Available online at www.worldscientificnews.com
WSN 36 (2016) 27-46 EISSN 2392-2192
Synthesis, spectral, molecular structure, HOMO-LUMO and NLO analysis of some (E)-N’-(3,3-
dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide
G. Sundaraselvan and S. Darlin Quine*
Department of Chemistry, Government Arts College, C. Mutlur, Chidambaram - 608102, India
*E-mail address: [email protected]
ABSTRACT
(E)-N’-(3,3-dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide (DDMs) have
been synthesized and their IR and 1H spectra were recorded. The optimized geometric parameters
(bond lengths, bond angles and dihedral angles) were in good agreement with the corresponding
experimental values. In addition, HOMO-LUMO, MEP and atomic charges of carbon, nitrogen and
oxygen were calculated using B3LYP/6-311G(d,p) level theory. The polarizability and first order
hyperpolarizability of the title molecule were calculated and interpreted.
Keywords: piperidin-4-one; DFT; HOMO – LUMO energies; NLO
1. INTRODUCTION
The piperidone and its derivatives are a class of nitrogen containing heterocycles that
have received much attention because of their wide range of biological activities1-5
as well as
properties useful from the technological point of view 6,7
. Pipeeridin-4-ones were also used as
corrosion and oxidation inhibitors8. Regardless of this fact, studies regarding the investigation
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of their molecular structure and their electronic structure by computational techniques are
lacking in the chemical literature 9-11
. Density functional theory (DFT) calculations are the
excellent alternative methods in the design of NLO molecules and it helps to predict
properties of the new materials, such as molecular dipole moments, polarizabilities, and
hyperpolarizabilities12
. The present work reports the results of a systematic study of the
geometrical and electronic structure, electrostatic potential surfaces and molecular
hyperpolarizability based on their density functional theory computations.
2. EXPERIMENTAL DETAILS
Synthesis of 3,3-Dimethyl-2,6-diarylpiperidin-4-ones ( 1-5)
Dry ammonium acetate (100 mmol), 3-methyl-2-butanone (100 mmol) and
appropriate substituted benzaldehyde (200 mmol) in ethanol were just heated to boil and
allowed to stand at room temperature overnight. The reaction mixture was diluted with ether
(100 mL) and treated with Conc. HCl (20 mL). The precipitated hydrochloride was washed
with ethanol–ether. The hydrochloride was suspended in acetone and neutralized with
aqueous ammonia. Dilution with water gave the free base which was recrystallized from
ethanol.
Synthesis of ethyl 4-methoxybezoate (6) and 4-methoxybezo hydrazide (7) Ethyl
4-methoxybezoate (6) and 4-methoxybezo hydrazide (7) were synthesized as per the
procedure described in literature 13
.
Synthesis of (E)-N’-(3,3-dimethyl-2,6-diarylpiperidin-4-ylidene)-4-methoxybenzohydrazide (8-12)
A mixture of 3,3-Dimethyl-2,6-diarylpiperidin-4-ones (1 mmol), 4-methoxybezo
hydrazide (1.5 mmol) in ethanol and a few drops of acetic acid was added and refluxed for 2–
4 h. On completion of the reaction time, a solid mass was formed, which was then cooled to
room temperature. The precipitate was filtered off and washed with ice-cooled water– ethanol
mixture. The crude product was recrystallized from ethanol. Synthetic routes of compounds
are given in scheme 1.
(E)-N’-(3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-methoxybenzohydrazide (8)
Pale Yellow solid; Yield 65%., M.P: 191 °C, MF: C27H29N3O2; elemental analysis:
Calcd (%): C, 75.85; H, 6.84; N, 9.83; O, 7.48; found (%): C, 75.74; H, 6.86; N, 9.79; IR
(KBr, cm-1
): 3464 (N-H), 3068 (Ar-C-H), 2935 (AliC-H), 1647 (C=O); 1H-NMR (CDCl3)
7.26-8.01 (m, Ar-H), 2.14 (1H, N-H), 7.26 (1H, N-H), 3.01 (1H, H5ax,), 3.13 (1H, H5eq),
3.88 (1H, H2), 3.54 (1H, H6), 3.50 (3H, OCH3), 1.62 (3H, CH3); Mass (m/z): 426 (M+), 350,
265, 164, 107, 96, 77.
