Journal of Molecular Structure 1250 (2022) 131930

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

One-pot synthesis of some new 7–hydroxy-5-(4-substitutedphenyl)-

9-methyl-1,5-dihydro-2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–
dione derivatives and it’s optoelectronic, DFT, photocatalytic studies
and latent fingerprint applications
K. Upendranath a, Talavara Venkatesh a,∗, M. Shashank b, G. Nagaraju c,
K. M. Mussuvir Pasha d
a
Department of P.G. Studies and Research in Chemistry, Kuvempu University, Jnana Sahyadri, Shankaraghatta, Karnataka 577451, India
b
Department of P.G. Studies and Research in Industrial Chemistry, Kuvempu University, Jnana Sahyadri, Shankaraghatta, Karnataka 577451, India
c
Department of Chemistry, Energy Materials Research Laboratory, Siddaganga Institute of Technology, Tumakuru, Karnataka 572103, India
d
Department of P.G. Studies and Research in Chemistry, Vijayangara Sri Krishnadevaraya University, Ballari, Karnataka 583105, India

a r t i c l e i n f o a b s t r a c t

Article history: Metal-free organic dyes are gaining interest and demands in the field of light absorption and light-
Received 20 July 2021 emitting applications. In this study, we developed efficient one-pot synthesis of 7–hydroxy-5-(4-
Revised 25 October 2021
substitutedphenyl)-9-methyl-1,5-dihydro-2H-dipyrimido[1,2-a:4 ,5 d]pyrimidine-2,4(3H)–dione derivatives
Accepted 12 November 2021
4(a-d) using L-proline as a catalyst and structures were confirmed by analytical and spectroscopic tech-
Available online 15 November 2021
niques. Photophysical properties have been studied in a liquid medium; compounds are absorbed in
Keywords: bathochromic shift at ∼30 0–50 0 nm and blue emission at 530 nm, 560 nm, 401 nm and 614 nm, 622 nm
Pyrimidine respectively. Electrochemical behavior was studied at different scan rates in CH Potentiostat. CV results
Photoluminescence revealed that all the compounds shows quasi reversible behavior and experimental HOMO-LUMO have
Electrochemical been calculated. FMOs, optimized structure and quantum parameters along with UV, FT-IR and COSMO-
DFT RS were investigated theoretically. From the theoretical results, compounds are in good agreement with
Photocatalytic
experimental values with better photostability and chemical reactivity. Further, compounds are excel-
LFPs
lent photocatalysts towards the dye degradation of malachite green dye by reaching 65%, 83%, 87% and
65% respectively. In addition, LFPs images were developed on porous/nonporous materials and visualized
under UV light, compounds are excellent adhesion and sensitivity on the porous/nonporous materials.
Hence, the obtained compounds can be used as organic electronics application-oriented materials and in
forensic Science.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction as photo-sensitizers due to their better photophysical properties,

high electron affinity and act as π -acceptor character. Particu-
Metal-free organic dye compounds containing heterocyclic moi- larly, pyrimidine was exhibited higher fluorescent properties when
eties like coumarin indole, pyridine, pyrimidine, etc., are shows having different electron-withdrawing and donating groups [8,9].
better light absorption and light-emitting properties due to their Moreover, it acting as an electron-withdrawing character due to
aromatic conjugations and electronic transitions [1–3]. In gen- its π -deficient nature hence increase color sensitivity, higher mo-
eral, pyrimidines are well-known drugs in the field of medici- lar extinction co-efficient with solvatochromic behavior [10,11].
nal chemistry as anti-analgesic, anti-microbial, anti-inflammatory Photocatalysts play a vital role in purifying the water pollutions
and anti-cancer agents [4–7]. As knows of drug molecules, re- caused by the textile, leather, pulp and paper industries. Till now,
searchers have gained interest to develop and design pyrimi- Nanocomposite metal oxides have been used as photocatalysts un-
dine moieties as photonic materials, as optical chemosensors and der UV-irradiation by dye degradation method. Due to the in-
solubility of metal oxide nanoparticles and the formation of by-
products in the water molecule, researchers interesting to design
∗
Corresponding author. and develop a simple metal-free organic light-absorbing and emis-
E-mail address: [email protected] (T. Venkatesh).

https://doi.org/10.1016/j.molstruc.2021.131930
0022-2860/© 2021 Elsevier B.V. All rights reserved.
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

sion materials as photocatalysts [12]. Additionally, these metal-free Table 1

Analytical data of synthesized compound 4(a–d).
organic compounds can be used to develop latent fingerprints on
porous/nonporous materials and visualized under UV light. [13,14]. Entry R1 R2 Entry Yield MP
Latent fingerprints are commonly, easily and predominantly
used by every forensic analyzer in criminal activities due to the in-
visible to naked eyes [15,16]. At the crime spot, the visualization of
LFPs is suffered a lot because of their low optical contrast, which
4a OH H 84% 235–238 °C
is difficult to see and develop; hence chemical or physical treat-
ment is required to develop for visualization. The visualization of
LFPs requires a good optical contrast and adherence between fin-
gerprints ridges and materials to develop. In earlier days, there are
several methods were carried out for the visualization of LFPs such
as powder dusting, iodine fuming, electrochemistry, vacuum metal
deposition, mass spectrometry and fluorescence spectroscopy [17–
19]. Among these approaches, powder dusting method were com- 4b Cl H 85% 230–235 °C
monly encouraged to use in every crime spot because of the eas-
iest method for visualization of LFPs and data can be stored for
a longer time. However, in general, there are three types of pow-
ders were well known to use such as regular, metallic and organic
fluorescent materials. Regular powders contain polymers and col-
orant powders which are hard to develop on a difficult surface and
metallic powders are injurious to humans due to metals [20–22].
Among these powders, the organic fluorescent powders have been 4c OH OCH3 87% 237–239 °C
using recently due to their high emission properties and found a
good optical contrast between fingerprint ridges and surface mate-
rials, therefore organic fluorescent materials are needed to design
and develop a visualization of LFPs [23].
Considering above results and our research group has been
published pyrimidine derivatives as various biological agents [24–
26]. In this investigation, we report; one-pot synthesis of some
novel 7–hydroxy-5-(4-substitutedphenyl)−9-methyl-1,5-dihydro- 4d Br H 85% 230–232 °C
2H-dipyrimido[1,2-a:4 ,5 -] pyrimidine-2,4(3H)–dione derivatives
4(a–d) using a catalytic amount of l-Proline and studied their
optical, electrochemical, theoretical, photocatalytic studies and
latent fingerprint application.
Time- 8h∗ .
2. Experimental

