Synthesis, molecular structure and vibrational analysis of D-D-A based carbazole decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR, UV and NMR) and density functional theory (DFT) calculations

Article abstract of DOI:10.1016/j.molstruc.2016.09.026

A novel molecule, 10-(9-hexyl-9H-carbazol-3yl)-10H-phenothiazine-3-carbaldehyde (CZPTZA) has been synthesized and characterized through FT-IR, UV–Vis, NMR spectroscopic studies and molecular orbital calculations. Optimized geometrical structure, harmonic vibrational frequencies and NMR are computed with B3LYP method using 6-311++G (d,p) basis set. The geometrical parameters of the title compound obtained from Single Crystal XRD studies have been found in accord with the calculated (DFT) values. The experimentally observed vibrational frequencies are compared with the calculated ones, which were found to be in good agreement with each other. UV–Vis spectra of the title compound have also been recorded and the electronic properties, viz. excitation energies, calculated energies, oscillator strengths, frontier orbital energies and band gap energies are computed with TD-DFT/CAM-B3LYP method using 6-311++G (d,p) as the basis set. The ¹H and ¹³C NMR chemical shifts of the molecule have been calculated by the Gauge Independent Atomic Orbital (GIAO) method and compared with the experimental outcome. Also, the values of dipole moment, polarizabilities and first order hyperpolarizabilities have been computed.

Full text of DOI:10.1016/j.molstruc.2016.09.026

Accepted Manuscript
Synthesis, molecular structure and vibrational analysis of D-D-A based carbazole
decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR, UV and NMR) and
density functional theory (DFT) calculations
Ayyanar Karuppasamy, Kannan Gokula Krishnan, Muthiah Pillai Velayutham Pillai,
Chennan Ramalingan
PII:
S0022-2860(16)30953-X
10.1016/j.molstruc.2016.09.026
MOLSTR 22938
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 3 June 2016
Revised Date: 8 September 2016
Accepted Date: 8 September 2016
Please cite this article as: A. Karuppasamy, K. Gokula Krishnan, M. Pillai Velayutham Pillai, C.
Ramalingan, Synthesis, molecular structure and vibrational analysis of D-D-A based carbazole
decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR, UV and NMR) and density functional
theory (DFT) calculations, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.09.026.
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ACCEPTED MANUSCRIPT
Synthesis, molecular structure and vibrational analysis of D-D-A based
carbazole decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR,
UV and NMR) and density functional theory (DFT) calculations
Ayyanar Karuppasamy, Kannan Gokula Krishnan, Muthiah Pillai Velayutham Pillai,
Chennan Ramalingan*
Department of Chemistry, Kalasalingam University, Krishnankoil – 626 126, Tamilnadu, India
Corresponding author E-mail: ramalinganc@gmail.com (C. Ramalingan)
GRAPHICAL ABSTRACT

ACCEPTED MANUSCRIPT
Synthesis, molecular structure and vibrational analysis of D-D-A based carbazole
decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR, UV and NMR) and
density functional theory (DFT) calculations
Ayyanar Karuppasamy, Kannan Gokula Krishnan, Muthiah Pillai Velayutham Pillai,
Chennan Ramalingan*
Department of Chemistry, Kalasalingam University, Krishnankoil – 626 126, Tamilnadu, India
*Corresponding author E-mail: ramalinganc@gmail.com (C. Ramalingan)
ABSTRACT
A novel molecule, 10-(9-hexyl-9H-carbazol-3yl)-10H-phenothiazine-3-carbaldehyde
(CZPTZA) has been synthesized and characterized through FT-IR, UV-Vis, NMR spectroscopic
studies and molecular orbital calculations. Optimized geometrical structure, harmonic vibrational
frequencies and NMR are computed with B3LYP method using 6-311++G(d,p) basis set. The
geometrical parameters of the title compound obtained from Single Crystal XRD studies have
been found in accord with the calculated (DFT) values. The experimentally observed vibrational
frequencies are compared with the calculated ones, which were found to be in good agreement
with each other. UV-Vis spectra of the title compound have also been recorded and the electronic
properties, viz. excitation energies, calculated energies, oscillator strengths, frontier orbital
energies and band gap energies are computed with TD-DFT/CAM-B3LYP method using 6-
1
13
311++G(d,p) as the basis set. The H and C NMR chemical shifts of the molecule have been
calculated by the Gauge Independent Atomic Orbital (GIAO) method and compared with the
experimental outcome. Also, the values of dipole moment, polarizabilities and first order
hyperpolarizabilities have been computed.

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Key words:
Carbazole, Phenothiazine, Vibrational analysis, HOMO-LUMO, Electrostatic potential.