(E)-N’-(2,6-bis(4-fluorophenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-
methoxybenzohydrazide (9)
Yellow solid; Yield 63%., M.P: 204 °C, MF: C27H27F2N3O2; elemental analysis:
Calcd (%): C, 69.96; H, 5.87; F, 8.20; N, 9.07; O, 6.90; found (%): C, 69.665; H, 5.83; N,
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9.03; IR (KBr, cm-1
): 3477 (N-H), 3064 (Ar-C-H), 2920 (AliC-H), 1674 (C=O); 1H-NMR
(CDCl3) 6.84-7.75 (m, Ar-H), 2.14 (1H, N-H), 7.28 (1H, N-H), 2.18 (1H, H5ax,), 2.54 (1H,
H5eq), 4.36 (1H, H2), 4.00 (1H, H6), 3.91 (3H, OCH3), 1.61 (3H, CH3); Mass (m/z): 462
(M+), 368, 328, 273, 150, 107.
(E)-N’-(2,6-bis(4-chlorophenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-
methoxybenzohydrazide (10)
Pale Yellow solid; Yield 66%., M.P: 189 °C, MF: C27H27Cl2N3O2; elemental analysis:
Calcd (%): C, 65.32; H, 5.48; Cl, 14.28; N, 8.46; O, 6.45; found (%): C, 65.302; H, 5.45; N,
8.43; IR (KBr, cm-1
): 3427 (N-H), 3059 (Ar-C-H), 2927 (AliC-H), 1653 (C=O); 1H-NMR
(CDCl3) 7.47-8.18 (m, Ar-H), 1.97 (1H, N-H), 7.28 (1H, N-H), 2.37 (1H, H5ax,), 2.54 (1H,
H5eq), 3.19 (1H, H2), 4.78 (1H, H6), 3.68 (3H, OCH3), 1.66 (3H, CH3); Mass (m/z): 458
(M+), 444, 352, 324, 282, 135, 93.
(E)-N’-(3, 3-dimethyl-2,6-di-p-tolylpiperidin-4-ylidene)-4-methoxybenzohydrazide (11)
Pale Yellow solid; Yield 60%., M.P: 214 °C, MF: C29H33N3O2; elemental analysis:
Calcd (%): C, 76.45; H, 7.30; N, 9.22; O, 7.02; found (%): C, 76.30; H, 7.29; N, 9.12; IR
(KBr, cm-1
): 3464 (N-H), 3068 (Ar-C-H), 2918 (AliC-H), 1597 (C=O); 1H-NMR (CDCl3)
7.05-7.60 (m, Ar-H), 2.15 (1H, N-H), 6.75 (1H, N-H), 2.48 (1H, H5ax,), 2.66 (1H, H5eq),
3.65 (1H, H2), 3.65 (1H, H6), 3.45 (3H, OCH3), 1.62 (3H, CH3); Mass (m/z): 454 (M+), 440,
349, 329, 293, 135.
(E)-I’-(2,6-bis(4-methoxyphenyl)-3,3-dimethyl-2,6-diphenylpiperidin-4-ylidene)-4-
methoxybenzohydrazide (12)
Pale Yellow solid; Yield 61%., M.P: 231 °C, MF: C29H33N3O4; elemental analysis:
Calcd (%): C, 71.44; H, 6.82; N, 9.22; O, 13.13; found (%): C, 71.43; H, 6.70; N, 9.12; IR
(KBr, cm-1
): 3462 (N-H), 3070 (Ar-C-H), 2920 (AliC-H), 1656 (C=O); 1H-NMR (CDCl3)
6.75-7.32 (m, Ar-H), 2.17 (1H, N-H), 6.90 (1H, N-H), 2.70(1H, H5ax,), 3.06 (1H, H5eq),
3.82 (1H, H2), 3.44 (1H, H6), 3.88 (3H, OCH3), 1.68 (3H, CH3); Mass (m/z): 486 (M+), 472,
456, 380, 352, 349, 164, 111.