2.1. Materials and methods were carried by the reaction of 2-amino-4–hydroxy-6-methyl

pyrimidine (1, 1 mmol) barbutric acid (2, 1 mmol) and different
All the chemicals and solvents were purchased from Sigma aromatic aldehydes (3, 1 mmol) in presence of 20 mL of ethanol
Aldrich used without further purification. The 1 H NMR and 13 C using 10 mol% of l-Proline as catalyst. The reaction mixture was
NMR spectra were recorded a Joel delta-2 NMR using DMSO–d6 as reflux with constant stirring for about 6 h and reaction progress
solvent. The absorption spectrum was recorded by UV-Visible spec- was monitored by TLC (Ethyl acetate and Petroleum ether). After
trophotometer (USB-40 0 0, Ocean optics, USA) and the emission the completion, the reaction mixture was cooled to room temper-
spectrum was recorded by Shimadzu RF-5301 PC spectrophotome- ature and poured into the 100 mL flake ice with vigorous stirring
ter. The electrochemical studies were done by Cyclic Voltammo- to get solid colored precipitated. The crude mixture was filtered,
grams (CHI66OD) potentiostat CH instruments using Pt wire as a washed and recrystallized with hot ethanol to afford pure solid
counter electrode, non-aqueous Ag/AgCl as reference electrode and products 4(a–d) (Scheme 1) and analytical data has been appended
Glassy Carbon paste as a working electrode in 1 M KOH solution as in Table 1.
electrolyte. Geometrical optimized structure, FMOs, quantum pa-
rameters, UV-Visible, FT-IR and COSMO-RS values were estimated
by theoretically in Gaussian 09 program at gaseous phase. A pho-
tocatalytic experiment was carried out for the degradation of mala- 2.2.1. 7–hydroxy-5- (4-hydroxyphenyl) −9-methyl −1,5 -dihydro −2H
chite green (MG) dye compound using a UV–Vis spectrophotome- -dipyrimido [1,2-a:4 ,5 -d] pyrimidine-2,4(3H)–dione derivatives (4a)
ter. Latent Fingerprint application was carried out by powder dust- Yield: 84%, mp: 235–238 °C, Color: Reddish orange powder. IR
ing method on using synthesized compounds 4 (a-d) on the dif- (KBr, ν , cm−1 ): 3428 (OH), 3267 (NH), 3185 (C–H), 1663 (C = O)
ferent substrates (Knife, steel coin and mobile phone) and pictures and 1611 (C = N). 1 H NMR (400 MHz, DMSO–d6 , δ ppm): 11.22 (s,
were photographed under UV-light. 1H, NH), 11.09 (s, 1H, NH), 10.77 (s, 2H, OH), 8.30–8.28 (d, J = 8 Hz,
3H, Ar-H), 8.16 (s, 1H, Ar-H), 6.84–6.82 (d, J = 8 Hz, 1H, Ar-H),
2.2. General procedure for the one-pot synthesis of 7–hydroxy-5-(4- 5.73 (s, 1H, CH) and 1.95 (s, 3H, CH3 ). 13 C NMR (100 MHz, DMSO–
substitutedphenyl)−9-methyl-1,5-dihydro-2H-dipyrimido[1,2-a:4 ,5 -d] d6 , δ ppm): 165.30, 164.65 (C = O), 163.54, 162.84 (C = C–NH),
pyrimidine-2,4(3H)–dione derivatives 4(a-d) 156.00, 155.72, 150.76, 139.99, 138.85, 124.30 (C = C), 116.03,
114.71, 100.87 (C=CH) and 23.66 (C–CH3 ). HRMS (m/z): 341.3083
The 7–hydroxy-5-(4-substitutedphenyl)−9-methyl-1,5-dihydro- [M+ ]. Mol. formula: C15 H12 N5 O5 , Anal. Calcd for C 56.64, H 3.86
2H-dipyrimido[1,2-a:4 ,5 -d] pyrimidine-2,4(3H)–dione derivatives and N 20.64%, found: C 55.25, H 3.75 and N 18.97%.

2
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Scheme 1. One-pot synthesis of some new 7-hydroxy-5-(4-substitutedphenyl)−9-methyl-1,5- dihydro-2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives 4(a–
d).

