INTRODUCTION:

Quinoline is a bicyclic heterocyclic moiety with massive remedial potential. Quinolines are known for their excellent antimalarial^1-3, anti-inflammatory⁴, analgesic⁵, antibacterial⁶, antifungal⁷, anticancer^8,9, antiviral¹⁰, anthelmintic¹¹, antiprotozoal¹², and other miscellaneous biological activities^13,14. Some quinoline derivatives have also been used in the treating erectile dysfunction ¹⁵, and Alzheimer’s disease¹⁶.

Likewise 2-arylidene indanone skeleton has also received tremendous attention of the medicinal chemists due to its involvement in various applications. The diverse biological profile of compounds containing 2-arylidene indanone skeleton includes properties like antimalarial1⁷ antioxidant¹⁸ antimicrobial¹⁹ anti-inflammatory²⁰, etc. The structure of 2-arylidene indanone is similar to chalcones. Chalcones act as vital intermediates in synthetic organic chemistry, and additionally, they are found to show powerful and many biological properties²¹. The noteworthy biological activities shown by chalcones include anti-tubercular²², antihypertensive²³, antioxidant²⁴, anticancer²⁵, antiviral²⁶, antimicrobial²⁷, etc.

Green chemistry based organic synthesis has expanded tremendously in past few years^28-37. Researchers are currently focusing on development of green strategies for the synthesis of organic compounds of biological importance^38,39. Theoretical chemistry calculations are dependent on physicochemical calculations and quantum chemistry. DFT can predict various molecular properties. Especially, different spectroscopic investigations can be achieved: UV/Vis spectra, IR and Raman frequencies and intensities, NMR chemical shifts, and spin-spin coupling constants^40-44. Likewise, DFT calculations can predict HOMO-LUMO energies, bond lengths, bond angles, dihedral angles, and spectroscopic properties^45-66. The comparison of theoretical calculations with experimental results provides good deal of information. By using computation results, it has become possible to arrive at reaction mechanistic pathway. DFT method via B3LYP functional has been shown to predict theoretical properties that agree well with experimental spectroscopic findings^67-74. The assignment of absorption bands and, as a result, the prediction of electronic and chemical properties of molecules is found to be accurate when using the B3LYP functional with a 6-311G(d,p) basis package^{49,75, 76}. In light of various aspects discussed above, here in this paper, we wish to report density functional theory investigation of previously synthesized (E)-7-((2-chloroquinolin-3-yl)methylene)-1,2,6,7-tetrahydro-8H-indeno[5,4-b]furan-8-one³² (2-CQMIF). To the best of our knowledge, this the first report on computational study of the title molecule.

METHODS:

Computational study:

DFT calculations were performed on an Intel (R) Core (TM) i5 computer using Gaussian-03 program package without any constraint on the geometry⁷⁷. The geometry of the molecules studied in this is optimized by DFT/B3LYP method using 6-311G(d,p) basis set. The FMO analysis and quantum chemical study was performed using same basis set. The electronic excitations of title molecule have been calculated at TD-B3LYP/6-311G(d,p) level of theory for B3LYP/6-311G(d,p) optimized geometries. To investigate the reactive sites of the title molecules, the MEP was computed using the same method. All the calculations were carried out for the optimized structure in the gas phase. The experimental UV-Visible spectrum is recorded in dimethyl sulfoxide (DMSO) solvent.

RESULTS AND DISCUSSION:

Optimized Molecular Structure:

The optimized molecular structure of the title 2-CQMIF molecule is given in Figure 1. In Figure 2, the optimized molecular structures are presented along x,y and z Cartesian axes. The 2-CQMIF molecule is having C1 point group symmetry and the dipole moment is 5.0279 Debye. The optimized geometrical parameters; bond lengths and bond angles of the title molecule have been computed and presented here in Table 1 and Table 2. In the 2-CQMIF molecule, the C=O (C16-O20) bond length is 1.2169 Å and the C=C (C21-C22) bond length in alkene is 1.3453 Å. The C-Cl (C26-Cl35) bond length is 1.7713 Å. The imine bond lengths are 1.2912 Å (C26-N34) and 1.3639 Å (C27-N34). Amongst aromatic C=C bond lengths, C32-C36 bond is the longest (1.4148 Å) and the shortest is C30-C32 (1.3741 Å). Other bond lengths are also in good agreement. All the bond angles are also in good agreement.