Spectral measurements
The FT-IR spectrum of the synthesized DDMs was measured in the range 4000-500
cm-1
on a AVATAR-330 FT-IR spectrometer (Thermo Nicolet) using KBr (pellet form). 1H
NMR spectrum was recorded at 400 MHz on a BRUKER model using CDCl3 as solvent.
Tetramethylsilane (TMS) was used as internal reference for all NMR spectra, with chemical
shifts reported in δ units (parts per million) relative to the standard.
Computational studies
Structure optimizations of DDMs were performed at the Density Functional Theory
(DFT) level employing B3LYP/6-311G(d,p) functional as implemented in the Gaussain
03W14
. To investigate the reactive sites of the title molecules, the Mulliken and molecular
electrostatic potential were evaluated.
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Scheme 1. Synthetic routes of compounds (8-12).
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Moreover, in order to show nonlinear optical (NLO) activity of studied molecules, the
dipole moment, linear polarizability and first order hyperpolarizability were obtained from
molecular polarizabilities based on theoretical calculations. Also, the HOMO-LUMO on
optimized structures is accomplished at B3LYP/6-311G(d,p) level computation. The
electronegativity (χ) were reported by Iczkowski et al.15
is performed as χ = (EHOMO +
ELUMO)/2. The global electrophilicity16
(ω) is also calculated following the expression ω =
(μ2/2η), where μ is the chemical potential (μ ≈ (EHOMO + ELUMO) / 2), and η is the chemical
hardness (ELUMO − EHOMO)/2)17
.
3. RESULTS AND DISCUSSION
Molecular geometry
The chair conformer of piperidine molecule is the most stable conformer18,19
.
Therefore, we neglected other conformations i.e. boat, envelope or twist boat because of their
high energy. Piperidine molecules show the equatorial disposition of N-H in chair conformer
as the most stable one 20
.
Fig. 1. Numbering Pattern of DDMs.
The optimized structural parameters such as bond lengths, bond and dihedral angles
of DDMs were determined at B3LYP level theory with 6-311G(d,p) basis set and are
presented in Table 1 in accordance with the atom numbering scheme of the molecule shown
in Fig. 1. To the best of our knowledge, no single crystal X-ray crystallographic data of
DDMs has yet been reported. However, the theoretical results obtained are almost
comparable with closely related molecules such as E)- N’-(3,3-Dimethyl-2,6-diphenylpiperidin-
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4-ylidene)isonicotinohydrazide21
. The C2-N1 and C6-N1 bond nearly 1.464 Å by B3LYP,
which is coincide with literature value 1.463 Å21
.
(8)
(9)
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(10)
(11)
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(12)
Fig. 2. Optimized structures of DDMs.
Table 1. Selected bond lengths, bond angles and dihedral angles of DDMs.
Bond length (Å) XRDa 8 9 10 11 12
C2-N1 1.463 1.464 1.465 1.465 1.464 1.465
N1-H1 0.900 1.016 1.016 1.016 1.026 1.016
C6-N1 1.458 1.479 1.481 1.481 1.481 1.479
C2-C3 1.554 1.592 1.591 1.591 1.581 1.591
C3-C4 1.524 1.548 1.548 1.548 1.528 1.548
C4-C5 1.506 1.514 1.515 1.515 1.507 1.515
C5-C6 1.530 1.558 1.556 1.557 1.548 1.557
C3-C8 1.531 1.547 1.547 1.547 1.547 1.546
C3-C7 1.530 1.547 1.547 1.547 1.589 1.547
C4-N17 1.274 1.289 1.289 1.289 1.263 1.290
N17-N18 1.389 1.363 1.362 1.363 1.294 1.364
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N18-H18 0.890 1.014 1.014 1.014 1.094 1.014
N18-C19 1.345 1.394 1.395 1.393 1.329 1.393
C19-O19 1.228 1.229 1.229 1.229 1.430 1.229
C24-025 - 1.420 1.421 1.421 1.421 1.420
Bond angle (°)