2.2.2. 7–hydroxy-5- (4-chlorophenyl) −9-methyl- 1,5-dihydro 2.3. Preparation of carbon paste electrode
−2H-dipyrimido [1,2-a:4 ,5 -d] pyrimidine −2,4(3H)–dione
derivatives (4b) Carbon electrode paste has been prepared by mixing 75% of
Yield: 85%, mp: 230–235 °C, Color: pale yellow powder. IR (KBr, the graphite powder and 10% of silicone oil was added (20 °C,
ν , cm−1 ): 3400 (OH), 3274 (NH), 3054 (C–H), 1668 (C = O), 1635 0.98–1.0 g/mL and 370–500 mP as viscosity) with a mass ratio of
(C = N) and 786 (C–Cl). 1 H NMR (400 MHz, DMSO–d6 , δ ppm): 15:70:15 was manually mixed in a mortar for about 25 min to en-
11.03 (s, 1H, NH), 10.90 (s, 1H, NH), 8.39–8.37 (d, J = 8, Hz, hance the mechanical strength of the electrode. The well grinded
2H, Ar-H), 8.10 (s, 1H, Ar-H), 6.76–6.73 (d, J = 9.6 Hz, 2H, Ar-H), mixture was pasted into a homemade Teflon cavity (0.3 mm of sur-
5.35 (s, 1H, CH), 1.93 (s, 3H, CH3 ). 13 C NMR (100 MHz, DMSO– face area) tube and then the surface was smoothed, pressing gently
d6 δ ppm): 165.19, 164.23 (C = O), 155.05, 150.71, 140.71, 131.29, on weighing paper to ensure better electrical contact [27].
130.69, 129.58, 129.19 (C = C), 118.99, 101.35 (C=CH) and 22.62
(CH3 ). HRMS (m/z): 358.0815 [M+ ]. Mol. formula: C16 H12 ClN5 O3 ,
Anal. calcd for C 53.73, H 3.38, N 19.58, found: C 53.55, H 3.20, 2.4. Electrochemical studies
N 19.48%.
Electrochemical studies were analyzed at CH Potentiostat
CHI604D electrochemical work station using three-electrode sys-
2.2.3. 7–hydroxy-5-(4–hydroxy-3-methoxyphenyl)−9-methyl-1,5- tems. The electrochemical cell was constructed with Ag/AgCl as
dihydro-2H-dipyrimido[1,2-a:4 ,5 ’-d]pyrimidine-2,4(3H)–dione reference electrode, Glassy carbon as the working electrode and Pt
derivatives (4c) wire as a reference electrode in 1 M KOH aqueous electrolyte so-
Yield: 87%, mp: 237–239 °C, Color: pale yellow powder. IR (KBr, lution [28]. The experiment was carried out at different scan rate
ν , cm−1 ): 3355 (OH), 3176 (NH), 2952 (Ar–OCH3 ), 2849 (C–H), between 10 mVs−1 and 50 mVs−1 , further the redox onset poten-
1661 (C = O) and 1555 (C = N). 1 H NMR (400 MHz, DMSO– tial was determined which use to calculate the energy of molecules
d6 , δ ppm):11.24 (s, 1H, NH), 11.11 (s, 1H, NH), 9.97 (s, 1H, OH), HOMO-LUMO.
8.44–8.43 (d, J = 8, Hz, 2H, Ar-H), 8.18 (s, 1H, Ar-H), 7.77–7.75 (d,
J = 8 Hz, 1H, Ar-H), 5.391 (s, 1H, CH), 3.78 (s, 3H, OCH3 ) and 1.96
(s, 3H, CH3 ). 13 C NMR (100 MHz, DMSO–d6 δ ppm): 164.72, 164.53 2.5. Theoretical studies
(C = O), 156.40, 155.67, 153.59, 147.454, 133.09, 124.70 (C = C),
118.46, 115.83, 114.49, 100.97 (C = C–H), 55.99 (OCH3 ) and 23.34 The geometrical optimized structure, FMOs, quantum chemical
(CH3 ). HRMS (m/z): 369.9939 [M+ ]. Mol. formula: C17 H15 N5 O5 , parameters with UV-Visible, FT-IR and COSMO-RS were analyzed
Anal. calcd for C 55.28, H 4.09 and N 18.96% found: C 55.12, H 4.00 theoretically at a gaseous phase in density functional theory (DFT)
and N 18.72%. using the Gaussian09 program and Gauss View 6.0.16 graphical in-
terference with the help of (DFT)/B3LYP method using 6–311++
G(d, p) basis set [29,30].
2.2.4. 7–hydroxy-5- (4-bromophenyl) −9-methyl −1,5-dihydro
−2H-dipyrimido [1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives
(4d) 2.6. Photocatalytic activity
Yield: 85%, mp: 230–232 °C, Color: red powder. IR (KBr, ν ,
cm−1 ): 3550 (OH), 3282 (NH), 3157 (C–H), 1675 (C = O), 1638 Shimadzu’s UV–Vis spectrophotometer model 2600 was used
(C = N) and 678 (C-Br). 1 H NMR (400 MHz, DMSO–d6 , δ ppm): to carry out the photocatalytic activity. Malachite green dye was
11.03 (s, 1H, NH), 10.90 (s, 1H, NH), 8.39–8.37 (d, J = 8, Hz, 2H, chosen as the dye model and the 20 ppm of 250 mL aqueous
Ar-H), 8.10 (s, 1H, Ar-H), 6.76–6.73 (d, J = 9.6 Hz, 2H, Ar-H), 5.35 dye solution was prepared followed by the addition of 60 mg
(s, 1H, CH) and 1.93 (s, 3H, CH3 ). 13 C NMR (100 MHz, DMSO–d6 of 7–hydroxy-5-(4-substitutedphenyl)−9-methyl-1,5-dihydro-2H-
δ ppm): 165.25, 163.27 (C = O), 155.98, 155.87, 154.65, 150.85, dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives
139.61, 120.48 (C = C), 111.71, 110.02, 100.35 (C=CH) and 23.92 4(a-d) as catalyst was stirred in glass reactor at dark condition
(CH3 ). HRMS (m/z): 401.9598 [M+ ], 402.9841 [M + 2]. Mol. for- before irradiation of light, after 30 min the UV-light was irradiated
mula: C16 H12 BrN5 O3 , Anal. calcd for C 47.78, H 3.01, N 17.41%, in open-air condition and was monitored in UV–Vis 20 0–80 0
found: C 47.69, H 2.99, N 17.39%. range [31].

3
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Scheme 2. Proposed Mechanism of synthesized 7-hydroxy-5-(4-substitutedphenyl)−9-methyl-1, 5- dihydro-2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives

4(a–d).

2.7. Latent fingerprints 3.2. Characterization

The LFPs method was carried out by powder dusting method. The multicomponent reaction of synthesized 7–hydroxy-5-
Generally, fingerprint powder of synthesized compounds 4(a-d) is (4-substitutedphenyl)−9-methyl-1,5-dihydro-2H-dipyrimido[1,2-
applied to the surface bearing the latent print with a fingerprint a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives 4(a–d) was con-
brush, while applying the powder with a fingerprint brush extra firmed by spectral techniques such as IR, 1 H NMR, 13 C NMR and
care should be taken to avoid damaging the latent print and visu- HRMS. The IR spectrum of synthesized compound 4a showed a
alized it in UV-light. LFPs are categorized into three different steps, stretching vibration band at 3428 cm−1 due to the hydroxyl group
namely Steps 1, 2 and 3. Among, the Step 1 relives, namely delta, and another band at 3267 cm−1 is due to starching vibration
loop and whorl are unclear and not enough for personal identifi- amide group functionality. Aromatic stretching frequency appeared
cation. Further, Step 2 details consist of various minutiae, such as at 3185 cm−1 and absorption bands at 1663 cm−1 correspond to
bifurcation, cross over, lake, hook, short ridge, island, etc., which C=O stretching present in the pyrimidine nucleus. The stretching
are clear and distinctive. However, Step 3 details are encompassing vibration frequancy band at 1611 cm−1 is correspond to C=N
sweat pores, small deviations in ridge track and edge contours. functionality. In 1 H NMR spectrum of compound 4a exhibited two
singlet peaks at δ 11.22 and 11.09 ppm due to two NH protons of
3. Result and discussion the pyrimidine nucleus and another two singlet peaks observed at
δ 10.77 and 10.79 ppm which corresponds to two OH protons. Fur-
3.1. Chemistry thermore, the doublet peak at δ 8.30–8.28 ppm of three aromatic
protons (d, J = 8 Hz, 3H, Ar-H) and a singlet peak at δ 8.16 ppm
Proposed mechanism of formation of new 7–hydroxy-5-(4- correspond to aromatic proton (s, 1H, Ar-H), another doublet peak
substitutedphenyl)−9-methyl-1,5-dihydro-2H-dipyrimido[1,2- observed at 6.84–6.82 ppm due to another one aromatic proton
a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives proposed in (d, J = 8 Hz, 1H, Ar-H). A singlet peak has been observed at δ
Scheme 2. The enol (I) from barbituric acid attack substituted 5.73 ppm of junction proton (s, 1H, CH) between the phenyl and
benzaldehyde (II) through l-Proline and was coordinated through pyrimidine ring and another singlet peak at 1.95 ppm corresponds
a hydrogen bond to oxygen atom (III). Nucleophilic attack from to methyl protons (s, 3H, CH3 ). Also, 13 C NMR spectrum of syn-
primary amine (IV) to the carbonyl group of the activated ben- thesized 4a appearance of a signal at δ 165.30 and 162.84 ppm
zaldehyde (III) and formation of Knoevenagel intermediate (V). due to the C=O carbon and δ 156.00, 155.72 correspond to C=N
Michael addition reaction has taken place from pyrimidine ring carbons, and a methyl carbon has been observed at δ 23.66 ppm.
leads to formation intermediate (VI). Further, cyclocondensation to The mass spectrum showed molecular ion peak [M + 2]+ at m/z
afford the targets (VII) 4(a-d) [32].