Introduction
Organic molecules with donor-acceptor deeds are found as emerging materials towards
solar energy cells [1] owing to their low cost, chemical versatility and trouble-free fabrication
compared to other alternative solar cell technologies. In addition, the conjugated π-electron
systems with specific functional scaffolds like cyanoacrylic acid [2] and carboxylic acid [3] have
been stimulated to enhance the electrical and optical properties. In the past decades, a diverse
range of molecules including organic dyes [4], metal-based dyes [5], dendrimers [6] and
polymers [7] has been extensively used as efficient sensitizers in organic solar cells (OSCs).
Recently, smaller molecules attracted the study in order to improve the efficiency of energy
conversion and to realize the structure-property relationship. Thus, many researchers around the
globe focused their attention to organic photoactive materials with simple synthetic processes
and low costs.
Carbazole (CZ), also known as 9-azafluorene, is a nitrogen containing heteroaromatic
compound. The presence of nitrogen at position 9 of the CZ ring increases the electron rich
nature of CZ. Carbazole derivatives have been widely studied in OSC due to their ability to form
stable radical cations [8], excellent thermal and photochemical stabilities [9] and easy
availability. Further, the synthesis and applications of its derivatives have been an increasing
area of research in the past couple of decades.
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On the other hand, phenothiazine (PTZ) is an excellent electron donating chromophore as
a result of its good thermal [10] and electrochemical stability [11]. Hence, it is widely used in
chemical manufacturing as organic light emitting diodes (OLEDs) [12], semiconductors [13] and
in solar cells applications [7]. Phenothiazine ring system has been chemically modified to exhibit
various activities like anti-malarial [14], anti-cancer [15], anti-helminthic [16], anti-histamine
[17] and anti-psychotic ones [18].
The wide variety of applications of organic molecules possessing carbazole and
phenothiazine structural motifs reported in the literature inspired us to prosecute research on
novel system carrying these two carbazole and phenothiazine moieties and, we herein report a D-
D-A
type
molecule
10-(9-hexyl-9H-carbazol-3yl)-10H-phenothiazine-3-carbaldehyde
(CZPTZA), in which the phenothiazine moiety is employed as primary unit. The compound
CZPTZA was synthesized by adopting multi-steps synthetic strategy and analyzed using both
experimental as well as computational methods. Optimized structural parameters were obtained
by Density Functional Theory (DFT) by performing B3LYP/6-311++G(d,p) level of
calculations. From the theoretical results, optimized structural parameters, vibrational
assignments and chemical shift values are deduced and compared with the experimental results.
The theoretical results are found to be in good agreement with the experimental ones.
Experimental section
General
The melting point of the title compound was measured in open capillary and is
uncorrected. FT-IR spectrum of the synthesized compound was recorded on Shimadzu IR
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Tracer-100 in the range of 400-4000 cm-1 using KBr pellet form. The spectral features are
1
reported in wavenumber (cm-1). H and 13C NMR were recorded on a Bruker 400 MHz
spectrometer. Chemical shift values are reported in parts per million (ppm) from
tetramethylsilane (TMS). Single Crystal XRD data were collected on a Bruker, 2008 SMART
APEX II diffractometer. All diffraction measurements were performed at 273 K using graphite
monochromated Mo Kα radiation (λ = 0.71073 Å).
Synthesis of 10-(9-hexyl-9H-carbazol-3yl)-10H-phenothiazine-3-carbaldehyde (CZPTZA)
The intermediates, 10H-phenothiazine-3-carbaldehyde and 9-hexyl-3-iodo-9H-carbazole
are synthesized by adopting literature methods.
To a solution of 10H-phenothiazine-3-carbaldehyde (0.50 g, 2.4 mmol) and 9-hexyl-3-
iodo-9H-carbazole (0.94 g, 2.5 mmol) in 1,2-dichlorobenzene (20 mL) under nitrogen
atmosphere, were added copper powder (0.30 g, 4.7 mmol), powdered potassium carbonate
(0.90 g, 6.5 mmol) and 18-crown-6 (0.11 g, 0.4 mmol). The reaction mixture was heated to
reflux for 48 h and filtered after cooling to room temperature. The solvent was removed under
reduced pressure and the mixture was extracted with dichloromethane after the addition of water.
The organic phase was then separated, dried over anhydrous sodium sulphate and concentrated
under reduced pressure. The solid thus obtained was subjected to column chromatography using
5~25% ethylacetate in hexane as eluent to afford pure 10-(9-hexyl-9H-carbazol-3-yl)-10H-
phenothiazine-3-carbaldehyde. Yield: 0.79 g (69%).