Figure 1 Optimized molecular structure of 2-CQMIF molecule

Figure 2 Optimized molecular structures along x, y and z Cartesian axes

Table 1 Optimized geometrical parameters of 2-CQMIF molecule at B3LYP/6-311G(d,p) basis set

Bond lengths (Å)
C1-C2	1.3988	C9-C12	1.547	C25-C28	1.4115
C1-C6	1.3946	C12-H13	1.0937	C25-H29	1.0815
C1-H7	1.083	C12-H14	1.0892	C26-N34	1.2912
C2-C3	1.3912	C12-O15	1.4586	C26-Cl35	1.7713
C2-H8	1.0849	C16-O20	1.2169	C27-H28	1.4247
C3-C4	1.4025	C16-C21	1.5051	C27-N34	1.3639
C3- C17	1.518	C17-H18	1.0964	C27-H38	1.4137
C4- C5	1.3884	C17-H19	1.097	C28-C30	1.4182
C4-C16	1.4785	C17-C21	1.5144	C30-H31	1.0849
C5- C6	1.3918	C21-C22	1.3453	C30-C32	1.3741
C5- C9	1.5068	C22-H23	1.0853	C32-H33	1.0838
C6- O15	1.3609	C22-C24	1.4587	C32-C36	1.4148
C9-H10	1.0947	C24-C25	1.3852	C36-H37	1.084
C9-H11	1.0908	C24-C26	1.4412	C36-C38	1.3756
-	-	-	-	C38-H39	1.0828

Global descriptor analysis:

The pictorial representation of HOMO-LUMO orbitals is given in Figure 3. The electronic parameters such as E_HOMO, E_LUMO, ionization enthalpy (I), and electron affinity are given in Table 3. The quantum chemical parameters like electronegativity (χ), absolute hardness (η), softness (σ), electrophilicity (ω), chemical potential (Pi) are presented in Table 4. The frontier molecular orbital (FMO) analysis suggests that the energy gap in the 2-CQMIF molecule is 3.4626 eV. The lower HOMO-LUMO energy gap demonstrates the inevitable charge transfer is happening within the molecule. The global softness (σ), and the absolute hardness (η) values are 1.7313 eV and 0.5776 eV respectively. The ease of removal of an electron is governed by its chemical potential Pi and it is likewise identified with its electronegativity (χ). A good electrophile is described by a higher value of global electrophilicity (ω) and the higher value of ω indicates good nucleophile. Our results suggest that the 2-CQMIF molecule has a higher value of global electrophilicity (ω = 5.2948 eV), so it is most likely to accept electrons readily and also would undergo nucleophilic attack easily. As Pi value increases, the ability of a molecule to lose an electron increases. The maximum charge transfer is in the title molecule is 2.5673 eV.

Figure 3 HOMO-LUMO pictures

Table 3 Electronic parameters of 2-CQMIF molecule

Parameter	Values
E (a.u.)	−1474.33
E_HOMO (eV)	−6.1761
E_LUMO (eV)	−2.7135
I (eV)	6.1761
A (eV)	2.7135
Eg (eV)	3.4626

Table 4 Global reactivity parameters of 2-CQMIF molecule

Parameter	Values
χ (eV)	4.4448
ɳ (eV)	1.7313
σ (eV^-1)	0.5776
ω (eV)	5.7056
Pi (eV)	−4.4448
ΔNmax (eV)	2.5673
Dipole Moment (Debye)	5.0279

UV-Visible study:

