Noncovalent interaction stabilizes the 2,4-Dinitrophenylhydrazone Derivatives over g-C3N4 surface to enhance optical properties: Synthesis, characterization, and DFT investigation

Article abstract of DOI:10.1016/j.molstruc.2020.128192

Immobilization of organic compounds on semiconductor surface was recently exploited to enhance the semiconductor light absorption and photocatalytic performance. Here, synthesis of 2,4-Dinitrophenylhydrazone-benzaldehyde (DPHH), 2,4-Dinitrophenylhydrazone

Full text of DOI:10.1016/j.molstruc.2020.128192

Journal Pre-proof
Noncovalent interaction stabilizes the 2,4-Dinitrophenylhydrazone Derivatives over
g-C N surface to enhance optical properties: Synthesis, characterization, and DFT
3
4
investigation
Mohammed T. Alotaibi
PII:
S0022-2860(20)30517-2
DOI:
https://doi.org/10.1016/j.molstruc.2020.128192
MOLSTR 128192
Reference:
To appear in: Journal of Molecular Structure
Received Date: 18 January 2020
Revised Date: 31 March 2020
Accepted Date: 1 April 2020
Please cite this article as: M.T. Alotaibi, Noncovalent interaction stabilizes the 2,4-
Dinitrophenylhydrazone Derivatives over g-C N surface to enhance optical properties: Synthesis,
3
4
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AUTHORSHIP STATEMENT
Manuscript
title:
Noncovalent
interaction
stabilizes
the
2,4-
Dinitrophenylhydrazone Derivatives over g-C N Surface to Enhance Optical
3
4
Properties: Synthesis, Characterization, and DFT Investigation
Authorship contribution
I herby declare that I, Mohammed T. Alotaibi performed the
Conception and design of study, acquisition of data, analysis and/or
interpretation of data, Drafting the manuscript, and Approval of the
version of the manuscript to be published
Author name
Mohammed T. Alotaibi

Noncovalent interaction stabilizes the 2,4-Dinitrophenylhydrazone Derivatives over g-
C N Surface to Enhance Optical Properties: Synthesis, Characterization, and DFT
3
4
Investigation
Mohammed T. Alotaibi
Department of Chemistry, Turabah University collage, Taif University, Turabah, Saudi
Arabia
Abstract
Immobilization of organic compounds on semiconductor surface was recently
exploited to enhance the semiconductor light absorption and photocatalytic performance.
Here,
Dinitrophenylhydrazone-2-thiophenecarboxyaldehyde (DPHS), 2,4-Dinitrophenylhydrazone-
-dimethylaminobenzaldehyde (DPHN) and 2,4-Dinitrophenylhydrazone-4-aminobenzoic
synthesis
of
2,4-Dinitrophenylhydrazone-benzaldehyde
(DPHH),
2,4-
4
acid (DPHB) was introduced and characterized with different spectroscopic techniques such
as FT-IR and UV-Vis spectroscopy. The UV-vis absorption spectra of the hydrazone
compounds were stabilized (red shifted) in polar solvents such as N,N-dimethylformamide
(DMF) and acetonitrile (ACN). Density functional theory (DFT) was used to investigate the
structures conformations and stabilizing forces. Doping of g-C N nanosheets with 5% of the
3
4
hydrazone derivatives decreases the optical band gap from 2.71 eV to 2.62 eV with DPHN
derivatives. The DFT investigation coupled with reduced density gradient (RDG) show that
hydrazone derivatives was stabilized on g-C N by vdW forces. These results shows that the
3
4
hydrazone derivatives could be potentially used as sensitizers for photocatalysis and solar
cells systems.
1

