Synthesis, molecular characterization of pyrimidine derivative: A combined experimental and theoretical investigation

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ScienceDirect Karbala International Journal of Modern Science xx (2017) 1e11 http://www.journals.elsevier.com/karbala-international-journal-of-modern-science/

Synthesis, molecular characterization of pyrimidine derivative: A combined experimental and theoretical investigation D. Durga devi a, S. Manivarman a,*, S. Subashchandrabose b a

PG and Research Department of Chemistry, Government Arts College, C. Mutlur, Chidambaram 608102, Tamil Nadu, India b Centre for Functional Magnetic Material, Uni-Immanuel Kant Baltic Federal University, Kaliningrad, 236 041, Russia Received 18 November 2016; revised 24 January 2017; accepted 24 January 2017

Abstract A simple and efficient method has been developed for the synthesis of fused pyrimidine derivative 5,6,7,8-tetrahydro-5methyl-7-thioxopyrimido[4,5-d]pyrimidine-2,4(1H,3H)-dione (TMTPD) through Biginelli's one-pot multicomponent condensation reaction. The FT-IR and FT-Raman spectra were recorded to study the vibrations of the functional group presence. The UVeVisible spectrum also used to identify the electronic excitation from the ground state to excited state. Molecular structure of the synthesized compound has been studied using DFT/B3LYP/6-31G(d,p) level of theory. The Non-linear optical behaviour of the title compound was measured using first order hyperpolarizability calculation. The donoreacceptor stabilizing interactions have been analysed. © 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Keywords: TMTPD; FT-IR; FT-Raman; PED; NLO

1. Introduction Fused pyrimidines continue to attract considerable attention because of their great practical usefulness, primarily due to very wide spectrum of biological activities. Barbiturates (barbituric acid derivatives) are a class of central nervous system depressants (CNS) [1].

* Corresponding author. E-mail address: [email protected] (S. Manivarman). Peer review under responsibility of University of Kerbala.

They were also found totally new bio-medicinal applications in fields of cancer and AIDS therapy [2]. Some of the pyrimidine derivatives were found to reduce body weight, liver weight, visceral fat and regulated serum levels of biochemical markers [3]. Pyrimidine-2,4,6(1H,3H,5H)-trione is a strong acid with an active methylene group and can be involved in condensation reaction with aldehyde and ketone that do not contain a-Hydrogen [4]. Literature survey reveals that fair amount of work were published on the condensation reactions of barbituric acid with carbonyl compounds [5e10]. Introduction of an additional ring

http://dx.doi.org/10.1016/j.kijoms.2017.01.001 2405-609X/© 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Please cite this article in press as: D. Durga devi et al., Synthesis, molecular characterization of pyrimidine derivative: A combined experimental and theoretical investigation, Karbala International Journal of Modern Science (2017), http://dx.doi.org/10.1016/j.kijoms.2017.01.001

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to the pyrimidine core tends to exert a profound influence in conferring novel biological activities in these molecules [11e13]. Pyrimidine and their fused derivatives play an essential role in several biological processes and have considerable chemical and pharmacological importance. In particular, pyrimidine nucleus can be found in a broad variety of antibacterial and antitumor agents, as well as in agrochemical and veterinary products [14]. Pyrimidine, which is a highly deficient aromatic heterocycles, can therefore be used as electron withdrawing part in pushepull molecules [15,16]. Moreover, the intramolecular charge transfer along the molecule backbone can also induce luminescence properties [17]. Recent reports exhibits pyrimidine derivatives is a good non linear material [18]. Keeping in view, the above importance of the compounds possessing pyrimidine moiety, we thought it worthwhile to report a multi-component condensation of barbituric acid, aldehyde and thiourea via Biginelli reaction. The structure of product is deduced from FT-IR, FT-Raman, 1H and 13C NMR spectral data. In addition, the detailed fundamental vibrational

assignments of the synthesized molecule were assigned with the help of potential energy distribution analysis. The first hyperpolarizability and electrochemical properties of the title molecule have been investigated by density functional theory. 2. Experimental 2.1. Synthesis of 5,6,7,8-tetrahydro-5-methyl-7thioxopyrimido [4,5-d] pyrimidine-2,4(1H, 3H)-dione The compound 5,6,7,8-tetrahydro-5-methyl-7thioxopyrimido [4,5-d] pyrimidine-2,4(1H, 3H)-dione has been synthesized by Biginelli condensation method, taking equal mole ratio of barbituric acid, thiourea and acetaldehyde are dissolved in ethanol. To this mixture, 5 ml of Con. HCl is added then the content is condensed on oil bath for 1 h then the completion of the reaction was monitored by thin layer chromatography. Finally the reaction mixture is poured into water to get the solid product and recrystallized using absolute ethanol. Melting point ¼ 158  C ; Yield ¼ 85%.