Pale Yellow solid; mp: 158-160 °C; FT-IR (KBr, cm-1): 3052-2805 (C-Haromatic & aliphatic),
1
1661 (C=Oaldehyde), 1594 (C=C), 1245, 1204 (C-N), 1072 (C-S); H NMR (δ, CDCl3, 400 MHz):
13
9.66 (s, 1H), 6.16-8.08 (m, 14H), 4.35 (d, 2H, CH2); 1.33-1.94 (m, 8H); 0.87 (t, 3H, CH3); C
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NMR (δ, CDCl3, 100 MHz): 14.07 (C1), 22.62 (C2), 27.07 (C4), 29.06 (C5), 31.61 (C3), 43.49
(C6), 189.82 (C=Oaldehyde), 109.24, 110.93, 115.28, 116.78, 118.86, 119.55, 119.87, 120.69,
122.35, 122.45, 123.30, 124.75, 126.57, 126.65, 127.11, 127.37, 127.54, 130.01, 130.80, 130.82,
139.91, 141.07, 143.34, 150.07 (aromatic carbons).
Computational details
The entire set of calculations was performed in DFT-B3LYP method with
6-311++G(d,p) basis set using Gaussian 09 program package [19]. The gradient corrected
density functional theory (DFT) with the three parameter hybrid functional Becke3 (B3) for the
exchange part and the Lee-Yang-Parr (LYP) correlation function [20] have universally been used
as a cost effective approach. The frequency values computed at these levels contain known
systematic errors. To bring the theoretical frequencies in close proximity to the experimental
values, the scaling factor value [21] of 0.96 was used. UV-Vis absorption spectra were calculated
by time dependent-DFT with CAM-B3LYP/6-311++G(d,p) basis set in both gas and solution
phase. NMR chemical shifts were computed at B3LYP/6-311++G(2d,p) level using the Gauge
Independent Atomic Orbital (GIAO) method [22]. The 1H and 13C isotropic chemical shift values
were referenced to the corresponding values of TMS, which was calculated at the same level of
theory.
Results and Discussion
Synthesis
Copper mediated Ullman type coupling reaction between 10H-phenothiazine-3-
carbaldehyde,[23] synthesized by adopting Duff reaction on commercially available 10H-
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phenothiazine and 9-hexyl-3-iodo-9H-carbazole, [23] synthesized by using alkylation followed
by iodination reaction on commercially available carbazole, provided the title compound 10-(9-
hexyl-9H-carbazol-3-yl)-10H-phenothiazine-3-carbaldehyde in good yield (69 %). The
schematic representation for the synthesis of CZPTZA is outlined in Scheme 1. The product
was then characterized by FT-IR, 1H and 13C NMR and Single crystal X-ray diffraction analysis.
Scheme 1.
Molecular geometry
The analyzed crystal (CCDC No. 1479040) was grown by slow evaporation technique
using chloroform as solvent at room temperature. Crystal system of the compound CZPTZA
belongs to monoclinic with P21/n symmetry. Details of the crystal data and refinement
parameters of CZPTZA are summarized in Table 1. An ORTEP view and numbering scheme of
CZPTZA is shown in Fig. 1a. Selected bond lengths, bond angles and dihedral angles of
CZPTZA are summarized in Table 2.
XRD single crystal structure reveals that the CZ and PTZ motifs are nearly perpendicular
to each other as evidenced by the dihedral angle of C4/C8 and C22/C18 through N7-C17 are
93.1(4), -85.1(4), -89.3(4) and 92.5(4)°, respectively. The mean C-C single bond length is
Å, which is in good agreement with the expected range for a C-C single bond. Single bond
lengths of carbon-nitrogen and carbon-sulfur are about 1.40, and 1.74 Å, respectively. Bond
lengths among the CZ and PTZ ring carbons are around 1.39 Å, the expected range. Bond angles
̴ 1.46
̴
̴
̴
of sp2 hybrid of CZ and PTZ rings are around 120º. The values of selected bond lengths, angles
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and torsion angles are given in Table 2. The geometric parameters of theoretically computed
optimized structure of compound CZPTZA have been compared with the X-ray crystal structure
which showed no significant difference; the largest deviation in bond distance is 0.1 Å.