Keywords: 2,4-Dinitrophenylhydrazone derivatives; solvent effect; g-C N ; optical bandgap;
3
4
DFT
1
. Introduction
Recently, photocatalysis has been emerged as promising process for different applications
1,2]. For example, harvesting sunlight by semiconductors for renewable energy production
[
such as H under visible light is a promising economic and clean technology [3]. On another
2
hand, removal of organic/inorganic pollutants from wastewater is efficient and cheap
photocatalysis applications [4,5]. In photocatalysis, semiconductor plays the vital role in light
absorption and subsequent electron/hole generation process [6]. Different semiconductors
materials have been used such as TiO [7,8], MoS [9,10], V O [11], and g-C N [6,12]. The
2
2
2
5
3
4
metal free 2D dimension g-C N is one of the promising materials in these applications. The
3
4
structure of g-C N has been theoretically investigated by different researchers [13-16]. The
3
4
corrugated structure was more stable than the corresponding planar isomer, which stabilizes
the Fermi level and increasing the active site through π-hole formation [13,14]. The
mechanical properties of g-C N such as strain response, elastic constant electronic and
3
4
magnetic properties was explored [17,18]. The electric properties of the nanosheet was stable
under 10 V/nm electric field. However, the pristine g-C N material suffers from different
3
4
drawback such as the lack of visible light absorption and the fast electron/hole recombination.
In order to overcome these drawbacks, several techniques have been used such as doping g-
C N with metal nanoparticles [19,20] to prevent the electron/hole recombination process or
3
4
with organic dyes to extend the visible light absorption efficiency. To increase the g-C N4
3
visible light absorption, several dyes have been used such as Montmorillonite [21], Bentonite
[
22], Erythrosine B [23], Fluorescein [19,24], Eosin Y, basic fuchsin [25] and Rose Bengal
2

[
26]. However, most of the used dyes suffer from stability, expensive, and in some cases the
tedious preparation method.
On the other hand, 2,4-dinitrophenyhydrazine (2,4 DNP) reacts with different
aldehydes and ketones by condensation reactions to give the corresponding hydrazine
compounds in high yield and moderate conditions [27-29]. The reaction results on colored
compounds, which is the basis for the visual detections of aldehydes and ketones in vivo and
vitro applications [30]. It is also used in high throughput detection of mutants strains [31]. 2,4
DNP was used in combination with nanoalumina for adsorption of heavy metals from water
[
32]. In addition, pyrazolone derivatives were reported as an antibacterial and anti-
tuberculosis agents [33].
Here, we use the simple synthesized of 2,4 DNP hydrazine derivatives coupled with g-C N4
3
to enhance the optical band gap. The synthesized compounds were characterized with
different spectroscopic techniques such as FT-IR and UV-Vis in different solvents.
Theoretical calculations with density functional theory (DFT) were corroborated experimental
results to further investigate the titled compounds.
2
. Experimental
2
.1 Materials: 2,4-dinitrophenylhydrazine (2,4-DNP), 4-dimethyaminobenzaldehyde, 2-
thiophenecarbaldehyde, and 4-aminobenzoic acid was purchased from Sigma-Aldrich,
Germany. All solvents wear supplied by Sigma-Aldrich, Germany and used without further
purification.
2
2
.2 Preparations
,4-DNP derivatives: preparation of 2,4-DNP derivatives wear performed according to the
literature [28]. For example, DPHN was synthesized by taking 0.99 g (5 mmole) from 2,4-
DNP and 0.745 g (5 mmole) from 4-dimethylaminobenzaldehyde in ethanol. The 2,4-DNP
3

color was orange which turns to deep brown after DPHN formation. The solution was
reflexed for 4 h at 120 °C for complete reaction. The deep brown DPHN solid product was
collected by filtration and washed with ethanol several time. Similarly, 2,4-DNP was reacted
with 2-thiophene-carbaldehyde, 4-aminobenzoic acid, and benzaldehyde and the products
wear coded as DPHS, DPHB, and DPHH respectively.
g-C N nanosheet: the bulk g-C N was synthesized by adding 10 g from urea in a closed
3
4
3
4
crucible and heated in furnace at 550 °C for 2h (5 °C/min). g-C N nanosheet was prepared by
3
4
dissolving 100 mg of the bulk g-C N in methanol and sonicated for 4 hrs. Then the solution
3
4
was centrifuged and removes the remained solid product. The suspended g-C N nanosheet
3
4
was collected and stored for further use.
.3 Characterization
2
The UV-Vis absorptions measurements of hydrazone derivatives in different solvents were
performed using Perkin-Elmer Lambda 11 UV/VIS spectrophotometer using 1 cm quartz cell.
Reflectance measurements were performed using Ocean optic spectrometer USB4000-
UV-VIS-ES.
The fluorescence measurements wear performed using JASCO
spectrofluoremeter (model-FB-8300). IR was measured using Perkin-Elmer FT-IR
-1
spectrophotometer in 4000-400 cm range.
2
.4 Computational details
The structures were optimized to the minimum energy using Gaussian09 package
[
34]. Frequency calculations were performed in order to confirm that the optimized structures
have minimum energy at the potential energy scan. B3lyp functional wear used with the 6-
11G(d,p) basis set. Time-dependent density functional theory (TD-DFT) was performed to
calculated the molecular frontier HOMO and LUMO orbitals. Non-covalent interactions
3
(NCI) were investigated using Multiwfn program [35] and visualized by VMD (1.9) [36].
4

