Vibrational spectra, conformation and molecular transport of 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one
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Vibrational spectra, conformation and molecular transport of 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one. / Bazrafshan, Mahmoud; Vakili, Mohammad; Tayyari, Sayyed Faramarz; Kamounah, Fadhil S.; Hansen, Poul Erik; Housaindokht, Mohammad Reza.
In: Journal of Molecular Structure, Vol. 1272, 134178, 2023, p. 11.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Vibrational spectra, conformation and molecular transport of 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one
AU - Bazrafshan, Mahmoud
AU - Vakili, Mohammad
AU - Tayyari, Sayyed Faramarz
AU - Kamounah, Fadhil S.
AU - Hansen, Poul Erik
AU - Housaindokht, Mohammad Reza
PY - 2023
Y1 - 2023
N2 - In this research, the molecular structure and intramolecular hydrogen bonding (IHB) of 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one (AMTMH) were studied using spectroscopic techniques (IR, Raman, UV, and NMR) and computational analysis (density functional theory (DFT) and the second-order Moller-Plesset (MP2) methods). The results of this study compared with those of 4-amino-3-penten-2-one (APO) and 3-methyl-4-amino-3-penten-2-one (3-MeAPO). The averaged calculated geometrical parameters of AMTMH (obtained by considering the populations of all conformers) agree with the averaged geometrical parameters obtained by X-ray crystallography of two conformations found in the crystal. Comparison of different parameters related to the IHB strength, such as NH stretching, experimental proton chemical shift, and deuterium isotope effects on C-13 chemical shifts of AMTMH with those of APO and 3-MeAPO, suggests the following trend for the IHB strength: 3-MeAPO > AMTMH > APO. All normal modes of AMTMH were successfully assigned and compared to the corresponding band frequencies of APO. The appearance of more than one band for several vibrational normal modes is related to the coexistence of different conformers in the sample. The molecular transport results show that the conductivity of the enol form (on-state) to keto form (off-state) changes, which suggests that this system has the potential to function as a molecular switch. In addition, the experimental fluorescence and the calculated TD-DFT results confirmed both aminoketone and iminoenol forms are in the excited state. (C) 2022 Elsevier B.V. All rights reserved.
AB - In this research, the molecular structure and intramolecular hydrogen bonding (IHB) of 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one (AMTMH) were studied using spectroscopic techniques (IR, Raman, UV, and NMR) and computational analysis (density functional theory (DFT) and the second-order Moller-Plesset (MP2) methods). The results of this study compared with those of 4-amino-3-penten-2-one (APO) and 3-methyl-4-amino-3-penten-2-one (3-MeAPO). The averaged calculated geometrical parameters of AMTMH (obtained by considering the populations of all conformers) agree with the averaged geometrical parameters obtained by X-ray crystallography of two conformations found in the crystal. Comparison of different parameters related to the IHB strength, such as NH stretching, experimental proton chemical shift, and deuterium isotope effects on C-13 chemical shifts of AMTMH with those of APO and 3-MeAPO, suggests the following trend for the IHB strength: 3-MeAPO > AMTMH > APO. All normal modes of AMTMH were successfully assigned and compared to the corresponding band frequencies of APO. The appearance of more than one band for several vibrational normal modes is related to the coexistence of different conformers in the sample. The molecular transport results show that the conductivity of the enol form (on-state) to keto form (off-state) changes, which suggests that this system has the potential to function as a molecular switch. In addition, the experimental fluorescence and the calculated TD-DFT results confirmed both aminoketone and iminoenol forms are in the excited state. (C) 2022 Elsevier B.V. All rights reserved.
KW - 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one
KW - Intramolecular hydrogen bond
KW - Vibrational spectroscopy
KW - NMR
KW - DFT-NEGF
KW - SCHIFF-BASE LIGAND
KW - COMPLEXES
KW - CRYSTAL
KW - NI(II)
KW - CU(II)
KW - CO(II)
KW - ACETYLACETONE
KW - ASSIGNMENT
KW - SULFUR
U2 - 10.1016/j.molstruc.2022.134178
DO - 10.1016/j.molstruc.2022.134178
M3 - Journal article
VL - 1272
SP - 11
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
M1 - 134178
ER -
ID: 333042756