Assessing density functional theory approaches for predicting the structure and relative energy of salicylideneaniline molecular switches in the solid state

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Résumé

The geometrical structures of salicylideneaniline (anil) molecular switches in the solid state have been determined using periodic structure calculations and a variety of density functional theory (DFT) exchange-correlation (XC) functionals, of which several have been tuned for the solid state. The first target was on predicting the unit cell and intramolecular geometrical parameters for three anil derivatives, i.e., the (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3) and N-(5-chloro-2-hydroxybenzylidene)-aniline (HC) crystals, where the enol (E) form is dominant in the crystalline state at low temperature (∼100 K), and the N-(5-chloro-2-hydroxybenzylidene)-hydroxyaniline (POC) crystal, which is mostly composed of the keto (K) form. The best performance for the unit cell parameters, in comparison with single-crystal X-ray diffraction (XRD) data, is achieved with XC functionals developed for the solid state (PBEsol and PBEsol0) as well as with ωB97X. On the other hand, the differences between the functionals are much smaller when considering the bond lengths and the valence angles so that the deviations with respect to XRD data in the bond length alternations of the key O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment are smaller than 0.02 Å for PBEsol0 and ωB97X. Similar trends are observed for the two polymorphic cocrystals of PYV3 with fumaric or succinic acid. The second target was the characterization of the variations of energy and structural parameters when switching between the enol and keto forms. All XC functionals predict that PYV3 presents a larger ΔEKE value than HC, and as expected, both are larger than for POC. Still, only hybrid functionals correctly predict which form is the most stable in the crystalline state. Then, the bond length changes in the O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment that occur upon enol to keto transformation are similarly predicted by all functionals and are consistent with the reversal of the single/double bonds pattern. (Graph Presented).

langueAnglais
Pages6898-6908
Nombre de pages11
journalThe Journal of Physical Chemistry C
Volume121
Numéro12
Les DOIs
étatPublié - 7 mars 2017

Empreinte digitale

Bond length
functionals
Density functional theory
switches
Switches
density functional theory
solid state
Aminophenols
Crystalline materials
X ray diffraction
Crystals
Periodic structures
Succinic Acid
Aniline
Phenol
Pyridine
Phenols
energy
Single crystals
Derivatives

mots-clés

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    @article{ab64ba5bcb7d479798973cdc08435d9c,
    title = "Assessing density functional theory approaches for predicting the structure and relative energy of salicylideneaniline molecular switches in the solid state",
    abstract = "The geometrical structures of salicylideneaniline (anil) molecular switches in the solid state have been determined using periodic structure calculations and a variety of density functional theory (DFT) exchange-correlation (XC) functionals, of which several have been tuned for the solid state. The first target was on predicting the unit cell and intramolecular geometrical parameters for three anil derivatives, i.e., the (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3) and N-(5-chloro-2-hydroxybenzylidene)-aniline (HC) crystals, where the enol (E) form is dominant in the crystalline state at low temperature (∼100 K), and the N-(5-chloro-2-hydroxybenzylidene)-hydroxyaniline (POC) crystal, which is mostly composed of the keto (K) form. The best performance for the unit cell parameters, in comparison with single-crystal X-ray diffraction (XRD) data, is achieved with XC functionals developed for the solid state (PBEsol and PBEsol0) as well as with ωB97X. On the other hand, the differences between the functionals are much smaller when considering the bond lengths and the valence angles so that the deviations with respect to XRD data in the bond length alternations of the key O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment are smaller than 0.02 {\AA} for PBEsol0 and ωB97X. Similar trends are observed for the two polymorphic cocrystals of PYV3 with fumaric or succinic acid. The second target was the characterization of the variations of energy and structural parameters when switching between the enol and keto forms. All XC functionals predict that PYV3 presents a larger ΔEKE value than HC, and as expected, both are larger than for POC. Still, only hybrid functionals correctly predict which form is the most stable in the crystalline state. Then, the bond length changes in the O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment that occur upon enol to keto transformation are similarly predicted by all functionals and are consistent with the reversal of the single/double bonds pattern. (Graph Presented).",
    keywords = "molecular switches, Quantum chemistry",
    author = "Jean Quertinmont and Andrea Carletta and Tumanov, {Nikolay A.} and Tom Leyssens and Johan Wouters and Beno{\^i}t Champagne",
    note = "doi: 10.1021/acs.jpcc.7b00580",
    year = "2017",
    month = "3",
    day = "7",
    doi = "10.1021/acs.jpcc.7b00580",
    language = "English",
    volume = "121",
    pages = "6898--6908",
    journal = "Journal of Physical Chemistry C",
    issn = "1932-7447",
    publisher = "American Chemical Society",
    number = "12",

    }

    TY - JOUR

    T1 - Assessing density functional theory approaches for predicting the structure and relative energy of salicylideneaniline molecular switches in the solid state

    AU - Quertinmont,Jean

    AU - Carletta,Andrea

    AU - Tumanov,Nikolay A.