4
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 1a. Electronic absorption graphs of synthesized compounds 4(a–d) in different solvents (a) DMSO, (b) Acetonitrile, (c) Methanol, and (d) Acetone.

is 341.3083 corresponding to molecular weight of compound 4a and 469 nm due to the influence of two hydroxyl groups as an
(supplementary files S1 -S20 ). electron-donating group present in the phenyl ring and high polar-
ity of the solvent and single absorbance in all solvent at the nearer
3.3. Electronic absorption studies visible region, similarly the compound 4b were observed a dual
absorption appeared at bathochromic (red) shift at 297 nm and
Electronic absorption spectral properties of newly synthesized 404 nm in DMSO, 295 nm and 376 nm in acetonitrile, 299 nm
4(a-d) were recorded in different solvents at the concentration and 405 nm in methanol, and 389 nm in acetone. Absorption
of 6 × 10−6 M using a UV-Visible spectrophotometer. The sol- peaks were influenced by the electron-withdrawing cholro group
vents were selected with their dielectric constant. From Fig. 1a, on phenyl ring and electron-donating hydroxyl group on pyrimi-
we observe that all the compounds have shown strong absorp- dine ring. While compounds 4a and 4c were shown redshifts in
tion bands at region (λabs ) ∼350–500 nm due to the π -π ∗ and the solvent which is influenced by the hydroxyl on the pyrimidine
n-π ∗ transitions and aromatic conjugation also influence by the ring and methoxy group on the phenyl ring [35]. Synthesized com-
electron-donating and electron-withdrawing groups by acting as pounds 4(a-d) have a higher molar extinction coefficient due to the
chromophores [33,34]. Where the compound 4a shows the dual extent of conjugation of phenyl rings. The experimental absorption
absorbance peaks in DMSO solvent at visible region 383 nm

5
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Table 2
Electronic absorption spectral data of synthesized compounds 4(a–d).

Solvents Entry λ abs (nm) Eg OTP (eV) Molar absorptivity(ԑ × 10−5 L mol−1 cm−1 )

Acetone 4a 374 3.31 6.2

DMSO 384, 469 3.22, 2.64 6.4
Acetonitrile 374 3.31 7.8
MeOH 385 3.22 6.4
Acetone 4b 389 3.18 6.4
DMSO 297, 404 4.17, 3.06 6.7
Acetonitrile 295, 376 4.20, 3.29 6.2
MeOH 299,405 4.14, 3.06 6.7
Acetone 4c 332 3.73 5.5
DMSO 307 4.03 5.1
Acetonitrile 301, 331 4.11, 3.74 5.5
MeOH 312 3.97 5.2
Acetone 4d 335 3.70 5.5
DMSO 311, 3.98 5.2
Acetonitrile 306 4.05 5.1
MeOH 334 3.71 5.5

Fig. 1b. Electronic absorption graphs of synthesized compounds 4(a–d) estimated from theoretically, TD-DFT B3LYP method using 6–311++ G (d, p) basis set at gaseous
phase.

spectral data has been summarized in Table 2 and the optical band sorption bands at 316 nm, 328 nm, 383 nm and 317 nm, 341 nm
gap was calculated using Eq. (1) [36]. and 384 nm respectively. Compound 4b exhibited peak at 328,
Further, absorption properties of synthesized compounds were 383 nm and 4d have showed only a single absorption band at
analyzed by experimental and correlated with the time-dependent 383 nm. From theoretical studies, all bands are observed at a
density functional theory (TD-DFT) method at gaseous phase longer wavelength which exhibits the bathochromic shift, while
[37,38]. From Fig. 1b, compounds 4a and 4c are showed three ab- in the solvent system compounds observed dual absorption bands

6
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Table 3 Table 5a
Theoretically calculated absorption spectral data of synthesized compounds 4(a–d). CV Studies of synthesized compounds 4(a–d).

Entry λ abs (nm) Eg OTP (eV)a∗ Entry EPa (V) EPC (V) HOMO (eV) LUMO (eV)

4a 317, 326, 383 3.90, 3.80, 3.24 4a −0.29 −0.63 −4.11 −3.77
4b 328, 383 3.78, 3.24 4b −0.62 −1.2 −3.78 −3.20
4c 317, 341, 384 3.90, 3.64, 3.23 4c 0.39 0.34 −4.79 −4.74
4d 383 3.24 4d 0.21 −0.34 −4.61 −4.06
a∗
Eg = 1240/λonset eV.
Table 5b
Table 4 Experimental chemical parameters of synthesized compounds 4(a-d).
Emission spectral data of synthesized compounds 4(a–d).
Entry I (eV) A (eV) ƞ (eV) σ (eV) χ (eV) μ (eV) ω (eV)
Entry λ exe (nm) λ emi (nm)
4a 4.11 3.77 0.17 5.88 3.94 −3.94 45.65
4a 469 530 4b 3.78 3.20 0.29 3.44 3.49 −3.49 20.64
4b 404 560 4c 4.79 4.74 0.11 9.09 4.76 −4.76 102.7
4c 331 461, 614 4d 4.61 4.06 0.27 3.70 4.73 −4.73 41.43
4d 334 622