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2.2. Mechanism of TMTPD The plausible mechanism of this multi component reaction begins with rate determining nucleophilic addition by the urea to the acetaldehyde. The ensuing condensation step is catalyzed by the addition of acid, resulting in the imine nitrogen. The barbituric acid then adds to the imine bond and consequently the ring is closed by the nucleophilic attack by the amine onto the carbonyl group. 2.3. Structural determination The newly synthesized fused pyrimidine derivative TMTPD was confirmed by FT-IR, NMR spectral analysis. A peak at 2956 cm1 in FT-IR spectrum and a signal at 4.75 ppm in 1H NMR spectrum confirms the formation of required product. The 1H and 13C NMR spectrum of title compound have shown in Figs. S1 and S2, respectively. The spectral data of TMTPD is given below. 1 H NMR (400 MHz, DMSOd6): d ¼ 4.75 (s, 1H, ArCH), 7.19 (s, 1H, NH), 9.16 (s, 1H, NH), 10.13 (s, 1H, NH), 11.14 (s, 1H, NH), 1.13 (s, 1H, CH3); 13C-NMR (100 MHz, DMSOd6): d ¼ 165.25, 175.97, 183.70, 45.47, 60.85, 20.27; IR (KBr) ncm1; 3057 cm1 (eCH3), 2956 cm1 (C9eH22), 1774, 1687 cm1 (C]O). 3. Theoretical simulations 3.1. Computational details All the theoretical calculations such as, molecular geometry, natural bond orbitals, electronic excitations, frontier molecular orbitals and vibrational wavenumbers

3

belonging to the TMTPD compound are performed using Gaussian03w package utilizing DFT/B3LYP/6-31G(d,p) level of theory. The vibrational modes were assigned on the basis of PED analysis using VEDA4 program [19]. The theoretical wavenumbers were scaled down uniformly by a factor of 0.9608 for obtaining good agreement with experimental results. 3.2. Molecular geometry In TMTPD compound, the bond lengths of CeH and NeH bonds are calculated as 1.09 and 1.01 Å respectively. The CeN bond length lies in the range of 1.37e1.39 Å. But C9eN14 value deviated by 0.10 Å. This is due to formation of a new bond between C9 and N14 atom, also C9 atom is Sp3 hybridized carbon atom. Furthermore, C13eN14 bond length is considerably shorter than other CeN bond length. This is because, sulphur atom bonded with carbon (C13) atom, which is less polar, so the carbon atom attracted towards nitrogen atom. The C6]O12 and C2]O8 bond lengths are calculated as 1.21 Å and 1.22 Å, respectively. The Sp3 hybridized carbon atom bonded with C3(sp2) and C17(sp3) atoms, shows their bond lengths 1.50 Å and 1.53 Å respectively. The bond length of C2(sp2)eC3(sp2) is 1.36 Å, which is slightly lower value, this is due to double bond conjugation of carbonyl group. Whereas C3eC4 bond length is 1.36 Å, which shows its double bond character. The Sp3 hybridised C17 atom, which shows the bond angle with its surrounding atoms at 108e110 . Similarly, C9 also a Sp3 hybridised atom which shows bond

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angle value 107e112 with its neighbouring atoms. Similarly, C3eC2eO8 has bond angle 125 , which is much greater due to the presence of highly electronegative oxygen atom. Where, C3eC4eN5, C3eC4eN10 bond angles are 121 , But, C2eC3eN1 bond angle is much lower. This is due to electronegative oxygen and nitrogen atoms present in neighbouring position towards C2 atom. In pyrimidine ring, the bond angle of CeCeC show around 120 , except, C3eC9eC17, this is because C9 atom is Sp3 hybridized. The bond lengths and bond angles of TMTPD listed in Table S1. The optimized molecular structure of TMTPD is shown in Fig. 1. 3.3. Natural bond orbital analysis The delocalization effect and stabilization energy from the interaction between the lone pair (donor) and antibonding (acceptor) can be estimated by second order perturbation interaction energy from NBO analysis [20]. For each donor (i) and acceptor (j), the stabilization energy E(2) associated with the delocalization i/ j is estimated as 2