Scheme 1: structure of 2,4 DNP derivatives.
3
. Results and Discussion
3
.1 Structures geometry optimization of hydrazone derivatives
The reaction between 2,4 DNP and different aldehydes through condensation yields
Schiff bases, DPHH, DPHS, DPHN, and DPHB (Scheme 1). The optimized structure of 2,4
DNP showed that the compound was stabilized by the strong hydrogen bonding between
H18…O11 (Fig.1a). The calculated electrostatic potential shows the presence of electron
deficiency region over the –NH group which could be the possible position for the
2
nuclophilic attach (Fig 1b). The condensation reactions on the NH group for 2,4 DNP was
2
confirmed by the HOMO and LUMO energy calculations (Fig.1c and d). The HOMO orbital
of 2,4 DNP was distributed over the whole molecule, particularly the NH group, while the
2
LUMO orbitals was situated on the phenyl ring [37]. The reaction of 2,4 DNP with different
aldehyde in ethanol yields 2,4 DNP hydrazine derivatives (Scheme 1). DFT calculations show
that the products were stabilized by strong hydrogen bond (HB) between the NO oxygen
2
atom and the -N-H group hydrogen atom, which is reported for similar hydrazine compounds
in solid state [38] and solution [28]. The HB distance was 1.85, 1.84, 1.85, 1.84 Å and the
0
bond angle of 129.1, 129.8, 129.7, 129.5 for DPHH, DPHS, PDHN, and DPHB respectively
º
(Fig. 2). DPHS and DPHN were planar molecules with dihedral angle around the N-N of 180
5

º
º
[
28], while the DPHH and DPHB was offset by a dihedral angle of 62.4 and 156.6
respectively.
Fig.1: a) optimized 2,4-DNP structure, b) MEP of 2,4-DNP, c) HOMO orbital of 2,4-DNP, d)
LUMO orbital of 2,4-DNP calculated at B3lyp/6-311g(d,p).
6

Fig.2: optimized structures of 2,4-DNP hydrazone derivatives a) DPHH, b) DPHN, c) DPHS,
and d) DPHB calculated at B3lyp/6-311g(d,p).
The reaction of 2,4 DNP with different aldehyde was investigated by the FT-IR spectroscopy.
-1
2
,4-DPN shows vibration peaks at 3390 and 3300 cm , which corresponds to the NH and N-
2
H groups respectively (Fig.3a) [28]. The C-H stretching aromatic mode for benzene ring
-1
-1
vibration appears at 3072 cm in addition to the in plane-bending mode (1400-850 cm ) and
-1
out of plane bending mode (950-600 cm ) (Fig.3b). In addition, 2,4 DNP has two NO
2
-1
groups, which normally show up for free groups in the region 1600-1350 cm for symmetric
and antisymmetric stretching modes. However, in this work, the antisymmetric and
symmetric modes of NO observed at 1566 and 1367 respectively. The NO groups vibrations
2
2
-1
were red shifted compared to the literature values (1600-1349 cm ) [39], was attributed to
intramolecular hydrogen bond formation (N-H..Onitro). The in-plane and out-of plane modes
-1
of NO groups appear at 827 and 620 cm respectively. Upon reaction of 2,4-DNP with the
2
-1
corresponding aldehyde, for example DPHN, the peak at 3390 cm disappear and only sharp
-1
vibration peak at 3300 cm was observed indicated the formation of the corresponding Schiff
bases [32]. The formation of the Schiff bases were accompanied by the appearance of the
-1
C=N vibration peak at 1595 cm (Fig. 3a ).
7