The optimized molecular structure of CZPTZA is shown in Fig. 1b and geometrical
parameters are presented in Table 2. In the optimized geometry, the bond angles and the dihedral
angles between the planes C4-N7-C8 (121.7°)/C5-S10-C9 (98.9°) and N7-C4-C5-S10 (-6.9°)
N7-C8-C9-S10 (8.6°) imply that the central six membered ring in the PTZ scaffold exists in non-
planer geometry [24] and this ring adopts a boat conformation while the CZ unit adopts planar-
like geometry [25]. Further, the CZ structural motif is oriented in the equatorial position of the
central heterocyclic ring of phenothiazine with boat conformation and, as a whole; this CZ motif
is oriented in almost perpendicular to that of the phenothiazine structural unit. It is reported that
all the carbon-carbon bond lengths in the CZ and PTZ structural motifs are between carbon-
carbon single bond and double bond, implying that there exists an extensive electron
delocalization throughout the molecules [26]. The bond lengths in CZ and PTZ are ̴ 1.410Å;
closer to the calculated values for carbon-carbon bond. The C-N bond lengths of the investigated
compound are shorter than the average single C-N bond length of 1.472, being C4-N7 =
1.412(4), N7-C8 = 1.388(4), N7-C17 = 1.444(4), C20-N25 = 1.379(4), C24-N25 = 1.367(5) and
N25-C30 = 1.462(5) Å, thus showing varying degrees of single bond character [27]. The other
bond lengths and angles computed by DFT method show good agreement with their single
crystal XRD values [28].
Fig. 1.
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Table 1
Table 2
Vibrational analysis
The molecular structure of CZPTZA consists of 63 atoms, showing a total number of
183 normal modes of vibrations which are assigned by using PED. Most of the observed
vibrational patterns coincide with theoretically calculated vibrational modes. Both experimental
and theoretical FT-IR spectra of compound CZPTZA are shown in Fig. 2 and vibrational
frequencies are furnished in Table 3.
The C-H stretching in alkyl groups occurs at lower frequencies than those in aromatic
ring i.e., 2970-2840 cm-1 [29]. In the present case, the weak and medium bands for C-H
stretching vibrations of the hexyl side chain in CZ ring are observed at 2957-2805 cm-1 in FT-IR,
while the calculated stretching frequencies lies in the spectral range around 2963-2874 cm-1.
The deformation vibrations of C-H at 1402-1369 and 920-842 cm-1 in FT-IR are assigned to
mixture of deformation modes with C-H and skeleton vibrations. All these assignments are in
good agreement with literature values [28c, 30].
The C-H stretching vibrations in aromatic and hetero-aromatic rings appear in the range
3100-3000 cm-1 which is the characteristic region for the ready identification of such C-H
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stretching vibrations [29]. The C-H stretching frequency is observed at 3052-3007 cm-1 in the
FT-IR spectrum and the computed C-H stretching vibrations of CZ and PTZ rings obtained at
3087-3033 cm-1. Hence, these experimental and computational C-H stretching vibrations are in
good agreement with each other. The C-H in-plane bending vibrations of CZPTZA are observed
at 1134-1015 cm-1 in the FT-IR spectrum and the computed values of C-H in-plane and out of
plane bending vibrations, listed in Table 3, are in good agreement with the experimental values.
Fig. 2.
In general, ring carbon-carbon vibrations (C-C and C=C) are observed in the region
1630-1480 cm-1 [31]. In the present study, the wavenumbers observed in FT-IR at 1570-1463
cm-1 are due to C-C stretching vibrations. The computed frequencies at 1594-1457 cm-1 by DFT
method show a good agreement with experimental results. The in-plane and out-of plane bending
C-C-C modes of compound CZPTZA are presented in Tables 3.
Table 3
Compounds containing carbonyl group show a strong absorption in the region of 1750-
1650 cm-1 [32]. The characteristic FT-IR band appeared at 1661 cm-1 in the title compound
confirms the presence of carbonyl group in the same. The computed carbonyl stretching
vibration of aldehyde carbonyl is observed at 1687 cm-1 which correlates well with the
experimental value.
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The assignment due to the C-N and C-S stretching vibrations is difficult to identify in the
infrared spectrum as the band is of variable intensity and may be found over the wide range. The
C-N and C-S stretching bands are found to be present at 1220 and 1080 cm-1 [29,32].
The observed bands at 1204/1245 and 1072 cm-1 correspond to C-N and C-S units, respectively.
The corresponding calculated values for C-N and C-S are 1205/1248 and 1089 cm-1,
respectively.
The linear regressions between the experimental and theoretical scaled wavenumbers
obtained for CZPTZA with B3LYP/6-311++G(d,p) method are presented in supplementary
Fig. S1. The minimal RMS deviation confirms the reliability of the assignments of the
fundamental modes of the compound CZPTZA.
Fig. S1.
Mulliken population analysis
The partial atomic charge distribution of individual atom is established using Mulliken
population method. Electrons population of compound CZPTZA were obtained from the
optimized structural calculation at B3LYP/6-311++G(d,p) level and the values are listed in
supplementary Table S1. The net atomic charge distribution of compound CZPTZA is furnished
in Fig. 3. The charge distributions over the atoms suggest the formation of donor and acceptor
pairs involving the charge transfer in the molecule [33]. In the compound CZPTZA, nitrogen,
N7 and carbon, C13 atoms have attained more positive charge and become more acidic, whereas
the carbons, C17 and C35 have more negative charge than other atoms due to the connection
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through more electronegative nitrogen atom. In the carbazole and phenothiazine moieties, the
positive charges are localized on the hydrogen atoms and all the carbon atoms have negative
charges except C5, C6, C13, C15 and pyrrole skeleton in carbazole which suggests that the
electron delocalization takes place in the entire molecule [34].