−0.27 V, −0.62 V, 0.39 V, 0.21 V and gives −4.11 eV, −3.78 eV,
with higher intensity. Theoretically calculated absorption spectral −4.79 eV, −4.61 eV of higher the HOMO values. Similarly, the
data has been appended in Table 3. quasi-reversible of cathodic reduction onset potential is −0.63 V,
−1.2 V, 0.34 V and −0.34 V gives −3.77 eV, −3.20 eV,−4.74 eV
Eg = 1240/λonset eV (1)
and −4.06 eV lower values of LUMO for the compounds 4(a-d).
Further, theoretically calculated energy molecules gives 4.11 eV,
3.3. Emission studies 3.78 eV, 4.79 eV, and 4.61 eV of HOMO for oxidation and reduc-
tion of LUMO gives the 3.77 eV, 3.20 eV, 4.74 eV and 4.06 eV re-
The emission of synthesized compounds 4(a–d) was analyzed spectively. From the theoretical and experimental results, we found
in a solvent system at the concentration of 6 × 10−6 M in DMSO good results in experimental by exhibiting the quasi-reversible of
solvent. The peaks were emitted with the corresponding excita- one wave electron transfer in redox process [44,45]. The exper-
tion wavelength and move towards the longer wavelength at red- imental HOMO-LUMO with quantum chemical parameters, redox
shifted at 530 nm and 560 nm for 4a and 4b respectively. While onset potential has been appended in Tables 5a and 5b.
compound 4c has shown dual adsorption bands at 401 nm and  
614 nm respectively because it is influenced by hydroxyl group E(HOMO) = − E(oxonset ) + 4.4 eV (2)
present on pyrimidine and phenyl rings as electron donor and
 
methoxy group present on phenyl ring as an electron-withdrawing E(LUMO ) = − E(redonset ) + 4.4 eV (3)
group, similarly the compound 4d has shown longer emission peak
at 622 nm due to presence of bromine group on phenyl ring 3.5. Frontier molecular orbitals
which is act as an electron-withdrawing group were displayed in
Fig. 2 [39,40]. Absorption and emission spectral data were listed in Frontier molecular orbital (FMOs) contains excitation of one
Table 4. electron from Energy of highest occupied molecular orbital (EHOMO )
to the energy lowest unoccupied molecular orbital (ELUMO ). HOMO
3.4. Electrochemical studies and LUMO plots of our optimized structures are shown in Figs. 4
and 5. The EHOMO and ELUMO are some of the important pa-
The electrochemical studies were carried out of synthesized rameters in chemical quantum chemistry which describes the
compounds 4(a–d) with three-electrode systems in 1 M KOH aque- optical, electronic properties, chemical reactivity, stability, ICT,
ous electrolyte. A fine cathodic reduction potential (EPc ) and anodic chemical hardness, softness, and electronegativity of molecules
oxidation potential (EPa ) peaks were obtained as appeared in Fig. 3. [46,47].
The redox behavior has been measured at different scan rates at The EHOMO values of our synthesized derivatives 4(a–d) are
10 mVs−1 to 50 mVs−1 . Compound 4a has shown one-electron −0.222 eV, −0.233 eV, −0.219 eV and −0.237 eV, respectively, that
transfer of reversible reduction −0.64 V and quasi-reversible oxi- associated with electron-donating ability to the empty orbital with
dation of −0.29 V, similarly 4b and 4d compounds has the sim- the lesser energy and increase in intramolecular charge transfer to
ilar in redox behavior that reversibility of reduction and quasi- the molecules. Similarly, ELUMO is commonly known for accepting
reversible of oxidation and due to presence halogen groups (Cl and the excited electron and for our compound the ELUMO values are
Br) as electron-withdrawing groups −1.22 V, −0.62 V and −0.34 V, −0.103 eV, −0.139 eV, −0.078 eV and −0.141 eV, respectively. The
−0.21 V respectively. Further, the 4c compound has shown re- reactivity and chemical stability of the compound was determined
versibility electron transfer of redox potentials at 0.34 V and 0.39 V by the energy gap between EHO MO and ELU MO i.e. E = EH-EL [48].
due to the presence of hydroxyl and methoxy groups on the phenyl Increase in the energy gap leads to the greater kinetic stability of
ring [41,42]. molecule and chemical reactivity. Similarly, lower energy gap val-
From the electrochemical studies, the redox onset potentials ues reveal higher inhibition efficiency, chemical reactivity and bio-
were used to calculate the HOMO and LUMO experimentally us- logical activity of molecules [49]. The theoretically calculated ener-
ing Eqs. (2) and (3) [43]. The HOMO of oxidation onset poten- gies of HOMO and LUMO levels are given in Table 6.
tial (E onset- ox ) relates the ionization potential (IP) and LUMO of
reduction onset potential (E onset-red ) relates the electron affinity 3.6. Quantum chemical parameter
(EA) both experimentally and theoretically. The presence of hy-
droxy group on the pyrimidine ring undergoes anodic oxidation Koopmans theorem describes ionization potential as directly
easily by the loss of an electron and OH anion has been formed proportional (IP) to -EHOMO and electron affinity (EA) is related to
in all the compounds. The estimated oxidation onset potential is -ELUMO . The chemical reactivity and stability were measured from

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K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 2. Photoluminescence graphs of synthesized compounds 4(a–d).

Table 6 other important parameter that informs the absorption between

Frontier molecular orbital’s (FMOs) of synthesized compounds 4(a–d).
the metal surface and the chemical compound. While synthesized
Entry EHUMO ELUMO E compound 4(a–d) shows greater values 6.86 D, 9.05 D, 8.74 D and
4a −0.222 −0.103 0.119 7.62 D respectively, which increase the absorption on the metal
4b −0.233 −0.139 0.094 surface [50,51]. The quantum chemical parameters have been ap-
4c −0.219 −0.078 0.141 pended in Table 7.
4d −0.237 −0.141 0.096

the chemical hardness [ƞ = ½(I – A)] where it is known by higher 3.7. Vibrations analysis
energy gap and if lower the energy gap is known as chemical soft-
ness [σ = 1/ƞ]. The synthesized compounds are the hard molecules FT-IR spectral analysis of 7–hydroxy-5-(4-substitutedphenyl)−9-
that show better intra-molecular charge transfer (ICT) and an in- methyl-1,5-dihydro-2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-
crease in chemical reactivity and photostability. 2,4(3H)–dione derivatives 4(a–d) have been estimated theoretically
Electronegativity [χ = 1/2 (I + A)] tells the intrinsic properties, at gaseous phase using (DFT)/B3LYP method using 6–311++ G(d,
Chemical potential [μ = -χ ] is the negative value of the electroneg- p) basis set [52]. Obtained compounds contain 38 atoms that lead
ativity and global electrophilicity index [ω = μ2 /2ƞ] relates accep- to 108 to 120 fundamental vibrations which show the C1 point
tance of electron on the metal surface as a corrosion inhibitor and group. The estimated theoretical FT-IR spectra were shown in Figs.
increase in photostability where the synthesized compounds show S2, S7 S12 and S17 and obtained frequencies are appended in
higher electrophilicity index gives 0.21 eV, 0.32 eV, 0.14 eV and Table S1 with potential energy density (PED) into supplementary
0.40 eV which increase in photostability. Dipole moment is an- file.

