Assessing Density Functional Theory Approaches for Predicting the Structure and Relative Energy of Salicylideneaniline Molecular Switches in the Solid State

Quertinmont, Jean; Carletta, Andrea; Tumanov, Nikolay; Leyssens, Tom; Champagne, Benoı̂t

doi:10.1021/acs.jpcc.7b00580

Cited by 26 publications

(31 citation statements)

References 55 publications

(73 reference statements)

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“…In [9], Ruggiero and co-workers assessed the reliability of a range of XCFs for the optimization of three pyridine carboxylic acid crystals and they highlighted the performances of ωB97X [11]. In [10], we showed the effectiveness of three XCFs (HSEsol [12], PBEsol0, and ωB97X [11]) in optimizing the molecular and crystal structures of three salicylideneanilines. Still, with respect to the XCFs used so far, a more precise description of the solid state can be obtained by modifications to the DFT energy by adding London dispersion interactions (Equation (1)) in the form of empirical terms as proposed by Grimme [13].…”

Section: Introductionmentioning

confidence: 88%

“…In particular, accurate description of the intramolecular parameters (defined by the fractional coordinates of the asymmetric unit) and the intermolecular ones (defined by the unit cell parameters) is required as a starting point for the prediction and study of their properties. Density functional theory (DFT) was recently shown to be an efficient tool granted that the appropriate exchange-correlation functional (XCF) is used [9,10]. In [9], Ruggiero and co-workers assessed the reliability of a range of XCFs for the optimization of 2 of 8 three pyridine carboxylic acid crystals and they highlighted the performances of ωB97X [11].…”

Section: Introductionmentioning

confidence: 99%

“…This compound is in fact a molecular switch that can commute between an enol (E) and a keto (K) form, allowing in parallel to evaluate the effect on the relative energy of these two forms. The theoretical structures obtained with DFT-D2 and DFT-D* XCFs are compared to X-ray diffraction (XRD) data as well as to those results obtained with more traditional DFT functionals [10]. This paper is organized as follows: Section 2 summarizes the key computational aspects (additional details can be found in [10]), whereas Section 3 presents and discusses the results before conclusions are drawn in Section 4.…”

Section: Introductionmentioning

confidence: 99%

“…to be an efficient tool granted that the appropriate exchange-correlation functional (XCF) is used [9,10]. In [9], Ruggiero and co-workers assessed the reliability of a range of XCFs for the optimization of three pyridine carboxylic acid crystals and they highlighted the performances of ωB97X [11].…”

Section: Introductionmentioning

confidence: 99%

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Effects of Empirical Dispersion Energy on the Geometrical Parameters and Relative Energy of a Salicylideneaniline Molecular Switch in the Solid State

2018

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The geometries of the enol (E) and keto (K) forms of a crystalline salicylideneaniline molecular switch, (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3), have been determined using periodic density functional theory (DFT) calculations with a variety of exchange-correlation functionals (XCFs). They are compared to X-ray diffraction (XRD) data as well as to geometries obtained using empirical dispersion energy in the form of the second iteration of Grimme's scheme, either with its original parameters (DFT-D2) or with parameters revised for the solid state (DFT-D*). Using DFT, a good agreement with experiment on the unit cell parameters is obtained with the PBEsol, PBEsol0, and ωB97X XCFs. DFT-D2 contracts the unit cell too much with all considered XCFs, whereas DFT-D* lessens this effect thus allowing B3LYP, PBE, and PBE0 to achieve reasonable agreement with respect to XRD data. When considering molecular geometries, both DFT and DFT-D* have a similar effect on the bond lengths, both systematically underestimating (overestimating) the length of the single (double) bonds (within 0.003 Å), as well as on valence angles attaining differences of 2 • with respect to XRD data. The errors on the torsion angles are less spread out with DFT-D* (averaging 1 •) than DFT for which only PBEsol, PBEsol0, and ωB97X perform well. Finally, the relative keto-enol energies, ∆E KE , have been calculated, showing that the inclusion of dispersion energy stabilizes the keto form more than it does the enol form. This results in the PBE and PBEsol XCFs wrongly predicting the keto form as the most stable form.

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Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effects of Empirical Dispersion Energy on the Geometrical Parameters and Relative Energy of a Salicylideneaniline Molecular Switch in the Solid State

2018

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“…Based on the previous research, [62][63][64][65][66] we next investigated the redox properties of the complexes. We selected the complex 1 as the representative of the complexes.…”

Section: Electrochemistrymentioning

confidence: 99%

Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Peng

Liu

Han

et al. 2019

Applied Organom Chemis

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A series of neutral binuclear iridium and rhodium complexes were synthesized based on bis‐imine ligands under mild conditions. These half‐sandwich late transition metal complexes were isolated in good yields and characterized by elemental analysis, 1H NMR, 13C NMR, HR‐MS, and FT‐IR spectroscopies, and the solid state structure of complexes 1 and 2 were further confirmed by single‐crystal X‐ray diffraction. Cyclic voltammetry (CV) characterization indicated that the complex 1 has the best catalyst for water oxidation process with TOF of 0.8 s−1 at low overpotential of 0.325 V in methanol‐phosphate buffer. The proposed double‐site water oxidation mechanism had been also speculated.

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Periodic DFT Study of the Effects of Co‐Crystallization on a N‐Salicylideneaniline Molecular Switch

et al. 2019

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This work aims at better understanding the complex effects of co‐crystallization on a single salicylideneaniline molecular switch, (E)‐2‐methoxy‐6‐(pyridine‐3‐yliminomethyl)phenol (PYV3), which can tautomerize between an enol and a keto form. A combination of periodic boundary conditions DFT and molecular wavefunction calculations has been adopted for examining a selection of PYV3 co‐crystals, presenting hydrogen bonds (H‐bonds) or halogen bonds (X‐bonds), for which X‐ray diffraction data are available. Three aspects are targeted: i) the energy (H‐bond strength, enol to keto relative energy, and geometry relaxation energies), ii) the geometrical structure (PYV3 to co‐crystal and enol to keto geometrical variations), and iii) the electron distribution (PYV3 to co‐crystal and enol to keto Mulliken charge variations). These allow i) explaining the preference for forming H‐bonds with the nitrogen of the pyridine of PYV3 with respect to the oxygens and the importance of the crystal field, ii) distinguishing the peculiar behavior of the SulfonylDiPhenol (SDP) coformer, which stabilizes the keto form of PYV3, iii) describing the relative stabilization of the enol form upon co‐crystallization (with the exception of SDP) and therefore iv) substantiating the co‐crystallization‐induced reduction of thermochromism observed for several PYV3 co‐crystals.

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Assessing Density Functional Theory Approaches for Predicting the Structure and Relative Energy of Salicylideneaniline Molecular Switches in the Solid State

Cited by 26 publications

References 55 publications

Effects of Empirical Dispersion Energy on the Geometrical Parameters and Relative Energy of a Salicylideneaniline Molecular Switch in the Solid State

Effects of Empirical Dispersion Energy on the Geometrical Parameters and Relative Energy of a Salicylideneaniline Molecular Switch in the Solid State

Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Periodic DFT Study of the Effects of Co‐Crystallization on a N‐Salicylideneaniline Molecular Switch

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