N1-C2-C3 109.55 112.01 111.86 111.94 112.02 111.98
N1-C6-C5 108.38 111.80 111.83 111.78 111.82 111.72
H1-N1-C2 108.00 110.58 110.25 110.40 110.48 110.56
H1-N1-C6 108.40 109.05 108.66 108.73 108.57 108.91
C2-C3-C4 105.43 106.59 106.60 106.72 106.61 106.71
C3-C4-C5 115.62 104.01 117.02 116.99 117.30 117.00
C4-C5-C6 109.92 113.95 114.09 114.15 114.09 114.05
C2-N1-C6 112.55 113.25 113.04 113.30 113.14 113.44
C3-C4-N17 127.81 128.85 128.82 128.84 128.92 128.82
C5-C4-N17 116.53 114.01 114.05 114.07 114.03 114.09
H18-N18-C19 110.21 111.00 110.84 110.97 111.40 111.04
N18-C19-O19 115.98 116.34 116.24 116.42 116.34 116.49
Dihedral (°)
N1-C2-C3-C4 57.28 46.62 47.24 47.20 47.62 46.72
N1-C6-C5-C4 -53.75 30.91 30.71 31.26 31.71 31.22
C8-C3-C4-N17 -71.68 -54.35 -55.40 -55.42 -55.41 -54.52
C7-C3C4-N17 67.09 68.22 67.16 67.18 67.16 68.13
N1-C2-C9-C10 86.41 34.35 33.31 33.74 34.35 35.10
N1-C2-C9-C10’ -138.95 -144.37 -145.04 -110.65 -144.38 -143.21
N1-C6-C13-C14 -32.70 -77.54 -85.67 -84.13 -77.54 -79.71
N1-C6-C13-C14’ 99.63 100.64 91.63 93.24 100.62 98.03
N17-N18-C19-C20 -16.25 -17.32 -16.19 -16.58 -17.40 -17.96
a- Values are taken from Ref. 21
Piperidine ring essentially adopts chair conformation, with all substituents equatorial as
evident from the torsional angles [N1–C2–C3–C4 ≈ -47.00 and 57.28 and N1–C6–C5–C4
≈ -30.91 and -53.75° by B3LYP and XRD, respectively. In the molecular optimized
structure, the hydrazone analogue is nearly planar with the dihedral angle
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(N17-N18-C19-C20) around ~16.19° B3LYP and adopts an E configuration with respect to
the C4=N4 bond21
. Form the result we concluded that the E configuration is more stable than
the other possibilities.
Mulliken analysis
The calculation of Mulliken atomic charges plays an important role in the application of
quantum mechanical calculations to molecular systems. The Mulliken atomic charges for the
DDMs calculated at the B3LYP/6-31G(d,p) level in gas-phase are presented in Fig. 3 and Table
2. Results from Table 2 show that C7 has higher positive value than C8 in title compounds.
This difference is due to the from that C7 experiences –I effect from oxygen (N17) atom. The
Table 2 for DDMs shows that the high positive charge in molecule is [H1, C4, C12, C16,
H18, C19, C23]. The positive regions are related to nucleophilic reactivity. The negative
regions are located around the oxygen (O19, O27) and nitrogen (N1, N1 and N18) atoms
which are related to electrophilic reactivity22
. These data clearly show that DDMs are the
most reactive towards substitution reactions.
Table 2. Mulliken atomic charges of DDMs.
Atom 8 9 10 11 12
N1 -0.510 -0.509 -0.509 -0.511 -0.509
H1 0.240 0.240 0.240 0.242 0.239
C2 -0.012 -0.018 -0.019 -0.016 -0.018
C3 -0.251 -0.019 -0.018 -0.019 -0.018
C4 0.315 0.316 0.316 0.324 0.315
C5 -0.018 -0.254 -0.252 -0.261 -0.251
C6 0.038 0.033 0.033 0.040 0.033
C7 -0.327 -0.323 -0.323 -0.329 -0.323
C8 -0.314 -0.319 -0.319 -0.317 -0.319
C9 0.133 0.130 0.131 0.124 0.133
C12 0.386 0.353 0.310 0.327 0.351
R12 0.086 -0.297 -0.558 -0.381 -0.510
C13 0.132 0.083 0.082 0.066 0.088
C16 0.384 0.353 0.328 0.127 0.350
R16 0.086 -0.297 -0.558 -0.381 -0.518
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N17 -0.327 -0.327 -0.329 -0.328 -0.329
N18 -0.413 -0.413 -0.412 -0.413 -0.412
H18 0.260 0.259 0.259 0.259 0.260
C19 0.553 0.552 0.551 0.553 0.553
O19 -0.514 -0.512 -0.514 -0.515 -0.515
C20 0.041 0.041 0.042 0.037 0.042
C23 0.360 0.360 0.359 0.359 0.359
O27 -0.514 -0.513 -0.514 -0.514 -0.514
C25 -0.081 -0.081 -0.081 -0.080 -0.080
R = H, F, O, C and O for 8, 9, 10, 11 and 12, respectivel.
