Polymorphism and conformational equilibrium of nitro-acetophenone in solid state and under matrix conditions

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Polymorphism and conformational equilibrium of nitro-acetophenone in solid state and under matrix conditions. / Hetmańczyk, Łukasz; Szklarz, Przemysław; Kwocz, Agnieszka; Wierzejewska, Maria; Pagacz-Kostrzewa, Magdalena; Melnikov, Mikhail Ya; Tolstoy, Peter M.; Filarowski, Aleksander.

In: Molecules, Vol. 26, No. 11, 3109, 22.05.2021.

Research output: Contribution to journal › Article › peer-review

Author

Hetmańczyk, Łukasz ; Szklarz, Przemysław ; Kwocz, Agnieszka ; Wierzejewska, Maria ; Pagacz-Kostrzewa, Magdalena ; Melnikov, Mikhail Ya ; Tolstoy, Peter M. ; Filarowski, Aleksander. / Polymorphism and conformational equilibrium of nitro-acetophenone in solid state and under matrix conditions. In: Molecules. 2021 ; Vol. 26, No. 11.

BibTeX

@article{43e0c3db0a2c49d58fca9687c43b0215,

title = "Polymorphism and conformational equilibrium of nitro-acetophenone in solid state and under matrix conditions",

abstract = "Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound.",

keywords = "DFT, DSC, FT-IR, IINS, Isomerization, Matrix isolation, Nitro group, NQR, Phase transition, Polymorphism, Raman, X-ray, isomerization, COMPLEXES, nitro group, polymorphism, INELASTIC NEUTRON-SCATTERING, NUCLEAR-QUADRUPOLE RESONANCE, HYDROGEN, matrix isolation, COCRYSTALS, phase transition, PROTON-TRANSFER, SPECTRA",

author = "{\L}ukasz Hetma{\'n}czyk and Przemys{\l}aw Szklarz and Agnieszka Kwocz and Maria Wierzejewska and Magdalena Pagacz-Kostrzewa and Melnikov, {Mikhail Ya} and Tolstoy, {Peter M.} and Aleksander Filarowski",

note = "Publisher Copyright: {\textcopyright} 2021 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2021",

month = may,

day = "22",

doi = "10.3390/molecules26113109",

language = "English",

volume = "26",

journal = "Molecules",

issn = "1420-3049",

publisher = "MDPI AG",

number = "11",

}

RIS

TY - JOUR

T1 - Polymorphism and conformational equilibrium of nitro-acetophenone in solid state and under matrix conditions

AU - Hetmańczyk, Łukasz

AU - Szklarz, Przemysław

AU - Kwocz, Agnieszka

AU - Wierzejewska, Maria

AU - Pagacz-Kostrzewa, Magdalena

AU - Melnikov, Mikhail Ya

AU - Tolstoy, Peter M.

AU - Filarowski, Aleksander

PY - 2021/5/22

Y1 - 2021/5/22

N2 - Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound.

AB - Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound.

KW - DFT

KW - DSC

KW - FT-IR

KW - IINS

KW - Isomerization

KW - Matrix isolation

KW - Nitro group

KW - NQR

KW - Phase transition

KW - Polymorphism

KW - Raman

KW - X-ray

KW - isomerization

KW - COMPLEXES

KW - nitro group

KW - polymorphism

KW - INELASTIC NEUTRON-SCATTERING

KW - NUCLEAR-QUADRUPOLE RESONANCE

KW - HYDROGEN

KW - matrix isolation

KW - COCRYSTALS

KW - phase transition

KW - PROTON-TRANSFER

KW - SPECTRA

UR - http://www.scopus.com/inward/record.url?scp=85107162094&partnerID=8YFLogxK

U2 - 10.3390/molecules26113109

DO - 10.3390/molecules26113109

M3 - Article

C2 - 34067498

AN - SCOPUS:85107162094

VL - 26

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 11

M1 - 3109

ER -

ID: 85604967