The theoretical UV-Visible spectral study of 2-CQMIF molecule were performed at TD-DFT-B3LYP method with 6-311G(d,p) basis set. The theoretical UV-Visible simulation was carried out in gas phase and DMSO. The experimental UV-Visible spectrum was recorded in DMSO solvent. The theoretical and experimental UV-Visible spectra are depicted in Figure 4 and Figure 5 respectively. The computed UV-Visible data is compared with the experimental observations for the assignment of absorption signals. The UV-Visible computations were simulated up to three singlet excited states. The gas phase theoretical UV-Visible absorption signals are found at 400.39nm, 377.53nm, and 335.22 nm. The absorption peak at 400.39nm arises due to the n-p* transition. The other two peaks are comparatively more intense peaks and therefore arise due to the p -p* transitions. The theoretical UV-Visible spectrum in the DMSO solvent exhibited peaks at 388.77nm, 384.33 nm and 347.58nm for the first three singlet excited states. This infers that DMSO has hypsochromic shift on the first excited state and bathochromic shift on the second and third singlet excited states. This validates the correct assignment of the absorption bands. The experimental values for the absorption peaks are 384.25 nm and 337.12nm. These two peaks are rightly matching with the first and third singlet excited states recorded theoretically in DMSO solvent.

Figure 4 Simulated UV-Visible spectra of 2-CQMIF in gas phase and DMSO

Figure 5 Experimental UV-Visible spectrum of CQMIF in DMSO

Mulliken atomic charges:

The Mulliken atomic charges of the 2-CQMIF molecule are calculated by DFT/B3LYP method with 6-311G(d,p) basis set in the gaseous phase and are given in Table 5 and pictorial representation is given in Figure 6. Mulliken atomic charges reveal that all the hydrogen atoms have a net positive charge but H18 and H19 atoms have a more positive charge than other hydrogen atoms and therefore they are more acidic. These two hydrogen atoms are flanked between two C=C groups. Amongst, a carbon atom, the C6 atom has the highest net positive charge (0.238699) as it is attached to an electronegative oxygen atom. On the other hand C21 atom has the highest negative charge (-0.212075).

Figure 6 Mulliken atomic charge distribution in 2-CQMIF molecule

Table 5 Mulliken atomic charges in 2-CQMIF molecule

Atom	Charge	Atom	Charge
1 C	-0.063438	21 C	-0.212075
2 C	-0.071060	22 C	0.017836
3 C	-0.138021	23 H	0.137538
4 C	-0.031269	24 C	-0.104750
5 C	-0.146792	25 C	0.133430
6 C	0.238699	26 C	0.095249
7 H	0.106805	27 C	0.091854
8 H	0.083850	28 C	-0.112266
9 C	-0.167357	29 H	0.105150
10 H	0.142645	30 C	-0.062353
11 H	0.146102	31 H	0.090465
12 C	-0.012783	32 C	-0.087285
13 H	0.123688	33 H	0.102484
14 H	0.123675	34 N	-0.320277
15 O	-0.354584	35 Cl	-0.058044
16 C	0.229659	36 C	-0.084241
17 C	-0.098668	37 H	0.104824
18 H	0.148561	38 C	-0.035129
19 H	0.142213	39 H	0.109330
20 O	-0.313665	-	-

Vibrational Assignments:

Figure 7 2-CQMIF molecule with labeled rings

The titled 2-CQMIF molecule has 39 atoms and therefore has 111 fundamental modes of vibration according to 3N–6 formula. The 2-CQMIF molecule has labeled according rings present in it (Figure 7). Essentially all 111 fundamental modes of vibrations are IR active. The harmonic-vibrational frequencies calculated for a molecule at B3LYP level using basis set 6-311G(d,p) have been represented in Table 6. The comparison has been made between observed frequencies with scaled frequencies DFT hybrid B3LYP method, and it has been found that there is good agreement between scaled and experimental frequencies. Computed harmonic vibrational wavenumbers are usually higher than experimental ones owing to the anharmonicity of the incomplete treatment of electron correlation⁷⁸. 6-311G(d,p) basis set was used to determine harmonic frequencies, which were then scaled by an acceptable scaling factor^49,79.