Fig. 3: FT-IR of a) 2,4-DNP and DPHN, b) magnified spectra 2,4-DNP and DPHN.
.2 absorption spectra and solvent effect
3
The UV-Vis absorption spectra of 2,4-DPN derivatives are shown in Fig. 4. The synthesized
*
Schiff bases gives an absorption peak in the 250-300 nm which assigned to the π-π transition
[
27]. In addition, a strong and broad peak at 358, 370, 392, 424 for DPHB, DPHH, DPHS,
and DPHN in ethanol was observed respectively (Table 1). The red shifted UV-Vis peak of
*
2
,4-DNP derivatives was assigned to the n-π transition. For example, the higher red shifted
peak of DPHN at 424 nm in ethanol attributed to the intramolecular charge transfer (ICT)
between the N-dimethyphenyl moiety (donor) and the 2,4 dinitrophenylhydrazine moiety
(acceptor). The TD-DFT calculations were performed to determine the HOMO, LUMO
frontier orbitals and the oscillator strength of the electronic transition (Fig. 5 and Table 1).
The HOMO orbitals were distributed over the whole molecules, while the LUMO orbitals
was situated over the 2,4-DNP moiety [27]. The energy gap gives and indication for
important physical parameters such as stability and reactivity. Table 2 show that 2,4 DNP
hydrazones have small energy gap that indicates the presence of small energy barrier for
electron transfer transition. The red shifted peak in 2,4 DNP hydrazones was assigned to the
HOMO→LUMO transition (Fig. 5), which have the higher electronic transition and higher
oscillator strength (Table 2). The calculated transition (TD-DFT) The calculated band gap
8

was in the order of DPHH > DPHS > DPHB > DPHN, which in accordance with the
experimental absorption peak position the same order. The exceptional band gap decrease in
DPHB could be attributed to the offset structure from linearity and the higher charge transfer
to 2,4-DNP moiety (-0.25) compared to other derivatives (Table 2).
In order to investigate the solvent effect on the optical properties, the absorption spectra of
2
,4-DNP hydrazone derivatives were monitored in different solvents (Fig. 4). The absorption
spectra of the 2,4-DNP derivatives show significant change with the change in solvent
polarity, particularly, in polar solvents. The absorption spectra were red shifted with the
increase in the solvent polarity (Table 1) in DMF > ACN > MeOH > EtOH > CHCl . In order
3
to confirm the stability of 2,4 DNP hydrazones in polar solvents, the TD-DFT were
performed using self-consistent reaction field (SCRF) and polarized continuum model (PCM).
The predicted absorption peaks along with the oscillator strength for the singlet-singlet
transition are shown in Table 2. The results show that the ICT peak was red shifted from
ethanol to DMF, which attributed to the increase of the solvent polarity.
9

Fig. 4: Absorption spectra of 10 µm of a) DPHH, b) DPHN, c) DPHS, and d) DPHB in
different solvents.
Table 1: Measured and calculated (TD-DFT) absorption spectra of 2,4 DNP hydrazone
derivatives in different solvents (λmax in nm).
DPHB
Exp.
DPHH
DPHS
Exp.
DPHN
Exp.
ε
Calc.
378
Exp.
Calc.
Calc.
Calc.
DMF 37.22
372
391
395
403
408
441
446
a
(0.72)
(0.65)
(0.74)
(0.81)
ACN 35.68
367
382
424
428.6
10

MeOH 32.6
EtOH 24.85
360
358
378
370
392
392
422
424
367.2
0.63)
375
399
428
(
(0.64)
(0.74)
(0.84)
CHCl3
4.7
350
365
392
432
a
Oscillator strength for the HOMO-LUMO transition
11

Fig. 5: calculated HOMO and LUMO orbital for the optimized structures of 2,4-DNP
hydrazone derivatives a) DPHH, b) DPHN, c) DPHS, and d) DPHB calculated at B3lyp/6-
3
11g(d,p).
3
.3 Molecular Electrostatic potential of 2,4 DNP hydrazone derivatives
In order to investigate the reactivity of the 2,4 DNP hydrazone, the molecular
electrostatic potentials (MEP) for the optimized compounds were calculated. MEP predicts
the charge distribution over the molecule; the negative region is dominated by the high
electron density and prone to an electrophilic attack or performs as electron donor sites. On
the other hand, the positive region is an electron deficient region and prone to nucleophilic
attack or perform as electron acceptor sites. The MEP of the 2,4 DNP hydrazone derivatives
were performed at the optimized structure (B3lyp/6-311g(d,p)) (Fig. 6). The negative charge
sites were situated on the NO group of the 2,4 DNP moiety, while the positive sites were
2
localized on the substituted aryl moiety.
Fig. 6: Calculated molecular electrostatic potential of 2,4-DNP hydrazone derivatives a)
DPHH, b) DPHN, c) DPHS, and d) DPHB calculated at B3lyp/6-311g(d,p).
3
.4 Immobilization of hydrazone derivatives on g-C N surface
3 4
12