Fig. 3.
Table S1
UV-Vis spectral analysis
The UV-Vis spectroscopic parameters such as wavelengths, excitation energies, band gap
energies and oscillator strengths of the title compound have been computed by TD-DFT method
with CAM-B3LYP/6-311++G(d,p) basis set in both vacuum as well as solvent phase and their
pertinent parameters are tabulated in supplementary Table S2. The experimental UV-Vis
spectrum of the CZPTZA has been obtained in acetonitrile, dichloromethane, dimethylsulfoxide,
ethanol and hexane. The experimental and simulated UV-Vis spectra of the CZPTZA, are
displayed in Fig. 4.
As can be seen in Fig. 4 and supplementary Table S2, three distinctive bands are
observed for the compound CZPTZA in all solvents. The bands observed in the wavelengths of
400, 350 and 290 nm have been assigned to n→π* and π→π* transitions, associated with the
carbaldehyde functional group and CZ & PTZ groups, respectively (i.e., ~400 nm; n→π*; CHO
̴
̴
̴
and ~350 & 290 nm; π→π*; CZ & PTZ). The absorption intensities are slightly increased in non-
polar solvents compared to polar solvents (Fig. 4). This hyperchromic shift probably points to
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the deprotonation of the compound in the solution. The observed λmax values and the calculated λ
excitation wavelengths agree reasonably well except the lowest energy excitation above 300 nm.
Fig. 4.
Table S2
HOMO-LUMO analysis
The electron distribution of frontier molecular orbitals HOMO and LUMO of compound
CZPTZA is shown in supplementary Fig. S2 and their corresponding energy values are provided
in supplementary Table S3. The charge transport properties and electronic structure of the
molecule are mainly depending on energy differences; hence, it is necessary to examine the
HOMO-LUMO energy gap [35]. The difference in calculated HOMO-LUMO energy values of
ground state, first and second excited states are found to be 1.5484, 3.0809 and 4.1172 eV,
respectively. As can be seen from the molecular orbitals of CZPTZA, the HOMOs of molecular
charges are nearly located over the CZ moiety, while the LUMO and LUMO+1 are almost
localized over the entire CZ and PTZ moieties. Thus, the electronic transition from the HOMO
(ground state) to the LUMO (excited state) is mainly electron flowing from the CZ ring to the
PTZ ring, which belongs to π-π* transition. The Gauss-Sum 2.2 Program [36] has been used to
calculate the group contribution of molecular orbitals and to determine the density of states
(DOS) of the molecule as shown in supplementary Fig. S3. DOS plot shows the population of
orbital compositions with their contribution to chemical bonding and demonstrates a clear view
of the character of the molecular orbitals in a certain energy range.
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Fig. S2.
Fig. S3.
Table S3
Molecular electrostatic potential (MEP) analysis
The MEP of a molecule is related to electron density (ED), which measures the reactivity
of the molecule and determine the nature of the molecule [37]. The MEP, easily interpreted as a
color spectrum, with red and blue as the lowest and highest electrostatic potential energy values
respectively, employed to convey the varying intensities of the electrostatic potential energy
values. The supplementary Fig. S4 illustrates total density and electrostatic potential with its
contour model of the compound CZPTZA, computed at the 0.002 a.u isosurface of the molecule.
From the MEP pictures, it could be observed that the color code of the maps is in the
range between -0.111 (electrophilic attacking site) and 0.111 E (nucleophilic attacking sites), the
areas of high potential (red), are characterized by an abundance of electrons. Oxygen has a
higher electronegativity value than nitrogen and sulfur. Oxygen atom would consequently
possess higher electron density around it than nitrogen and sulfur atoms. Thus the spherical
region that corresponds to an oxygen atom would have a red portion on it. However, the light
yellow region spread on the MEP surface due to potential halfway between the two extreme
regions and this confirms the existence of an intermolecular interaction.
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Fig. S4.
