure, energetics, bonding, and diffusion behavior of Si interstitials and boron-interstitial pairs at the Si/SiO2 interface. We find that interstitials are significantly stabilized at the Si/SiO2 interface and prefer to reside on the SiO2 side rather than the Si side. Due to the interstitial stabilization, boron-interstitial pairs are likely to be easily dissociated in the vicinity of the Si/SiO2 interface. This study provides valuable insight into interstitial annihilation and boron precipitation at the interface.

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Mechanistic Insight into Construction of Axially Chiral Biaryls via Palladium/Chiral Norbornene Cooperative Catalysis: a DFT-Based Computational Study

Catalysis Science & Technology ◽

10.1039/d1cy01863a ◽

2021 ◽

Author(s):

Xuexiang Ma ◽

Aili Feng ◽

Chengbu Liu ◽

Dongju Zhang

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Computational Study ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Cooperative Catalysis ◽

Mechanistic Insight ◽

Aryl Bromides ◽

Axially Chiral ◽

Insight Into

Density functional theory calculations were performed on a prototype of three-component reactions involving aryl iodides, 2,6-substituted aryl bromides, and acrylates to understand the construction of axially chiral biaryls through the...

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Insight into carbon formation from acetic acid decomposition over Pd(100) via density functional theory calculations

Surface Science ◽

10.1016/j.susc.2017.07.002 ◽

2017 ◽

Vol 664 ◽

pp. 226-232 ◽

Cited By ~ 1

Author(s):

Yingzhe Yu ◽

Xuanyu Sun ◽

Minhua Zhang

Keyword(s):

Density Functional Theory ◽

Acetic Acid ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Carbon Formation ◽

Acid Decomposition ◽

Functional Theory ◽

Insight Into

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On the dissolution of lithium sulfate in water: anion photoelectron spectroscopy and density functional theory calculations

Physical Chemistry Chemical Physics ◽

10.1039/c4cp05698a ◽

2015 ◽

Vol 17 (8) ◽

pp. 5624-5631 ◽

Cited By ~ 9

Author(s):

Gang Feng ◽

Gao-Lei Hou ◽

Hong-Guang Xu ◽

Zhen Zeng ◽

Wei-Jun Zheng

Keyword(s):

Density Functional Theory ◽

Dft Calculations ◽

Photoelectron Spectroscopy ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Lithium Sulfate ◽

Functional Theory ◽

Anion Photoelectron Spectroscopy ◽

Insight Into

Microscopic insight into the dissolution of Li2SO4in water was gained using photoelectron spectroscopy combined with DFT calculations.

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Substituent effects in the decarboxylation reactions of coordinated arylcarboxylates in dinuclear copper complexes, [(napy)Cu2(O2CC6H4X)]+

European Journal of Mass Spectrometry ◽

10.1177/1469066717729067 ◽

2017 ◽

Vol 23 (6) ◽

pp. 351-358 ◽

Cited By ~ 5

Author(s):

Qiuyan Jin ◽

Jiaye Li ◽

Alireza Ariafard ◽

Allan J Canty ◽

Richard AJ O’Hair

Keyword(s):

Density Functional Theory ◽

Transition State ◽

Density Functional ◽

Copper Complexes ◽

Substituent Effects ◽

Density Functional Theory Calculations ◽

Molecular Formula ◽

Binuclear Complexes ◽

Aryl Group ◽

Functional Theory

A combination of gas-phase ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the role of substituents on the decarboxylation of 25 different coordinated aromatic carboxylates in binuclear complexes, [(napy)Cu2(O2CC6H4X)]+, where napy is the ligand 1,8-naphthyridine (molecular formula, C8H6N2) and X = H and the ortho ( o), meta ( m) and para ( p) isomers of F, Br, CN, NO2, CF3, OAc, Me and MeO. Two competing unimolecular reaction pathways were found: decarboxylation to give the organometallic cation [(napy)Cu2(C6H4X)]+ or loss of the neutral copper benzoate to yield [(napy)Cu]+. The substituents on the aryl group influence the branching ratios of these product channels, but decarboxylation is always the dominant pathway. Density functional theory calculations reveal that decarboxylation proceeds via two transition states. The first enables a change in the coordination mode of the coordinated benzoate in [(napy)Cu2(O2CC6H4X)]+ from the thermodynamically favoured O, O-bridged form to the O-bound form, which is the reactive conformation for the second transition state which involves extrusion of CO2 with concomitant formation of the CO2 coordinated organometallic cation, [(napy)Cu2(C6H4X)(CO2)]+, which then loses CO2 in the final step to yield [(napy)Cu2(C6H4X)]+. In all cases the barrier is highest for the second transition state. The o-substituted benzoates show a lower activation energy than the m-substituted ones, while the p-substituted ones have the highest energy, which is consistent with the experimentally determined normalised collision energy required to induce fragmentation of [(napy)Cu2(O2CC6H4X)]+.

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A Density Functional Theory Investigation of the Reaction of Water with Ce2O-

10.26434/chemrxiv.13041710.v3 ◽

2021 ◽

Author(s):

Hassan Harb ◽

Hrant Hratchian

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Hydrogen Formation ◽

Functional Theory ◽

Insight Into

Cerium suboxide clusters are a recent catalyst class that has received interest for the generation of H2 from water. Using density functional theory calculations, this work examines the reaction of Ce2O– clusters with H2O. It is shown that the reaction can proceed along both doublet and quartet pathways. In both cases, hydrogen formation is facilitated by intermediate structures featuring bridging hydride and hydroxide ligands. Interestingly, it is shown that metal d electrons facilitate the reduction of water. This work provides new understanding of this reaction and provides new insight into the reactivity of small lanthanide-based clusters with water.

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Insight into the Crystalline Structure of ThF4 with the Combined Use of Neutron Diffraction, 19F Magic-Angle Spinning-NMR, and Density Functional Theory Calculations

Inorganic Chemistry ◽

10.1021/acs.inorgchem.8b02683 ◽

2018 ◽

Vol 57 (24) ◽

pp. 15350-15360 ◽

Cited By ~ 2

Author(s):

Laura Martel ◽

Elisa Capelli ◽

Monique Body ◽

Marco Klipfel ◽

Ondrej Beneš ◽

...

Keyword(s):

Density Functional Theory ◽

Neutron Diffraction ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Magic Angle Spinning ◽

Magic Angle ◽

Functional Theory ◽

Combined Use ◽

Angle Spinning ◽

Insight Into

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DFT insight into axial ligand effects on electronic structure and mechanistic reactivity of oxoiron(iv) porphyrin

Physical Chemistry Chemical Physics ◽

10.1039/d0cp01867h ◽

2020 ◽

Vol 22 (21) ◽

pp. 12173-12179

Author(s):

Zhifeng Ma ◽

Naoki Nakatani ◽

Hiroshi Fujii ◽

Masahiko Hada

Keyword(s):

Density Functional Theory ◽

Electronic Structure ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Axial Ligand ◽

Functional Theory ◽

Ligand Effects ◽

Insight Into

The nature of axial ligand effects is revealed by density functional theory calculations, the ability of axial ligand bound to iron is strong, and the reaction is more reactive.

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