8
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 3. CV studies of synthesized compounds 4(a-d) at different scan rate in 1 M KOH.

Table 7
Theoretical chemical parameters of synthesized compounds 4(a–d).

Entry I (eV) A (eV) ƞ (eV) σ (eV) χ (eV) μ (eV) ω (eV) D

4a 0.22 0.10 0.06 16.6 0.16 −0.16 0.21 6.86

4b 0.23 0.13 0.05 20.0 0.18 −0.18 0.32 9.05
4c 0.29 0.07 0.11 9.09 0.18 −0.18 0.14 8.74
4d 0.23 0.14 0.04 22.2 0.18 −0.18 0.40 7.62

3.7.1. O-H vibration 3.7.3. C-H vibrations

The presence of hydroxyl group on pyrimidine ring in the ob- Generally, C–H vibration of aromatic compounds shows 3100–
tained compounds 4(a–d) shows symmetric stretching frequency 2800 cm−1 . In the titled compounds, symmetric stretching fre-
at 3823 cm−1 , 3824 cm−1 , 3826 cm−1 and 3820 cm−1 theoretically quency are observed at 3185 cm−1 for compound 4a, 3054 cm−1 ,
and found experimentally 3428 cm−1 , 3400 cm−1 , 3355 cm−1 and 2894 cm−1 and 3157 cm−1 shows symmetric starching frequency
3550 cm−1 respectively. of compounds 4b, 4c and 4d Further, we obtained 3213 cm−1 , 3204
cm−1 , 3213 cm−1 , 3212 cm−1 , 3203 cm−1 , and 3215 cm−1 , 3211
cm−1 , 3206 cm-1 theoretically.

3.6.4. C=O vibrations

3.7.2. N-H vibration The carbonyl functional groups present in aromatic compounds
Amide functionality is observed symmetric vibrations at 3200– have been shown in the region of 1780–1650 cm-1. The predicted
3600 cm−1 in the IR region. The amide (N-H) group present in theoretical vibrations are 1683 cm−1 , 1728 cm−1 , 1728 cm−1 , 1720
pyrimidine ring shows symmetric stretching frequency occurs at cm−1 , and 1687 cm−1 for the titled compounds 4(a–d). While we
3630 cm−1 , 3621 cm−1 , 3626 cm−1 and 3620 cm−1 by theoreti- found 1663 cm−1 , 1668 cm−1 , and 1654 cm−1 for the compounds
cally and from experimental found 3267 cm−1 , 3274 cm−1 , 3176 4a and 4b respectively. Similarly, compounds 4c and 4d have found
cm−1 and 3282 cm−1 compounds. 1661 cm−1 , and 1675 cm−1 respectively.

9
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 4. Optimized Structure of synthesized compounds 4(a–d).

3.6.6. C=N vibrations dicted bending vibrations value for C-Cl is 663 cm−1 and bending
After the carbonyl functional groups, the C=N were observed vibration for C-Br gives 693 cm−1 . In compounds 4b and 4d have
starching frequency at 1650–1550 cm−1 of aromatic compounds. been shown symmetric bending vibrations at 786 cm−1 and 678
From theoretically, compounds 4a and 4b have been observed C=N cm−1 respectively [52–55].
stretching frequency at 1683 cm−1 and 1589 cm−1 respectively,
while 4c and 4d observed at 1590 cm−1 and 1588 cm−1 for. In ex- 3.8. COSMO-RS
perimental IR spectrum of compounds 4(a-d) found at 1611 cm−1 ,
1635 cm−1 , 1661 cm−1 , 1555 cm−1 respectively and these results Conductor like screening model for real solvent (COSMO-RS) is
are good agreement with PED calculations. one of the theoretical approaches to predictions of thermodynamic
properties of fluids and liquid mixtures. The values were calcu-
3.6.7. C-Cl and C-Br lated theoretically using materials studio software, DMol3 calcu-
Halogen functional groups are showed stretching vibrations at lation in solvation method at triple zeta valance polarized basis
fingerprint regions of the IR spectrum. In aromatic compound C-Cl set (TVZP) [56–59]. This method describes the electrostatic inter-
and C-Br shows starching vibrations at 850–550 cm−1 . The pre- actions of synthesized compounds 4(a–d) with the selected sol-

10
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 5. Energy levels of EHOMO -ELUMO structures of synthesized compounds 4(a–d).

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K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 6. σ profiles for selected solvent using synthesized compounds 4(a-d) estimated in Turbomole software.

vents and provides screening charge distribution (σ , sigma) of spe- responding to the negative charge density 0.0081 e.Å−2 , 0.012
cific polarity on the molecular surface. Sigma (σ ) profile for each e.Å−2 of hydrogen acceptor bonds and more polarized than the sol-
selected solvents was given in Fig. 6 along with the estimated vent used; also, gives screening charge density at −0.011 e.Å−2 of
COSMO-RS file of synthesized compounds which helps to predict hydrogen donor regions and more polarity in acetonitrile solvent
the hydrogen bond interactions. The center peak of σ profile is re- than the other solvent. Cation was present in compound 4b asso-
lated to the molecule is nonpolar while the peak is far from the ciated with hydroxyl group will be more polar in selected solvent
center then the molecule is polar, similarly further peaks have ap- and attractive for strong hydrogen interaction and screening charge
peared in −0.0084 e/Å−2 and +0.0084 e/Å−2 are regions of hydro- density gives the 0.011 e.Å−2 , at acceptor hydrogen molecules and
gen bond donor and acceptor molecules. Further, the negative σ −0.012 e.Å−2 at donor hydrogen bonds. While compound 4d has
value indicates positive screening charges and positive σ values are been observed dual peaks at 0.081 e.Å−2 , 0.012 e.Å−2 of hydro-
the negative screening charges [60]. gen bond acceptor in selected solvent and compound will be more
Here, we found noteworthy results, for all the synthesized com- polar in nature increase in strong of the interaction of hydrogen
pounds in selected solvents were observed more polar. Compound bond donor atom [61].Theoretically estimated values are added in
4a was observed peak at negative charge and presence of func- Table 8.
tional group will be more polarized than the solvent at 0.010
e/Å−2 , 0.012 e.Å−2 of hydrogen bond acceptor regions and −0.011 3.9. Photocatalytic studies
e.Å−2 of hydrogen donor regions associated with hydroxyl as am-
photeric groups. Similarly, compound 4c observed dual peaks cor- Catalytic activity was carried out using synthesized compounds
4(a-d) over MG dye compound under the UV-light; at the time in-

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K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 7. UV absorbance spectra of MG dye during degradation.