Eð2Þ ¼ DEij ¼ qi

Fði; jÞ 3j  3i

ð1Þ

Where qi is the donor orbital occupancy, 3 i and 3 j are diagonal elements and F(i, j) is the off diagonal NBO Fock matrix element. The larger the E(2) value, the more intensive is the interaction between electron donors and electron acceptors, i.e. the more donating tendency from electron donors to electron acceptors and the greater the extent of conjugation of the whole system. NBO analysis has been performed on the TMTPD molecule at the DFT/B3LYP/6-31G(d,p) level of theory in order to elucidate the intra molecular delocalization, electron density, stabilization energy. The Second order

Fig. 1. The optimized molecular structure of TMTPD.

perturbation theory analysis of Fock matrix in NBO basis of TMTPD is tabulated in Table 1. The strong intramolecular hyper conjugative interactions of the s and p electrons of CeC, CeH, NeH and CeN to the anti CeC, CeH, NeH and CeN bond leads to stabilization of some part of the ring. In the present study, the ses* interaction have minimum delocalization energy then pep* interaction. Hence, the s bonds have higher electron density than the p bonds. The strong intramolecular hyperconjugative interaction are formed by orbital overlap between p(C3eC4) to corresponding p*(C2eO8) with increasing electron density 0.3303 resulting the stabilization energy of stabilization energy of 109.87 kJ/ mol, which result in intra molecular charge transfer causing stabilization of the molecule. Similarly p‒p* interaction takes place between p(C2eO8) and p*(C3eC4) with increase in electron density of 0.3242 that weakens the respective bonds with leading to the stabilization of 20.75 kJ/mol. The lone pair electrons are readily available for the interaction with excited electrons of acceptor antibonding orbital. The ne s* interaction from nonbonding O8 donates electron to anti-bonding s*(N1eC2, C2eC3) with considerably higher stabilization energy of about 123.26 and 76.32 kJ/mol. Similarly, intra molecular hyperconjugative interaction from n(O12) to s* (N1eC6, C6eN5) leading to the stabilization of 110.62 and 120.33 kJ/mol. Whereas nep* interaction take place between non-bonding N1 atom to their corresponding anti-bonding orbital of C2eO8 and C6eO12 with highest stabilization energy of 211.08, 267.02 kJ/mol, which result in intra molecular charge transfer causing stabilization of the molecular system. 3.4. Electronic properties 3.4.1. Electronic absorption spectra Molecular orbitals and their properties are used to explain several types of reactions for predicting the most reactive position in conjugated systems [21]. The UV spectrum of the TMTPD compound in ethanol solvent were recorded within the 200e600 nm range to investigate the properties of the electronic transitions of the title compound and the corresponding UV spectrum is shown in Fig. S3. As can be seen from the figure, the experimental electronic absorption spectrum of the TMTPD compound show a band at 240 nm with log 3 ¼ 3.870. In order to calculate theoretical electronic transition of the title compound, time dependent density functional theory (TD-DFT) calculations were

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Table 1 Second order perturbation theory analysis of Fock matrix in NBO basis for TMTPD. Type

Donor (i)

ED/e

Acceptor (j)

ED/e

a (2)

a (2)

b

c

pep*

C2eO8

1.98164

ses*

C3eC4

1.96865

pep*

C3eC4

1.81537

nep*

N1

1.65417

nep*

N5

1.67684

nes*

O8

1.97663

nes*

O8

1.85797

nep*

N10

1.67554

nes*

O12

1.976

nes*

O12

1.8367

nes*

N14

1.66238

s*e p* p*e s*

C13eS16 C13eS16

0.36356 0.20215

C2eO8 C3eC4 C2eC3 C2eO8 C3eC9 C4eN5 C4eN10 N5eH11 N10eH15 C2eO8 C3eC4 C9eC17 C9eH22 C2 ‒ O8 C6eO12 C3eC4 C6eO12 N1eC2 C2eC3 N1eC2 C2eC3 C3eC4 C13eS16 C13eS16 N1eC6 N5eC6 N1eC6 N5eC6 C9eC17 C9eH22 C13eS16 C13eS16 C13eN14 C13eS16 C9eN14

