Electronic and magnetic properties of the [Ni(salophen)]: An experimental and DFT study

Mendes, Rodrigo A.; Germino, José Carlos; Fazolo, Bruno Rodrigues; Thaines, Ericson H.N.S.; Ferraro, Franklin; Santana, A. M.; Ramos, R.J.; Souza, Gabriel L. C. de; Freitas, Renato G.; Vazquez, Pedro A. M.; Barboza, Cristina A.

doi:10.1016/j.jare.2017.10.004

Cited by 15 publications

(9 citation statements)

References 41 publications

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“…This peak, together with the previously discussed HOMO and LUMO levels, indicates an experimentally determined HOMO–LUMO gap of 3.28 eV and a (HOMO–1)–HOMO gap of 0.36 eV. These UHV single-molecule measurements, in comparison to the recent solution-phase absorption spectroscopy and computation study, provide a more direct and solvent-free determination of frontier MO energy gaps. Because each Ni(salophen) molecule experiences little distortion or interaction with Au(111), we further expect that these STM-determined MO gaps to be readily accounted for using gas-phase free-molecule calculations.…”

supporting

confidence: 64%

“…Because each Ni(salophen) molecule experiences little distortion or interaction with Au(111), we further expect that these STM-determined MO gaps to be readily accounted for using gas-phase free-molecule calculations. In fact, metal(salen) complexes have been intensely investigated computationally, with several reports describing that one computational method is better than the others. ,− Our STM-OMTS measurement thus provides a new foundation to re-examine these computational methods.…”

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confidence: 99%

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Connecting Solution-Phase to Single-Molecule Properties of Ni(Salophen)

Zhang

Chilukuri

Hanson

et al. 2019

J. Phys. Chem. Lett.

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We present a strong correlation of the Ni(salophen) structure and properties measured in single-molecule vs bulk quantities and in ultra high vacuum vs solution phase. Under a scanning tunneling microscope (STM), Ni(salophen) forms a self-assembled monolayer (SAM) on Au(111) at 23 °C with molecular structure identical to that of the X-ray crystallographic measurement. The HOMO and LUMO levels are determined using elastic tunneling spectroscopy at the single-molecule level with confirmation by monolayer-quantity ultraviolet photoelectron spectroscopy (UPS) and by cyclic voltammetry (CV) measurements. The STM-determined HOMO− LUMO gap of 3.28 eV and (HOMO−1)−HOMO gap of 0.36 eV form a new foundation for the selection of hybrid functionals with a simple basis set to be effective in accurately calculating single-molecule Ni(salophen) frontier MO levels. Our results suggest that microscopy-based experiments on a surface, along with free-molecule gas-phase calculations, can provide useful insights into the physical properties of metal(salen) complexes, especially when such direct measurements are not available in solution.Letter pubs.acs.org/JPCL

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confidence: 64%

mentioning

confidence: 99%

Connecting Solution-Phase to Single-Molecule Properties of Ni(Salophen)

Zhang

Chilukuri

Hanson

et al. 2019

J. Phys. Chem. Lett.

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“…The supramolecular attitude of these scaffolds makes them perfect candidates for a series of important applications especially in the field of materials [53,54] and biological studies [55][56][57]. …”

Section: Towards Conclusionmentioning

confidence: 99%

The Supramolecular Attitude of Metal–Salophen and Metal–Salen Complexes

Leoni

Cort

2018

Inorganics

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“…Salophen scaffold is very versatile and different electronic materials and technologies are designed from it, such as catalysts, corrosion inhibitors, data storage components, solar cells and sensors. [12][13][14] Its phenolic rings are easily derivatized with numerous substituents, whereas imine groups are useful for molecular self-assembly on reactive surfaces. 12 Salophens synthesized from renewable feedstocks are particularly interesting as they follow Green Chemistry principles and practices.…”

mentioning

confidence: 99%

“…[12][13][14] Its phenolic rings are easily derivatized with numerous substituents, whereas imine groups are useful for molecular self-assembly on reactive surfaces. 12 Salophens synthesized from renewable feedstocks are particularly interesting as they follow Green Chemistry principles and practices. Recent studies performed with cardanol extracted from cashew nut shell liquid (i.e., a brown viscous residue produced by the cashew processing industry, which contains high concentrations of phenolic lipids), for example, have revealed its great potential to synthesize new salophens.…”

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confidence: 99%

Cardanol-Based Salophen-Modified Electrode for Analysing Nitric Oxide Bioavailability under Nitrosative Stress Conditions

Reis¹,

Santos²,

Souza³

et al. 2022

J. Electrochem. Soc.

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High levels of nitric oxide (NO) can signal nitrosative stress, but its analysis is challenging considering the high reactivity, short half-life and transient behavior of this target molecule in biological milieu. In this work, a cardanol-based salophen-modified carbon paste electrode (CDN-salophen/MCPE) was developed and successfully applied to assess NO bioavailability in blood plasma of mice under induced stress. The results revealed that the modifier improved the device performance in terms of signal-to-noise ratio, charge-transport and fouling resistance. NO reactivity on CDN-salophen/MCPE was higher in 0.1 mol L‒1 H2SO4, and the resulting redox process involves adsorption steps that control the reaction kinetics. Monitoring molecule oxidation by square-wave voltammetry (100 s−1 frequency, 30 mV amplitude, 2 mV scan increment, after electrode preconditioning at 0.9 V for 15 s for analyte accumulation), it was possible to identify and quantify NO with great sensitivity (detection and quantification limit < 0.1 µmol L‒1) and low data variance (RSD ≤ 9.4% for repeatability and reproducibility tests), through a simple, fast and reliable electroanalytical protocol. The robustness acquired with CDN-salophen/MCPE allowed to detect changes in NO content in blood plasma during nitrosative stress, proving its efficiency for research on this subject.

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Electronic and magnetic properties of the [Ni(salophen)]: An experimental and DFT study

Abstract: Graphical abstract

Cited by 15 publications

References 41 publications

Connecting Solution-Phase to Single-Molecule Properties of Ni(Salophen)

Connecting Solution-Phase to Single-Molecule Properties of Ni(Salophen)

The Supramolecular Attitude of Metal–Salophen and Metal–Salen Complexes

Cardanol-Based Salophen-Modified Electrode for Analysing Nitric Oxide Bioavailability under Nitrosative Stress Conditions

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