Table 6 Selected experimental and scaledtheoretical vibrational assignments of 2-CQMIF molecule calculated at B3LYP/6-311G(d,p) level

Mode	Computed scaled frequencies (cm^-1)	IR Intensity (km) mol^-1	Observed frequencies (cm^-1)	Assignments
110	3196.23	9.74	-	v C-H (Ring A)
109	3193.24	1.67	-	v C22-H
107	3189.33	2.43	-	v C1-H, C2-H
106	3182.212	26.07	-	ν asym C9-H₂, ν asym C12-H₂
100	3127.53	8.49	-	v sym C9-H₂
99	3117.72	55.12	-	ν sym C12-H₂
98	3092.74	7.82	-	ν sym C17-H2
96	1626.98	26.04	1620.21	v C=C (Ring D)
95	1602.06	16.04	-	v C=C (ring D)
93	1546.38	104.51	-	v C=C (C21-C22)
91	1503.24	17.40	1473.62	v C=C (Ring B), v C=C (C21-C22)
84	1365.53	48.53	1338.60	β C25-H, - C17-H₂
79	1259.22	0.88	1253.73	-C12-H₂
77	1225.18	10.96	1230.58	β C22-H
73	1157.92	0.73	1139.93	t-C9-H₂, t-C12-H₂,β C1-H, β C2-H
58	924.78	33.57	929.69	C9-H₂
52	868.06	1.22	864.11	γ C1-H, γ C2-H
48	836.14	10.02	819.75	t-C12-H₂
46	776.28	33.56	771.53	β-H (Ring A)
38	684.67	5.50	684.73	γ C1-H, γ C22-H, γ C30-H, γ C39-H, Ring A,B,C, D, E def

v- stretching; sym- symmetric; asym- asymmetric; def- deformation; β- In-plane bending; γ- Out of plane bending; ρ- rocking; t- twisting; - wagging; - scissoring

Thermodynamic properties:

The thermodynamic data of 2-CQMIF molecule obtained from DFT method at B3LYP/6-311G(d, p) level is presented in Table 7. Here in this, E_total, Heat Capacity at constant volume, total entropy S, zero point vibrational Energy and Rotational constants have been presented. The data revealed in this could be useful for the further assessment of the other thermodynamic properties.

Table 7 Thermodynamic properties of the title molecule

Parameter

Value

E total (kcal mol^-1)

Translational

Rotational

Vibrational

194.867

0.889

193.090

Heat Capacity at constant volume,

Cv (cal mol^-1K^-1)

Translational

Rotational

Vibrational

74.163

2.981

68.202

Total entropy S (cal mol^-1K^-1)

Translational

Rotational

Vibrational

131.895

43.427

35.877

52.591

Zero point Vibrational Energy Ev₀ (kcal mol^-1)

184.02385

Rotational constants (GHZ)

0.41718

0.09596

0.07870

Molecular electrostatic potential surface analysis:

MEP plot is given in Figure 8. The phenomena like nucleophilic and electrophilic sites, solvent effects, hydrogen bonding interactions, etc. could be determined by the use of a molecular electrostatic potential. MEP is primarily used to find out the reactive sites of molecules empower to anticipate how one particle can interact with other molecules. The different values of the electrostatic potential at the surface of the molecule are represented by distinct colours. The red and yellow regions correspond to the region of high electron density and are associated with electrophilic reactivity. On the other hand, the blue parts represent low electron density and susceptible to nucleophilic reactivity and green colours represent regions of zero potential, respectively. The MEP surface analysis indicates that the benzene ring attached to the dihydrofuran ring is highly susceptible to aromatic electrophilic substitution reactions and quinoline moiety is prone to nucleophilic attacks.