Table 8 3.9.1. Photodegradation kinetics

COSMO-RS values of synthesized compounds in selected solvents.
The photodegradation of MG dye compound using synthesized
4a 4b 4c 4d compounds 4(a–d) under UV light irradiation exhibits the first-
Solvents pKa (kcal/mol) pKa (kcal/mol) pKa (kcal/mol) pKa (kcal/mol) order reaction pseudo-first-order kinetics model (photodegradation
DMSO −25.78 −28.07 −29.11 −25.79 kinetics) as shown in Fig. 8a, respectively using Eq. (5).
MeCN −26.00 −27.76 −28.79 −25.49
Ace −24.79 −27.71 −27.54 −24.39 lnC0 /Ct = kt (5)
MeOH −26.31 −27.52 −28.56 −25.27
Where Ct is the final concentration, C0 is the initial concen-
tration, t is the time interval and k apparent rate constant [68],
the dye degradation rate was decreased with the increases of time.
terval [62–64]. Fig. 7 shows the intensity of absorption peaks were
Hence, compounds 4(a-d) are good photocatalysts over the MG in
decrease continuously when an increase in time interval with-
the presence of light. The calculated% of dye degradation rates was
out changing any position of peaks and absorption was observed
summarized in Table 9.
575 nm. Moreover, the absorbance of dye degradation is propor-
tional to the concentration and at initial time being, the dye degra-
3.9.2. Theoretical approaches of photocatalytic
dation found to be very low, hence, the percentage of dye degra-
In photocatalytic degradation, hydroxy (OH) groups play vital
dation increase with the time interval [65].
roles by the formation of hydroxyl and superoxide radicals after
The percentage of dye degradation was calculated using
the incident of light and oxygen vaccines are also favorable for the
Eq. (4) where Ce and Ct are dye concentrations of initial and fi-
photocatalytic activity. Dye degradation of organic dye compounds
nal at time interval t [66,67]. An interesting result was found that
depends upon the chemical structure, aromatic rings, presence of
lower the catalytic efficiency was found to 4a by reaching 65% and
chromophores like nitro, hydroxyl and sulfur groups act as active
higher catalytic efficiency was found to be 4b and 4c by reliving
sites and bind to the malachite green dye compounds. Under the
83% and 87% under the UV radiation.
UV light, the chromophores are enhancing the light towards the
%Degradation = Ce − Ct /C0 × 100 (4) visible region and easily bind the pollutant compound and act as

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K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 8a. Kinetics study of dye degradation b) Effect of time interval of using synthesized compounds 4(a–d) over MG dye degradation and error bars represent the standard
deviation.

an efficient catalyst by degradation method following mechanism Table 9

Photocatalytic studies of synthesized compounds 4(a–d).
has taken place [69].
A 20 ppm +60 mg synthesized compounds +UV light
O2 + e− → O2 −
Time Entry Concentration C/C0 log C/C0 -log C/C0 %D

0 4a 0.2452 1 0 0 0
O2 − + H + → H O2 15 0.2337 0.9530 −0.020 0.0200 15%
30 0.1528 0.6231 −0.2054 0.2054 33%
45 0.1158 0.4772 −0.3212 0.3212 52%
HO2 . + HO2 . → H2 O2 + O2 60 0.1138 0.4641 −0.3333 0.3333 57%
75 0.1050 0.4282 −0.3683 0.3683 59%
90 0.0986 0.4021 −0.3956 0.3956 60%
105 0.0967 0.3943 −0.4017 0.4017 61%
H2 O2 + e− → H O. + H O− 120 0.0949 0.3870 −0.4122 0.4122 65%
0 4b 0.2323 1 0 0 0
15 0.1594 0.6861 −0.1636 0.1636 31%
− . −
H2 O2 + O2 → H O + H O + O2 30 0.0915 0.3938 −0.4047 0.4047 60%
45 0.0758 0.3263 −0.4863 0.4863 67%
60 0.0609 0.2621 −0.5815 0.5815 73%
75 0.0550 0.2367 −0.6258 0.6258 76%
H2 O2 → 2HO
90 0.0491 0.2113 −0.6751 0.6751 78%
105 0.0412 0.1773 −0.7512 0.7512 82%
120 0.0382 0.1644 0.7840 0.7840 83%
O2 + HO− → O2 − + HO 0 4c 0.1113 1 0 0 0
15 0.1096 0.9847 −0.0066 0.0066 12%
30 0.1053 0.9460 −0.0241 0.0241 44%
Dye + HO → Degradation products 45 0.1021 0.9173 −0.0374 0.0374 59%
60 0.0976 0.8769 −0.0570 0.0570 74%
75 0.0919 0.8256 −0.0832 0.0832 82%
90 0.0885 0.7951 −0.0995 0.0995 85%
Dye + h+ VB → oxidation products 105 0.0810 0.7277 −0.1380 0.1380 86%
120 0.0779 0.6999 0.1549 0.1549 87%
0 4d 0.0885 1 0 0 0
Dye + e− CB → reduction products 15 0.0770 0.8700 −0.0604 0.0604 11%
30 0.0631 0.7129 −0.1469 0.1469 27%
45 0.0598 0.6757 −0.1702 0.1702 31%
3.9.3. Effect of catalyst 60 0.0461 0.5209 −0.2832 0.2832 42%
Catalyst has been assessed over the MG dye compound keeping 75 0.0457 0.5163 −0.2870 0.2870 47%
dye concentration constant (20 ppm/250 mL aliquots). The catalyst 90 0.0385 0.4350 −0.3615 0.3615 55%
load 40, 50, 60, 70 and 80 mg in 250 mL solution were analyzed 105 0.0342 0.3864 −0.4129 0.4129 61%
120 0.0299 0.3378 −0.4701 0.4719 65%
as shown in Fig. 8c. We observe variation in degradation rates and
are increasing when the load of catalyst increases, compound 4b
and 4c shows higher degradation rates at 85% and 88%. Similarly, 3.9.4. Effect of pH
compounds 4a and 4d have shown increased catalytic activity by Here we performed the photocatalytic activity using different
reaching 68% and 72%. As catalyst load increases, the particles sus- pH variables at acidic (5, 6), neutral (7) and basic (8 and 9)
pension increases in which affect by the UV radiations. medium. In Fig. 8d, we observed at neutral pH-7, the photocatalytic

14
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Table 10
Effect of parameters of synthesized compound 4c for photocatalytic dye degradation of MG dye.