0.33032 0.32426 0.05888 0.00937 0.02471 0.02926 0.03363 0.01345 0.01637 0.33032 0.32426 0.02795 0.02418 0.33032 0.35400 0.32426 0.35400 0.09100 0.05888 0.09100 0.05888 0.32426 0.36356 0.20215 0.08129 0.08836 0.08129 0.08836 0.02795 0.02418 0.36356 0.20215 0.05337 0.20215 0.03528

4.39 20.75 10.42 10.33 11.55 10.46 9.5 10.04 9.96 109.87 25.44 15.27 8.33 211.08 267.02 194.72 214.93 6.28 12.64 123.26 76.32 188.78 86.36 34.89 11.05 9.29 110.62 120.33 24.89 10.59 152.26 32.26 44.98 309.11 7.95

1.05 4.96 2.49 2.47 2.76 2.5 2.27 2.4 2.38 26.26 6.08 3.65 1.99 50.45 63.82 46.54 51.37 1.5 3.02 29.46 18.24 45.12 20.64 8.34 2.64 2.22 26.44 28.76 5.95 2.53 36.39 7.71 10.75 73.88 1.9

0.37 0.38 1.25 1.35 1.17 1.19 1.19 1.19 1.19 0.31 0.31 0.66 0.75 0.28 0.27 0.31 0.29 1.07 1.16 0.64 0.73 0.3 0.34 0.46 1.11 1.08 0.68 0.64 0.63 0.73 0.31 0.43 0.67 0.12 0.16

0.019 0.042 0.05 0.052 0.051 0.049 0.047 0.048 0.048 0.083 0.04 0.046 0.036 0.107 0.117 0.107 0.11 0.036 0.053 0.125 0.105 0.105 0.075 0.057 0.049 0.044 0.122 0.124 0.06 0.042 0.096 0.053 0.077 0.158 0.045

a b c

E

E

F(i,j)

E(j)eE(i)

E(2) means energy of hyper conjugative interaction (stabilization energy). F(i,j) is the fork matrix element between i and j NBO orbitals. Energy difference between donor (i) and acceptor (j) NBO orbitals.

performed. The computed electronic values, such as absorption wavelength (lmax), excitation energies (E), oscillator strength (G) and assignments of electronic transitions belonging to the title compound are given in Table S2. The theoretical absorption band at 235 nm well agreed with the experimental absorption band at 240 nm. The experimental absorption band has slight red-shift with value of 5 nm, caused by attractive polarisation forces between the solvent and the absorber, which increase the energy level of excited state. So the energy difference between the excited and unexcited states is slightly increased, resulting in a small red shift and is assigned for pep* transition. The theoretical and experimental UVeVis spectrum is shown in Fig. S3.

3.4.2. Frontier molecular orbital analysis FMO analysis is widely employed to explain the electronic as well as the optical properties of organic compounds [22]. Knowledge of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and their properties such as their energy is very useful to gauge the chemical reactivity of the molecule. During molecular interactions, the HOMO donates electrons and its energy corresponds to the ionization potential (I.P.), whereas the LUMO accepts the electrons and its energy corresponds to the electron affinity (E.A.). The energy gap explains the eventual charge transfer interaction within the molecule and is useful in determining molecular electrical transport properties.