Figure 8. Molecular electrostatic potential

CONCLUSIONS:

In conclusion, structural, chemical and spectroscopic aspects of titled compound 2-CQMIF have been explored by utilizing DFT strategy at B3LYP/6-311G(d,p), and TD-DFT at B3LYP/6-311G(d,p) basis set. The molecule title molecule is having C1 point group symmetry and the dipole moment is 5.0279 Debye. Structural parameters are examined to comprehend understand the chemical structure of the title molecule. The lower energy gap in the titled molecule demonstrates the inevitable charge transfer is happening within the molecule. Our results suggest that the title molecule is most likely to accept electrons promptly and furthermore would go through nucleophilic attack easily. The comparison between the theoretical and experimental spectral analysis shows good agreement. The investigation uncovered that the first singlet excited state arises due to the n- p* transition. The MEP surface analysis shows that the benzene fused to dihydrofuran ring is highly susceptible to aromatic electrophilic substitution reactions and quinoline structure is prone to nucleophilic attacks. This study could provide a ladder for the further exploration of the title molecule in various fields.

ACKNOWLEDGEMENT:

Authors are grateful to Prof. (Dr.) A. B. Sawant for his guidance for the Gaussian study. Authors acknowledge Department of Chemistry, Arts, Science and Commerce College, Manmad, MS, India for research facilities.

CONFLICT OF INTEREST:

The authors declare no conflict of interest.

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Received on 24.01.2021 Modified on 20.05.2021

Research J. Pharm.and Tech 2022; 15(3):1101-1108.

DOI: 10.52711/0974-360X.2022.00184

Bond angles (°)
C2-C1-C6	118.6792	C9-C12-H14	114.0114	C24-C25-H29	119.831
C2-C1-H7	121.3271	C9-C12-O15	106.9746	C28-C25-H29	118.3896
C6-C1-H7	119.9937	H13-C12-H14	109.1494	C24-C26-H34	125.9158
C1-C2-C3	119.8758	H13-C12-O15	107.4423	C24-C26- C35	118.8301
C1-C2-H8	119.3895	H14-C12-C15	107.3166	C34-C26- C35	115.2504
C3-C2-H8	120.7338	C6-O15-C12	107.3502	C28-C27-H34	121.282
C2-C3-C4	120.2855	C4-C16-O20	127.2201	C28-C27-H38	119.5377
C2-C3-C17	128.6913	C4-C16-C21	106.2361	C34-C27-H38	119.1801
C4-C3-C17	111.0177	O20-C16-C21	126.5389	C25-C28-H27	117.4084
C3-C4-C5	120.5697	C3-C17-H18	112.3595	C25-C28-C30	123.4341
C3-C4-C16	110.0995	C3-C17-H19	110.3293	H27-C28-C30	119.1569
C5-C4-C16	129.3255	C3-C17-C21	103.7193	C28-C30-C31	119.1525
C4-C5-C6	118.2778	H18-C17-H19	106.8224	C28-C30-C32	120.2186
C4-C5-C9	133.1514	H18-C17-C21	111.8902	C31-C30-C32	120.6289
C6-C5-C9	108.5203	C19-C17-C21	111.8123	C30-C32-H33	120.0798
C1-C6-C5	122.3103	C16-C21-C17	108.8148	C30-C32-H36	120.4003
C1-C6-O15	124.3643	C16-C21-H22	119.1896	C33-C32-H36	119.5198
C5-C6-O15	113.3246	C17-C21-H22	131.8969	C26-C34-H27	118.9995
C5-C9-H10	110.6353	C21-C22-H23	114.2978	C32-C36-H37	119.4032
C5-C9-H11	113.058	C21-C22-C24	129.6375	C32-C36-H38	120.7067
C5-C9-C12	101.1396	H23-C22-C24	116.0475	C37-C36-H38	119.8901
H10-C9-H11	107.0772	C22-C24-C25	123.8786	C27-C36-H38	119.9795
H10-C9-C12	112.2751	C22-C24-C26	121.483	C27-C36-H39	117.9387
H11-C9-C12	112.7172	C25-C24-C26	114.6289	C38-C38- C39	122.0818
C9-C12-H13	111.6315	C24-C25-C28	121.7644	-	-