Effect Time Degradation (%) Weight of photocatalyst Degradation (%) Effect of pH Degradation (%)

0 0 40 68% 5 75%
30 44% 50 70% 6 76%
60 74% 60 75% 7 89%
90 85% 70 80% 8 79%
120 87% 80 88% 9 78%

Fig. 8b. Graphs of% dye degradation with effect of Catalyst in irradiation time of synthesized compounds 4(a–d), error bars represent the standard deviation.

activity was found to be more effective dye degradation of dye for each compound under UV light. Fig. 8b obverses as time in-
molecules by reaching 85% and 88% for 4b and 4c compounds. The crease the percentage of dye degradation (MG) was also increases.
dye degradation rates were decreasing when an increasing acidic Among the synthesized compounds 4b and 4c has been found to
medium, due to absorption of protonated H+ ions by the catalyst better photocatalytic activity by reaching dye degradation 83% and
and as well as organic dye molecules, stays positive. Compounds 87% at 120 min. we did not found any higher dye degradation after
4a and 4d have shown moderate degradation by reaching 62% and 120 min and hence compounds were better to have catalytic effect
64% rates. Effect of parameters of compound 4c was summarized with the respect of time. Effects of parameters (pH, catalytic load
in Table 10 [70–72]. and time interval) are carried out using compounds over MG dye
and compound 4c has been shown good catalytic activity under
3.9.5. Effect of time interval the UV light.
The photocatalytic activity was carried out using synthesized
compounds 4(a–d) over MG dye with a time interval of 0–120 min

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K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 8c. Graphs of% dye degradation with Effect of pH in irradiation time of synthesized compounds 4(a–d), error bars represent the standard deviation.

3.10. Latent fingerprints (LFPs) 4. Conclusion

LFPs are one of the advance and promising methods of applica- In this work, we were inspired to synthesize of one-pot synthe-
tion in the crime branch nowadays. The simplest, most common, sis of 7–hydroxy-5-(4-substitutedphenyl)−9-methyl-1,5-dihydro-
powder dusting method was used to perform the experiment with 2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione derivatives
the synthesized 7–hydroxy-5-(4-substitutedphenyl)−9-methyl- 4(a–d) using L-Proline as a catalyst, optical behavior was studied
1,5-dihydro-2H-dipyrimido[1,2-a:4 ,5 -d]pyrimidine-2,4(3H)–dione in different solvents, where absorption and emission bands were
derivatives 4(a–d) on different substrates such as knife, mobile and appeared at a longer wavelength with higher intensity due to
steel coin [73]. LFPs pictures were photographed under 365 nm aromatic extended π -conjugation. Similarly, redox peak current
UV light range in canon digital camera as arranged in Fig. 9. was studied in cyclic voltammogram at different scan rates of 10
A noteworthy result was found that the synthesized compounds mVs−1 to 50 mVs−1 , all the compounds have quasi-reversibility of
4(a–d) were carried out by powder dusting method and visualized an electron in cathodic reduction and quasi reversible of anodic
under normal light and UV-light. The compounds 4c and 4d de- oxidation peaks, with the help of redox onset potential, HOMO and
veloped on the knife and shows good contact on the substrate in LUMO has been calculated experimentally which informs the re-
UV light, similarly, 4a and 4b compounds also showed a better generation, recaptures of the injected electrons by the derivatives.
contact on steel coin and mobile phone substrates. Here, we ob- Likewise, FMOs, UV, FT-IR, quantum parameters and COSMO-RS
serve the powder dusting method was a useful method and com- were investigated theoretically at gaseous phase. Theoretical
pounds were physically and chemically stable in ambient as well as studies are good agreement with experimental results and the
moisture atmospheres. Based on the results, the synthesized com- higher energy gap relives that increase in chemical reactivity and
pounds have a greater potential for latent fingerprint application photostability of compounds. The photocatalytic activities were
in forensic science [74]. studied using synthesized compounds over MG dye molecule at

16
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Fig. 9. Latent fingerprints of synthesized compounds 4(a–d) under normal light and UV-light.

different time being and confirmed from dye degradation method Conceptualization, Visualization, Formal analysis, Data curation,
and results were achieved at 65%, 83%, 88% and 65% respectively. Writing – original draft. M. Shashank: Formal analysis. G. Na-
Further, LFPs images were visualized under UV light, compounds garaju: Formal analysis. K. M. Mussuvir Pasha: Writing – original
have better adherences to knifes, mobile phones, steel coin sub- draft.
strate and hence compounds are potential materials for forensic
science. Based on the above experimental and theoretical studies,
we conclude that synthesized compounds 4(a–d) will be used as Acknowledgement
photo tonic materials as luminescent, optoelectronic materials and
in forensic science. The authors express gratefulness to the Chairman, Department
of PG studies and research In chemistry, Kuvempu University,
Shankaragatta. The authors also thank to SAIF, Karnataka for pro-
Declaration of Competing Interest
viding spectral data. The authors thanks to UGC, New Delhi, UGC-
BSR startup Grant [F. No. F.30–486/2019 (BSR)].
The authors declare that there is no conflict of interest regard-
ing the publication of this work.
Supporting information
CRediT authorship contribution statement
Spectroscopic data (FT-IR, 1 H NMR, 13 C NMR, and Mass spec-
K. Upendranath: Conceptualization, Visualization, Formal anal- trometry) and theoretical IR spectra of the synthesized compounds
ysis, Data curation, Writing – original draft. Talavara Venkatesh: have been provided in the supporting information file.

17
K. Upendranath, T. Venkatesh, M. Shashank et al. Journal of Molecular Structure 1250 (2022) 131930

Supplementary materials component of white light-emitting diode applications, ACS Sustain. Chem. Eng.
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