Fig. 3. Mulliken charges of DDMs
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Molecular electrostatic potential analysis
(8)
(9)
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(10)
(11)
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(12)
Fig. 4. MEP diagram of DDMs.
Molecular electrostatic potential (MEP) is a helpful descriptor used to visualize the
electrophilic or nucleophilic reactive sites of molecules22
, and to show the electrostatic
potential regions in terms of color grading. In MEP map (Fig. 4), different values of the
electrostatic potential are represented by different colors: red and blue represents the regions
of the most negative and positive electrostatic potential whereas green represents the region of
zero potential. Potential increases in the order of: red < orange < yellow < green < blue. The
positive regions are placed around all hydrogen atoms attached with the nitrogen, which are
related to nucleophilic reactivity 22
.
The negative regions are located around the oxygen and nitrogen atoms. As shown in Fig.
4, the negative potential sites are around the electronegative (oxygen and nitrogen) atoms and
the positive potential sites are hydrogen and carbon atoms, while the remaining species are
surrounded by orange, yellow and green. As we conclude from this our title molecules are
ready for both electrophilic and nucleophilic reactions.
Frontier molecular orbital analysis
The frontier molecular orbitals play an important role in the electric and optical
properties, as well as in chemical reactions, UV–Vis and fluorescence spectra23,24
. The
contour surfaces of the frontier molecular orbitals for each molecule drawn in Fig. 5. In the
DDMs, the electron cloud distribution in HOMO is piperidine ring and hydrazone unit, but
the contribution of molecular fragment to LUMO are mainly from the hydrazone unit. The
difference of the charge separation between the HOMO and LUMO of those structure play
important role in the internal charge transfer (ICT).
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Furthermore, the difference on the values of ΔE of compounds 8-12 was observed, which
has different substituent at 12 & 16- sites of the phenyl core.
Table 3. Calculated energy values (eV) of DDMs in gas phase.
DFT/B3LYP/6-311G(d,p) 8 9 10 11 12
EHOMO -5.98 -6.07 -5.88 -5.94 -5.80
ELUOMO -0.88 -0.98 -0.83 -0.86 -0.80
ELUMO-HOMO 5.10 5.09 5.05 5.08 5.00
EHOMO-1 -6.04 -6.19 -5.96 -6.00 -5.89
ELUOMO+1 -0.28 -0.52 -0.22 -0.13 -0.15
E(LUMO+1)- (HOMO-1) 5.76 5.67 5.74 5.87 5.73
Electrinegativity(χ) -3.43 -3.53 -3.35 -3.41 -3.30
Hardness(η) 2.55 2.55 2.52 2.55 2.50
Electrophilicity index(ψ) 2.31 2.44 2.23 2.28 2.18
Softness(s) 145.23 145.24 146.67 145.40 148.15
For a system lower value of ΔE makes it more reactive or less stable and also has a
direct influence on the electron density difference for the stabilizing ICT process. In this
sense, it seems that the selection of a methoxy containing substituent has a beneficial effect
among the designed candidate. As a result, the trend of ΔE gap of inspected compounds
becomes 12 > 10 > 11 > 9 > 8.
We can observe from this Table 3, the introduction of different substituent at 12 & 16-
sites of the phenyl core significantly change the ΔE value.