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Concerning the value of the energy gap ELUMOeHOMO, larger values of the energy difference will provide low reactivity to a chemical species. Lower values of the energy difference will render good inhibition efficiency, because the energy to remove an electron from the last occupied orbital will be low. The highest occupied molecular orbital is localized mainly on thiocarbonyl moiety, with energy of 0.2394 eV and the lowest unoccupied molecular orbital is uniformly distributed all over the molecule with energy of 1.6118 eV except methyl group. This shows eventual charge transfer occurs within the molecule. The pictorial representation of HOMOeLUMO is shown in Fig. 2. The energies of HOMO and LUMO, Kubo gap, electronegativity, chemical hardness, global softness and electrophilicity index are calculated and presented in Table 2. The large energy gap of HOMOeLUMO indicates the title compound is less stable towards electronegativity. The chemical hardness is 2.3138 eV which considerably low and hence the compound is chemically more reactive. Similarly, the electro negativity is observed to be 3.9256 eV. The electro negativity is a measure of attraction of an atom for electrons in a covalent bond. The candidate molecule has higher electronegativity, thus it does high charge flow occur. The electrophilicity index is a measure of energy lowering due to the maximal electron flow between the donor (HOMO) and the acceptor (LUMO). The usefulness of this new reactivity quantity has been demonstrated recently in

Fig. 2. Frontier molecular orbitals of TMTPD.

Table 2 Global reactivity descriptors of TMTPD. Global reactivity descriptors

Values (eV)

HOMO LUMO energy gap (DE) ¼ HOMOeLUMO ionization energy I ¼ eEHOMO electron affinity A ¼ eELUMO Global hardness (h) ¼ 1/2(ELUMOeEHOMO) Global softness (s) ¼ S ¼ 1/2h Electronegativity (c) ¼ 1/2(ELUMO þ EHOMO) Chemical potential (m) ¼  c global electrophilicity index (J) ¼ m2/2h

6.2394 1.6118 4.6276 6.2394 1.6118 2.3138 0.2161 3.9256 3.9256 3.3300

understanding the toxicity of various pollutants in terms of their reactivity [23]. 3.4.3. Vibrational assignments The vibrational analysis of TMTPD was performed on the basis of the characteristic vibration of methyl, carbonyl, thiocarbonyl and methine modes. The molecule under consideration belongs to the C1 point group. TMTPD have 21 atoms, hence it have 54 normal modes of vibration. In order to obtain the spectroscopic signature of the investigated molecule, frequency calculation analysis has been performed by DFT method using B3LYP/631G(d,p) level of theory. The computed vibrational wavenumbers and their FT-IR and FT-Raman activities corresponding to the different normal modes are used for identifying the vibrational modes unambiguously. The calculated wavenumbers are usually higher than the corresponding experimental quantities. The reason for these discrepancies, calculated value is harmonic frequency while experimental is anharmonic frequency. Therefore, a uniform scaling factor is used to eliminate these errors in harmonic wavenumber output. For comparison, scaled theoretical and experimental FT-IR and FT-Raman wavenumber are summarised in Table S3 along with their PED contribution, intensity and force constants. Experimental and simulated FT-IR and FT-Raman spectra are shown in Figs. 3 and 4, respectively. For complete vibrational analysis of TMTPD molecule, the discussions are mainly under five heads (i) Methyl group vibration (ii) CeC and CeH vibrations (iii) CeN vibrations (iv) C]O vibrations (v) C] S vibration. 3.4.3.1. Methyl group vibration. For the assignments of CH3 group frequencies, nine fundamental vibrations can be expected to each CH3 group. The vibrations are CH3ss (symmetric stretching), CH3ips (in-plane

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Fig. 3. The recorded and simulated FT-IR spectra of TMTPD.

Fig. 4. The recorded and simulated FT-Raman spectra of TMTPD.

stretching). CH3ipb (in-plane bending), CH3sb (symmetric bending), CH3ipr (in-plane rocking), CH3opr (out-of-plane rocking), tCH3 (twist), CH3 ops (outplane stretching), CH3 opb (out-of-plane bending) vibrations respectively. The CeH stretching vibration of methyl group are usually observed in lower wavenumber region than aromatic CeH stretching. The aliphatic CeH stretching wavenumbers are normally observed in the region of 3000e2800 [24]. The asymmetric CeH stretching mode of CH3 group is expected around 2980 cm1 while the symmetric mode is expected around 2870 cm1 [25e28]. In the present study, weak band observed at 2922 cm1 in FT-IR spectrum assigned to CeH asymmetric stretching vibration of methyl group. The calculated values at 3026 and 2929 cm1 shows good agreement with experimental value and in line with literature value 2925 cm1 [29] and the asymmetric stretching vibration observed as a weak band at 3057 cm1 in FT-IR spectrum, correlates with calculated wavenumber at 3026 cm1. For methyl group, the symmetrical bending (dsCH3) occurs near 1375 cm1 and the asymmetrical bending vibration (dasCH3) near 1450 cm1. In the present study, asymmetric bending vibration observed at 1423 cm1 in FT-IR as a weak band and 1451 cm1 in FT-Raman as an