Nuclear Magnetic Resonance spectral analysis
1
The H and 13C NMR chemical shifts calculation of compound CZPTZA have been
made by B3LYP with 6-311++G(2d,p) basis set, compared with the experimental values and are
presented in supplementary Table S4 and the experimental and theoretical spectra are furnished
in supplementary Fig. S5. In the 1H NMR, a sharp triplet appeared in the up field region at 0.87
ppm with three protons integral reveals the presence of methyl protons of hexyl side chain (H61,
H62 and H63) and the experimental values are in good agreement with their computed chemical
shifts (at 0.82, 0.84 and 1.10 ppm). There are five methylene groups present in the hexyl side
chain. An eight protons multiplet appeared in the shielded region (1.33-1.94 ppm) corresponds to
protons of four methylene groups (H53-H60) and a two protons triplet observed in the
comparatively downfield region (4.35 ppm) corresponds to protons of other methylene group,
directly attached to nitrogen atom of CZ moiety. All these methylene protons are matched well
with their corresponding signals in computed one. A sharp singlet resonates in the extreme
downfield region at 9.66 ppm with one proton integral corresponds to proton of aldehyde moiety
and this value coincides with the computed one (9.34 ppm). A collection of signals obtained in
low field region at 6.16-8.08 ppm corresponds to aromatic protons of CZ and PTZ moieties and
these values are in harmony with the theoretical results.
Fig. S5.
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In the 13C-NMR, the aromatic carbon signals fall in overlapped areas of the spectrum
with the chemical shifts ranging from 100 to 160 ppm in organic molecules [38]. The aromatic
carbons appeared in the deshielded region from 109 to 150 ppm are in accordance with the
calculated results. The shielded signals around 14.0-43.4 ppm are assigned to the hexyl side
chain carbons (C30-C35) attached to the CZ ring, which are in good agreement with the
calculated values of 13.7-42.5 ppm. A signal for carbonyl carbon of PTZ appeared in the extreme
downfield region at 189.8 ppm. In the computed one, the characteristic signal appeared at 182.8
ppm is assigned to carbonyl carbon. The correlation coefficient values show a good agreement
between the experimental and the calculated results as shown in supplementary Fig. S6.
Fig. S6.
Table S4
Non-linear optical (NLO) properties
In order to investigate the relationship between molecular structure and non-linear optical
properties (NLO), the polarizabilities and first order hyperpolarizabilities of the molecule was
calculated. It is well known that molecules with high values of dipole moment, molecular
polarizability, and first hyperpolarizability show more active NLO behaviours [39]. The first
hyperpolarizability (β) and the components of hyperpolarizability (βx, βy and βz) of compound
CZPTZA and the related properties (ꢀ0, αtotal, and α0) are listed in supplementary Table S5.
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The calculated value of total dipole moment is found to be 7.7134 Debye and average
polarizability is 5.4894 x 10-23 Debye-Ang. However, the average polarizability of the
synthesized compound CZPTZA is greater than that of p-nitroaniline molecule which is a
typical NLO material [40]. The magnitude of molecular hyperpolarizability (β) is one of the
important key factors for a NLO system. As can be seen from supplementary Table S5, the
calculated first hyperpolarizability value (β) of compound CZPTZA is 3.9046 x 10-30 esu.
Further, the first hyperpolarizability value is compared with the standard material, urea (0.372 x
10-30 esu). The hyper-polarizability values (β) of CZPTZA is nearly ten times greater than that
of urea [41] and the dipole moment is also higher than that of urea (1.373 Debye). From the
above results, it is concluded that the molecular polarizability and hyperpolarizability of the
synthesized compound CZPTZA in all coordinates are active.
Table S5
Conclusion
The title compound CZPTZA was synthesized by copper mediated Ullman type coupling
reaction between 10H-phenothiazine-3-carbaldehyde and 9-hexyl-3-iodo-9H-carbazole in 1,2-
dichlorobenzene under phase transfer catalytic condition. The scaled vibrational frequencies are
in good agreement with the experimental results; the vibrational modes are assigned based on
1
TED calculation. The H and 13C NMR chemical shift values are in good harmony with the
experimental results. The small HOMO-LUMO energy gap indicates the compound CZPTZA
has potential applications in the field of OSCs. The predicted first hyperpolarizability value (β)
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of molecule is nearly ten times greater than that of urea, which shows that the title chemical
entity is an attractive object for future studies of nonlinear optical properties.
Acknowledgement
Financial assistance provided by the Council of Scientific and Industrial Research (CSIR), New
Delhi, India [02(0099)/12/EMR II] is gratefully acknowledged.
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Table 1
Crystal data of CZPTZA.