In order to investigate the optical properties of the 2,4-DNP derivatives on the g-C N4
3
surface, 5% from the DPHX compounds were added to the g-C N . The FT-IR spectrum of g-
3
4
-1
C N gives a broad peak for the N-H group in the range 3100-3300 cm , which was broadens
3
4
after the addition of hydrazone derivatives (Fig. 7a). Weak peaks in the 100-1200 were
observed due to the C-N stretching mode that confirm the successful integration of hydrazone
0
derivatives into g-C N structure [25]. The XRD diffraction of g-C N shows two peaks at 13
3
4
3
4
0
and 27 for the in-plane structure and the interlayer stacking respectively (Fig.7b) [40].
Doping of the g-C N with 5% of the DPHX derivatives did not change the peak position,
3
4
however, the peaks were broaden that confirm the intercalation of the Schiff bases between
the g-C N layers [40]. The UV-vis absorption of DPHS shows a peak at 390 nm in ethanol
3
4
solution. Upon addition of 3 mg/ml g-C N to an ethanolic solution of DPHS, the UV-vis
3
4
absorption spectra shows an enhanced absorption tail in the visible region in addition to the
main peak at 390 nm (Fig. 7c).
Fig. 7: a) FT-IR spectrum and b) XRD diffraction of g-C N and g-C N -DPHN, c)
3
4
3
4
absorption spectra of 10 µm DPHS and g-C N /DPHS in ethanol.
3
4
The emission spectra of 2,4-DNP derivatives show very low fluorescence peak at 470 nm.
The low emission of the 2,4-DNP derivatives attributed to the internal photo-electron transfer
(
PET) from the aryl moiety to the 2,4-DNP moiety. On the other hand, g-C N shows broad
3 4
fluorescence peak at 456 nm (λ = 400 nm), attributed to the fast electron/hole recombination
ex
process [41]. Upon immobilization of the 2,4-DNP derivatives on g-C N surface, the
3
4
13

emission peak at 456 nm was decreased due to inhibition of electron/hole recombination
process. For example, addition of 80 µM of PDHH to g-C N decreases the emission
3
4
intensity by 63% (Fig. 8a). The emission of g-C N was red shifted with the addition of 2,4-
3
4
DNP hydrazone derivatives (Fig. 8b), which ascribed to decreases of the band gap and
existence of sub-band gap levels [41].
Fig. 8: Fluorescence (λ = 400 nm) of a) g-C N with different concentration of DPHH and,
ex
3
4
b) g-C N with different 2,4 DNP hydrazone derivatives in MeOH.
3
4
Fig.9a show the reflectance spectra of 5%2,4 DNP derivatives deposited on g-C N . The
3
4
spectrum shows the change of g-C N reflectance with the 5%2,4 DNP derivatives. The
3
4
change in the band gap of g-C N was calculated after the addition of 5%2,4 DNP derivatives
3
4
(
Fig. 9b). The pristine g-C N posses band gap energy of 2.7 eV [42,43]. Table 2 shows that
3 4
addition of 5%2,4 DNP derivatives to g-C N decreases the band gap from 2.71 to 2.62 eV
3
4
with the addition of 5%DPHN [25]. The DFT calculations of DPHX/g-C N show the
3
4
stabilizations of the composite by noncovalent interactions. The calculated energy gap at the
optimized structures was used to corroborate the experimental data. The E of the optimized
g
structures indicate the decrease of the g-C N band gap with the addition of different
3
4
hydrazone derivatives in the order DPHH < DPHS < DPHB < DPHN (Table 2). This result is
in accordance with the increase of the charge transferred from g-C N to DPHX derivatives
3
4
14

(Table 2) that inhibit the electron/hole recombination [44]. In addition, the decrease in the
band gap intensity increases with the increase of the DPHX light absorption in the visible
region. Table 1 show that the absorption spectra of DPHN is more red shifted (λmax= 441 nm
in DMF), which improve the light absorption of g-C N and tune the band gap structure [25].
3
4
Fig. 9: a) reflectance spectra of g-C N and 5%2,4 DNP hydrazones, b) Diffuse reflectance of
3
4
g-C N and 2,4 DNP derivatives.
3
4
Table 2: Calculated HOMO, LUMO, energy gap (eV), electronic charge (C/e) on g-C N at
3
4
B3lyp/6-311g(d,p) and the measured band gap of the solid 2,4 DNP hydrazone derivatives.
a
a
a
EHOMO ELUMO Egap Band gap C/e
g-C N4
-6.70
-6.52
-3.03 3.67
-2.98 3.54
-2.94 3.39
-3.09 3.22
-3.08 3.04
-2.95 3.04
-3.22 2.29
-2.80 2.79
2.71
2.70
2.68
2.65
0
3
DPHH
g-C N / 5%DPHH -6.33
0.04
0.06
0.07
3
4
DPHS
-6.31
g-C N / 5%DPHS -6.12
3
4
DPHB
-5.99
-5.51
-5.59
g-C N / %DPHB
3
4
DPHN
15