intense band, these wavenumbers show good agreement with calculated wavenumber at 1443 and 1454 cm1. The rocking vibration for methyl group usually appears in the region of 1010e1070 cm1 [30]. The rocking vibration of methyl group theoretically calculated at 1039 cm1, which show good agreement with experimentally observed wavenumber at 1045 cm1. 3.4.3.2. CeC and CeH vibrations. The carbonecarbon stretching vibration occurs in the region of 1650e1200 cm1 [31]. The compound under investigation consist of three CeC and one C]C vibrations corresponds to C2eC3, C3eC9, C9eC17 and C3]C4 mode. The CeC stretching vibrations of pyrimidine ring observed at 1392, 1016 and 904 cm1 in FT-IR spectrum and 1374 cm1 in FT-Raman spectrum. These CeC stretching wavenumbers are in line with the calculated value 1381, 1006 and 899 cm1. The bond formed between aliphatic aldehyde and pyrimidine at the position of C3eC9 is computed at 1287 cm1 and it show good agreement with experimental observation at 1294 cm1 in FT-IR and 1271 cm1 in FT-Raman spectrum. The out of plane bending vibration observed at mode no. 46 and is correlate with the experimental wavenumber and also CCC deformation and torsional

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vibration is found at mode no. 55 and 59 correspondingly. Furthermore, the band appearing at 1624 cm1 in FT-Raman spectrum is assigned to C]C stretching vibration in pyrimidine ring and show good agreement with computed value at mode no. 11. The aliphatic CeH stretching vibrations normally appear in the region 2830e2695 cm1 [32]. A weak band is observed at 2956 in FT-IR and 2931 cm1 in FT-Raman spectrum, which are in accordance with calculated wavenumber at 2936 cm1 with 96% of PED contribution which is a pure mode of vibration. The increase in wavenumber is due to influence of methyl group present in adjacent position. The out-ofplane bending vibration of CeH bond is assigned at 1313 cm1 and is exactly correlated with computed wavenumber at 1319 cm1 with 75% of PED contribution. 3.4.3.3. CeN vibration. CeN vibrations are difficult to identify due to overlapping of other vibrations. Silverstein et al. [33], assigned CeN stretching absorption in the region of 1388e1266 cm1. In the present study, CeN stretching vibrations observed at 1490, 939 and 871 cm1 in FT-IR and 1214, 1143, 1091 and 929 cm1 in FT-Raman spectrum, these wavenumbers theoretically calculated 1497, 1210, 1179, 1092, 958, and 891 cm1. According to the literature [34] CeN stretching vibrations are found to be well within their characteristic region. The bands at 569, 529 and 335 cm1 are assigned for CeN deformation vibrations. 3.4.3.4. NeH vibration. The NeH stretching vibration of aromatic heterocyclic compounds commonly appears in the region of 3500e3000 cm1 [25]. From the theoretical investigation, the NeH stretching wavenumbers are computed at 3497, 3494, 3487 and 3482 cm1. Experimentally, weak band observed at 3089 cm1 in FT-IR and 3185 cm1 in FT-Raman spectrum are assigned for NeH stretching vibration of TMTPD compound. The NeH deformation vibration observed at 1539, 1365, 1337 660 and 618 cm1. 3.4.3.5. C]O vibration. Generally, the absorption of a carbonyl frequency is appeared as a strong peak, the position of absorption is very sensitive to various factors such as physical state, electronic effects by substituents, and ring strains [35]. The carbonyl C]O stretching vibration is expected to occur in the region 1715e1680 cm1 [36]. For title molecule the C]O stretching frequency observed at 1774 and 1687 cm1 in FT-IR spectrum and 1747 cm1 in FT-Raman spectrum are correlated with computed wavenumber at 1777