10-(9-hexyl-9H-carbazol-3yl-)-10H-phenothiazine-3-carbaldehyde
Empirical formula
Formula weight
Temperature
C31H28N2OS
476.60
273(2) K
Wavelength
0.71073 A
Crystal system, space group
Monoclinic, P 21/n
a = 11.9022(5) A
b = 9.2214(3) A
c = 22.7176(8) A
2454.76(16) A3
4, 1.284 Mg/m3
0.159 mm-1
α = 90°
β = 100.096(2)°
γ = 90°
Unit cell dimensions
Volume
Z, Calculated density
Absorption coefficient
F(000)
1000
Theta range for data collection
Limiting indices
1.815 to 28.898°
-16 < h < 16, -12 < k < 12, -30 < l < 30
35686/6449 [R(int) = 0.0522]
100.0 %
6449/0/327
1.042
Reflections collected/unique
Completeness to theta = 25.242
Data/restraints/parameters
Goodness-of-fit on F^2
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0915, wR2 = 0.2685
R1 = 0.1642, wR2 = 0.3327

ACCEPTED MANUSCRIPT
Table 2
Selected structural parameters for CZPTZA.
Bond length
C1-C2
C1-C6
C2-C3
C3-C4
C4-C5
C4-N7
C5-C6
C5-S10
N7-C8
Calc.
Expt.
Bond length
C17-C22
Calc.
1.406
1.396
1.420
1.446
1.398
1.386
1.390
1.419
1.398
1.392
1.397
1.456
1.390
1.404
1.391
1.535
1.533
1.533
1.533
1.531
Calc.
120.6
119.2
119.7
133.7
106.6
121.2
109.2
129.6
118.1
121.3
106.5
133.8
119.7
109.2
121.4
129.4
108.5
Expt.
1.396(5)
1.387(4)
1.405(5)
1.445(5)
1.390(5)
1.379(4)
1.372(5)
1.399(5)
1.391(5)
1.367(5)
1.407(5)
1.462(5)
1.368(6)
1.387(7)
1.376(7)
1.485(6)
1.455(8)
1.568(9)
1.020(11)
1.647(17)
Expt.
120.4(3)
119.0(3)
119.7(3)
133.4(3)
106.9(3)
121.5(3)
108.6(3)
129.9(3)
117.5(3)
121.9(3)
105.7(3)
133.8(3)
120.5(3)
110.1(3)
120.5(4)
129.4(4)
108.8(3)
1.391 1.376(7)
1.393 1.358(6)
1.393 1.379(5)
1.402 1.396(5)
1.406 1.395(5)
1.424 1.412(4)
1.393 1.396(5)
1.779 1.744(4)
1.406 1.388(4)
1.444 1.444(4)
1.411 1.408(4)
1.410 1.402(5)
1.780 1.753(4)
1.388 1.364(5)
1.384 1.366(5)
1.400 1.388(5)
1.400 1.387(5)
1.472 1.445(5)
1.214 1.202(5)
1.390 1.378(5)
C18-C19
C19-C20
C19-C23
C20-C21
C20-N25
C21-C22
C23-C24
C23-C26
C24-N25
C24-C29
N25-C30
C26-C27
C27-C28
C28-C29
C30-C31
C31-C32
C32-C33
C33-C34
C34-C35
N7-C17
C8-C9
C8-C11
C9-S10
C9-C14
C11-C12
C12-C13
C13-C14
C13-C15
C15-O16
C17-C18
Bond angle
Calc.
Expt.
Bond angle
C2-C1-C6
C1-C2-C3
C2-C3-C4
C3-C4-C5
C3-C4-N7
C5-C4-N7
C4-C5-C6
C4-C5-S10
C6-C5-S10
C1-C6-C5
C4-N7-C8
C4-N7-C17
C8-N7-C17
N7-C8-C9
N7-C8-C11
C9-C8-C11
C8-C9-S10
119.0 119.8(4)
120.6 120.2(4)
121.0 121.0(4)
117.9 118.1(3)
121.2 120.1(3)
120.9 121.8(3)
120.8 119.6(4)
120.1 122.4(3)
118.9 117.7(3)
120.6 121.2(4)
121.7 123.9(3)
118.1 117.2(3)
118.4 118.9(3)
120.9 122.3(3)
121.3 120.3(3)
117.9 117.4(3)
120.1 121.6(3)
C18-C17-C22
C17-C18-C19
C18-C19-C20
C18-C19-C23
C20-C19-C23
C19-C20-C21
C19-C20-N25
C21-C20-N25