Chemical hardness is related with the stability and reactivity of a chemical system, it
measures the resistance to change in the electron distribution or charge transfer. In this sense,
chemical hardness corresponds to the gap between the HOMO and LUMO. The larger the
HOMO–LUMO energy gap, the harder and more stable/less reactive the molecule. The
higher value of ΔE represents more hardness or less softness of a compound, thus compound
8 referred as hard molecule when compared to 9-1225
.
Another global reactivity descriptor electrophilicity index (ψ) describes the electron
accepting ability of the systems quite similar to hardness and chemical potential. High values
of electrophilicity index increases electron accepting abilities of the molecules. Thus, electron
accepting abilities of compounds 8-12 are arranged in following order: 9 > 8 > 10 > 11 > 12.
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Fig. 5. Molecular orbitals and energies for the HOMO and LUMO in gas phase.
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Non-linear optical activity
NLO is important property providing key for areas such as telecommunications, signal
processing and optical interactions26,27
. A large variety of NLO switches exhibiting large
changes in the first order hyperpolarizability (β), the molecular second-order NLO response.
In this context, the design of NLO switches, that is, molecules computed for their first
hyperpolarizability by alternate their substitution at 12 and 16- sites in phenyl core. The total
static dipolemoment (μ), the Mean polarizabilty (α) , Anisotropy of the polarisabiltiy (Δα)
and the first order hyperpolarizability (β0) using the x, y, z components are calculated using
the following equations.
μ = (μx2 + μy
2 + μz
2)
1/2
√ [( )
( )
( )
(
)]
( ) ( )
(
)
Table 4. Non-linear optical properties of DDMs calculated using B3LYP method using
6-311G(d,p) basis set.
NLO behavior 8 9 10 11 12
Dipole moment (μ) D 3.94 3.54 5.17 3.83 5.28
Mean polarizabilty (α) x10-23
esu 2.70 3.00 2.80 2.90 2.90
Anisotropy of the
Polarisabiltiy (Δα) x10-24
esu 6.66 4.50 7.91 7.09 9.53
First order polarizabilty (β0) x10-30
esu 1.29 2.01 2.06 1.23 2.41
As the results mentioned previously10,28,29
, hydrazones may have significance nonlinear
optical property. In this sense a series of new molecules possessing nonlinear optical property
are designed which includes S, F, OH, CH3 and OCH3 groups at 12 & 16- sites of the phenyl
core. According to Table 4, all values of each mentioned molecules are greater than their
urea30
values. Therefore, NLO properties of our compounds are better than urea.
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Results from Table 4, the general ranking of NLO properties should be as follows: 12 >
10 > 8 > 11 > 9. With results in hand, molecule 5 is the best candidate for NLO properties. To
sum up, it can be concluded that the presence of an electron donating group (methoxy) in the
para position at the phenyl ring contributes to decrease the dipole moments, mean
polarisability and first order hyperpolarizability of the DDMs probably because of an
inductive competition between the methoxy and the electronic density available in the
molecule.
When it is compared with similar compounds in the literature, the β0 value tittle
compounds are high than that of 3t-pentyl-2r,6c-diphenylpiperidin-4-one semicarbazone
(β0 = 0.65 x10-30
esu)28
and 3t-pentyl-2r,6c-diphenylpiperidin-4-one thiosemicarbazone (β0 =
1.28 x10-30
esu)29
. The above results show that DDMs can be best material for NLO
applications
4. CONCLUSIONS
Results from in hand, piperidone ring adopts chair conformation with equatorial
orientation of substituent at C2, C3, C6 and hyzrazone analogue adopts an E configuration
with respect to C4=N17. In addition, Mulliken charge and MEP analysis predicts the most
reactive parts in the molecule. The result of molecular orbital composition analysis revealed
for DDMs, that the ΔE gap could be lowered upon modifying the 12 & 16- sites of the phenyl
core. Among this, compound 12 is the best candidate for the stabilizing ICT process. Another
conclusion of the paper is the calculated first hyperpolarizability is comparable with reported
values of similar derivatives and the 12 is a strong candidate for future studies of nonlinear
optics.
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( Received 02 January 2016; accepted 13 January 2016 )