and 1710 cm1. A sharp band observed at 763 cm1 in FT-IR and 733 cm1 in FT-Raman assigned for deformation vibration of carbonyl group, which is in agreement with calculated wavenumber 730 cm1. 3.4.3.6. C]S vibration. The C]S is less polar than the C]O group and has a considerably weaker bond. In consequences, the band is not intense, and it falls at lower frequencies, where it is much more susceptible coupling effects. Therefore, identification is difficult and uncertain. Generally thio carbonyl group shows absorption in the 1250e1020 cm1 region. Spectra of some compounds in which the C]S group is attached to a nitrogen atom show an absorption band in the general C]S stretching region. In addition several other bands also appeared due to interaction between C]S stretching and CeN stretching [37]. In the present study, vibrational frequency of C]S observed at 1116 cm1 and it coincide with the computed value 1109 cm1. 3.5. Non-linear optics Nonlinear optics deals with the interaction of applied electromagnetic fields in various materials to generate new electromagnetic fields, altered in wavenumber, phase, or other physical properties [38]. The importance of NLO, in vital functions of wavenumber shifting, optical modulation, optical switching and logic, optical memory for emerging technologies in the areas of telecommunications, signal processing, and optical interconnections is at the forefront of current research [39e43]. The nonlinear parameters of title molecule are calculated using the B3LYP/6-31G(d,p) method based on the finite-field approach [44] and the hyperpolarizability components are listed in Table 3. Dipole moment reflects the molecular charge distribution and is given as a vector in three dimensions. Therefore, it can be used as descriptor to depict the charge movement across the molecule depends on the centres of positive and negative charges. As a result of B3LYP calculations, dipole moment (m) value observed for title compound is 0.2759 Debye. Molecules with electron conjugation incorporating electron donor and acceptor groups to influence the asymmetric polarization are candidates for NLO applications [45]. The organic chromophores with electron donor and electron acceptor groups at appropriate positions to facilitate the charge transfer have taken much attention due to their ultra-fast response times, lower dielectric constants and better polarizability characteristics and enhanced NLO responses. In our

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Table 3 Non-Linear Optical properties of TMTPD. Parameters

Dipole Moment

Parameters

Hyperpolarizability

mx my mz m Polarizability (a0) axx axy ayy axz ayz azz a

0.1051 0.2350 0.0992 0.2759 Debye £1030 esu 167.6767987 19.0734517 69.2756597 14.414215 23.8669328 137.0418568 2.441751945  1030 esu

bxxx bxxy bxyy byyy bxxz bxyz byyz bxzz byzz bzzz b0

560.65 204.23 67.29 10.91 425.69 110.73 1.93 102.53 31.93 217.86 6.703 £ 1030 esu

The bolded values represent the final parameters obtained from NLO study. Standard value for urea m ¼ 1.3732 Deb ye, b0 ¼ 0.3728  1030 esu.

title compound, the chromophores C]S, C]O facilitates charge transfer takes place in the molecule hence the title have higher hyperpolarizability (b0) value 6.703 £ 10¡30esu. This charge transfer also evident from HOMOeLUMO analysis and enormous stabilization energy of C]S from in NBO analysis. Urea is one of the prototypical molecules used in the study of the NLO properties of molecular systems. Therefore it was used frequently as a threshold value for comparative purposes. Theoretically, the first hyperpolarizability of the TMTPD compound is seventeen times greater than that of urea. According to the magnitude of the first hyperpolarizability, the title compound may be a potential applicant in the development of NLO materials. 4. Conclusion The TMTPD molecule was synthesized by one-pot Biginelli condensation method. A white amorphous powder obtained as a product and its structure is characterized by UV, FT-IR, FT-Raman and NMR spectral studies. A singlet at 4.75 ppm in 1H NMR spectrum confirms the formation of expected TMTPD compound. The experimentally observed FT-IR and FT-Raman wavenumbers were compared with theoretical wavenumbers show good agreement with each other. From the UV results, a peak at 240 nm corresponds to pep* transition. This results confirmed by frontier molecular orbital analysis, the transition mainly occur form thiocarbonyl moiety to all over the molecule with energy gap DE ¼ 4.6276 eV. This result also evident form, NBO analysis, which shows intra molecular charge transfer causing stabilization of the molecule.

Appendix A. Supplementary data Supplementary data related to this article can be found at http://dx.doi.org/10.1016/j.kijoms.2017.01. 001.

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