g-C N / 5%DPHN -5.43
-3.22 2.21
2.62
0.15
3
4
3
.5 Analysis of Noncovalent Interactions (NCI)
Noncovalent interactions such as hydrogen bonding, halogen bonding, π-π
interactions, and vdW forces were responsible for the assembly of molecular and
supramolecular systems [45-48]. In order to investigate the nature of the molecular
interactions between the 2,4-DNP derivatives with g-C N , NCI theory was used [35,49]. NCI
3
4
distinguishes weak interactions as low electron density (ρ) and low reduced density gradients
RDG) areas. In NCI, the blue isosurface value indicate the presence of strong attractive
(
interactions, while the green isosurface shows the presence of weak interactions such as vdW
forces [35,50]. Analyzing the NCI results shows that the main forces between g-C N and 2,4-
3
4
DNP derivatives is the vdW forces (green isosurface) and hydrogen bonding (Fig. 10). The
vdW forces appears at -0.01 a.u < (λ )ρ > 0.01 a.u (Fig. 11). In addition, the RDG plot shows
2
the presence of hydrogen bond (HB) at -0.02 a.u < (λ )ρ > -0.01 a.u, which ascribed to the
2
intramolecular hydrogen bonding within the hydrazine derivatives (Fig. 11) and
intermolecular hydrogen bonding in g-C N /2,4-DNP hydrazone derivatives.
3
4
16

Fig. 10: Noncovalent interaction isosurface plot of a) DPHH, b) DPHN, c) DPHS, and d)
DPHB
Fig. 11: NCI 2D plot of a) DPHH, b) DPHS, c) DPHN, and d) DPHB
17

The molecular interactions between g-C N and 2,4-DNP derivatives were investigated in
3
4
ethanol and DMF environments using the optimized structures at B3lyp/6-311g(d,p) level and
PCM solvent model. Table 3 shows the relative binding energies of the g-C N /DPHX and the
3
4
corresponding charge transfer form g-C N to DPHX derivatives. The calculated binding
3
4
energy of the investigated complexes was higher in DMF than ethanol with the increase of the
amount of the transferred charges in the same order. This indicates that the complexes are
stabilized in the polar solvents, which could be attributed to the facile charge transfer inside
the complexes in polar solvents.
Table 3: Relative binding energies (kcal/mole) of DPHX/g-C N in different solvents
3
4
calculated at B3lyp/6-311g(d,p) level and PCM solvent model.
EtOH
DMF
a
g-C N /DPHH
−4.6 (0.06)
−4.9 (0.08)
−5.4 (0.014)
−6.1 (0.020)
−7.2 (0.015)
−8.1 (0.025)
−8.6 (0.030)
−8.2 (0.040)
3
4
g-C N /DPHS
3
4
g-C N /DPHB
3
4
g-C N /DPHN
3
4
a
Data in parenthesis is the charge transferred from g-C N to DPNX
3
4
4
. Conclusion
Four hydrazone derivatives of 2,4 dinitrophenylhydarazine were synthesized and
characterized using different spectroscopic techniques. The optical properties of the
derivatives were investigated in different solvents. The UV-Vis absorption of the hydrazones
were stabilized in polar solvents, which confirmed by the TD-DFT calculations.
Immobilization of the hydrazone derivatives on g-C N surface were stabilized by
3
4
nonocovalent interactions such as hydrogen bonding and vdW forces. The optical band gap of
18

g-C N was decreased by doping of 5% of DPNX derivatives, which attributed to the
3
4
extended absorption of the complexes in the visible region and facile charge immobilization.
Acknowledgment
The author thanks Taif University, Deanship of scientific research for financial support with
project No.1/439/6061.
5
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20

Highlights
•
Synthesis, DFT calculations, and solvent effect of 2,4-DNP Derivatives.
•
•
Polar solvents stabilize the absorption of 2,4-DNP Derivatives under visible light.
The band gap of g-C nanosheet decreases by 2,4-DNP derivatives due to charge
3
N
4
transfer and light absorption increasing.
•
Nonocovalent interactions stabilize the 2,4-Dinitrophenylhydrazone Derivatives/g-
3 4
C N composite.

Conflict of interest: the author declare no conflict of interest