C20-C21-C22
C17-C22-C21
C19-C23-C24
C19-C23-C26
C24-C23-C26
C23-C24-N25
C23-C24-C29
N25-C24-C29
C20-N25-C24
2

ACCEPTED MANUSCRIPT
C8-C9-C14
S10-C9-C14
C5-S10-C9
C8-C11-C12
C11-C12-C13
C12-C13-C14
C12-C13-C15
C14-C13-C15
C9-C14-C13
C13-C15-O16
N7-C17-C18
N7-C17-C22
120.5 120.2(3)
119.1 117.9(3)
98.9 101.96(16)
C20-N25-C30
C24-N25-C30
C23-C26-C27
C26-C27-C28
C27-C28-C29
C24-C29-C28
N25-C30-C31
C30-C31-C32
C31-C32-C33
C32-C33-C34
C33-C34-C35
125.7
125.6
119.1
120.6
121.5
117.8
113.5
112.8
113.1
113.7
113.2
124.3(3)
126.9(3)
118.8(4)
120.7(4)
122.3(4)
117.2(4)
114.8(4)
114.8(5)
114.9(7)
129.8(12)
125.7(13)
121.2 121.3(3)
120.7 121.2(3)
118.6 117.7(3)
121.5 121.2(4)
119.9 121.1(3)
121.1 122.3(3)
125.2 126.3(4)
118.6 118.3(3)
120.7 121.3(3)
Dihedral angle
C6-C1-C2-C3
C2-C1-C6-C5
C1-C2-C3-C4
C2-C3-C4-C5
C2-C3-C4-N7
C3-C4-C5-C6
C3-C4-C5-S10
N7-C4-C5-C6
N7-C4-C5-S10
C3-C4-N7-C8
C3-C4-N7-C17
C5-C4-N7-C8
C5-C4-N7-C17
C4-C5-C6-C1
S10-C5-C6-C1
C4-C5-S10-C9
C6-C5-S10-C9
C4-N7-C8-C9
C4-N7-C8-C11
C17-N7-C8-C9
C17-N7-C8-C11
C4-N7-C17-C18
C4-N7-C17-C22
C8-N7-C17-C18
C8-N7-C17-C22
N7-C8-C9-S10
N7-C8-C9-C14
C11-C8-C9-S10
C11-C8-C9-C14
N7-C8-C11-C12
C9-C8-C11-C12
C8-C9-S10-C5
Calc.
-1.0
-0.9
1.2
Expt.
Dihedral angle
Calc.
179.8
0.0
-179.7
0.2
0.0
-179.9
0.0
179.7
179.8
-0.4
179.7
-0.3
-0.1
179.8
0.2
Expt.
178.2(3)
-0.1(5)
-178.4(3)
-0.2(5)
0.4(4)
-179.1(3)
-0.4(5)
179.8(3)
179.2(3)
-0.6(3)
179.5(3)
0.3(6)
-0.1(3)
-179.2(4)
0.2(5)
1.0(7)
-2.8(7)
1.5(7)
-2.2(6)
N7-C17-C18-C19
C22-C17-C18-C19
N7-C17-C22-C21
C18-C17-C22-C21
C17-C18-C19-C20
C17-C18-C19-C23
C18-C19-C20-C21
C18-C19-C20-N25
C23-C19-C20-C21
C23-C19-C20-N25
C18-C19-C23-C24
C18-C19-C23-C26
C20-C19-C23-C24
C20-C19-C23-C26
C19-C20-C21-C22
N25-C20-C21-C22
C19-C20-N25-C24
C19-C20-N25-C30
C21-C20-N25-C24
C21-C20-N25-C30
C20-C21-C22-C17
C19-C23-C24-N25
C19-C23-C24-C29
C26-C23-C24-N25
C26-C23-C24-C29
C19-C23-C26-C27
C24-C23-C26-C27
C23-C24-N25-C20
C23-C24-N25-C30
C29-C24-N25-C20
C29-C24-N25-C30
C23-C24-C29-C28
0.5
-179.9 176.4(4)
-2.4 0.5(6)
172.8 175.3(3)
178.0 -178.2(4)
-6.9
-3.4(5)
150.7 163.1(3)
-13.7
-29.6
166.0 159.2(3)
2.6 2.1(7)
-172.6 -173.0(4)
33.8 20.0(4)
-151.0 -165.1(3)
28.7 16.8(6)
-19.5(5)
-18.3(6)
-179.5
0.9
175.3
-179.5
-5.0
179.8(3)
1.0(4)
179.9(3)
-178.7(3)
0.2(6)
-152.1 -164.2(4)
-167.0 -160.6(3)
12.2
-97.9
82.0
97.2
-82.9
8.6
-177.4 178.7(3)
-170.7 -173.0(3)
3.3
18.4(5)
-85.1(4)
93.1(4)
92.5(4)
-89.3(4)
6.0(5)
-0.2
0.7
0.2(5)
0.7(4)
-179.7
-179.3
0.4
179.9
-0.2
-179.0(3)
180.0(3)
0.3(5)
178.8(4)
-0.3(5)
-0.9
-1.1(4)
-0.3(5)
-175.4
179.4
4.9
-179.9(3)
178.6(4)
-0.2(6)
179.4 -177.5(4)
-1.3
-34.7
1.6(6)
-21.2(3)
-0.3
0.1(6)
3