    AU - Leyssens,Tom

    AU - Wouters,Johan

    AU - Champagne,Benoît

    N1 - doi: 10.1021/acs.jpcc.7b00580

    PY - 2017/3/7

    Y1 - 2017/3/7

    N2 - The geometrical structures of salicylideneaniline (anil) molecular switches in the solid state have been determined using periodic structure calculations and a variety of density functional theory (DFT) exchange-correlation (XC) functionals, of which several have been tuned for the solid state. The first target was on predicting the unit cell and intramolecular geometrical parameters for three anil derivatives, i.e., the (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3) and N-(5-chloro-2-hydroxybenzylidene)-aniline (HC) crystals, where the enol (E) form is dominant in the crystalline state at low temperature (∼100 K), and the N-(5-chloro-2-hydroxybenzylidene)-hydroxyaniline (POC) crystal, which is mostly composed of the keto (K) form. The best performance for the unit cell parameters, in comparison with single-crystal X-ray diffraction (XRD) data, is achieved with XC functionals developed for the solid state (PBEsol and PBEsol0) as well as with ωB97X. On the other hand, the differences between the functionals are much smaller when considering the bond lengths and the valence angles so that the deviations with respect to XRD data in the bond length alternations of the key O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment are smaller than 0.02 Å for PBEsol0 and ωB97X. Similar trends are observed for the two polymorphic cocrystals of PYV3 with fumaric or succinic acid. The second target was the characterization of the variations of energy and structural parameters when switching between the enol and keto forms. All XC functionals predict that PYV3 presents a larger ΔEKE value than HC, and as expected, both are larger than for POC. Still, only hybrid functionals correctly predict which form is the most stable in the crystalline state. Then, the bond length changes in the O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment that occur upon enol to keto transformation are similarly predicted by all functionals and are consistent with the reversal of the single/double bonds pattern. (Graph Presented).

    AB - The geometrical structures of salicylideneaniline (anil) molecular switches in the solid state have been determined using periodic structure calculations and a variety of density functional theory (DFT) exchange-correlation (XC) functionals, of which several have been tuned for the solid state. The first target was on predicting the unit cell and intramolecular geometrical parameters for three anil derivatives, i.e., the (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3) and N-(5-chloro-2-hydroxybenzylidene)-aniline (HC) crystals, where the enol (E) form is dominant in the crystalline state at low temperature (∼100 K), and the N-(5-chloro-2-hydroxybenzylidene)-hydroxyaniline (POC) crystal, which is mostly composed of the keto (K) form. The best performance for the unit cell parameters, in comparison with single-crystal X-ray diffraction (XRD) data, is achieved with XC functionals developed for the solid state (PBEsol and PBEsol0) as well as with ωB97X. On the other hand, the differences between the functionals are much smaller when considering the bond lengths and the valence angles so that the deviations with respect to XRD data in the bond length alternations of the key O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment are smaller than 0.02 Å for PBEsol0 and ωB97X. Similar trends are observed for the two polymorphic cocrystals of PYV3 with fumaric or succinic acid. The second target was the characterization of the variations of energy and structural parameters when switching between the enol and keto forms. All XC functionals predict that PYV3 presents a larger ΔEKE value than HC, and as expected, both are larger than for POC. Still, only hybrid functionals correctly predict which form is the most stable in the crystalline state. Then, the bond length changes in the O-C=C-C=N-C (or O=C-C=C-N-C) π-conjugated segment that occur upon enol to keto transformation are similarly predicted by all functionals and are consistent with the reversal of the single/double bonds pattern. (Graph Presented).

    KW - molecular switches

    KW - Quantum chemistry

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    U2 - 10.1021/acs.jpcc.7b00580

    DO - 10.1021/acs.jpcc.7b00580

    M3 - Article

    VL - 121

    SP - 6898

    EP - 6908

    JO - Journal of Physical Chemistry C

    T2 - Journal of Physical Chemistry C

    JF - Journal of Physical Chemistry C

    SN - 1932-7447

    IS - 12

    ER -