Synthesis, structural, vibrational, electronic, thermal and Fukui analysis of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate

Accepted Manuscript Synthesis, structural, vibrational, electronic, thermal and Fukui analysis of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate

Anshul Uppal, Parteek Kour, Anil Kumar, Yugal Khajuria PII:

S0022-2860(18)30488-5

DOI:

10.1016/j.molstruc.2018.04.046

Reference:

MOLSTR 25119

To appear in:

Journal of Molecular Structure

Received Date:

07 March 2018

Revised Date:

11 April 2018

Accepted Date:

11 April 2018

Please cite this article as: Anshul Uppal, Parteek Kour, Anil Kumar, Yugal Khajuria, Synthesis, structural, vibrational, electronic, thermal and Fukui analysis of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate, Journal of Molecular Structure (2018), doi: 10.1016/j.molstruc.2018.04.046

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ACCEPTED MANUSCRIPT

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Synthesis, structural, vibrational, electronic, thermal and Fukui analysis of

2

diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate

3

Anshul Uppala, Parteek Kourb, Anil Kumarb, Yugal Khajuriaa*

4

a Department of Physics, Shri Mata Vaishno Devi University, Kakryal, Katra-182320, Jammu &

5

Kashmir, India.

6

b Synthetic Organic Chemistry Laboratory, Faculty of Sciences, Shri Mata Vaishno Devi

7

University, Kakryal, Katra-182320, Jammu & Kashmir, India.

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*Corresponding

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Abstract

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author: [email protected]

In this paper diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate has been synthesized

11

and characterized by

FTIR, FT-Raman UV-Vis. The structural geometrical parameters,

12

vibrational, electronic, HOMO-LUMO, Fukui analysis, and the thermodynamic properties of the

13

molecule were performed on the basis of DFT calculations at B3LYP/6-311G(d,p) basis set

14

using Gaussian 09 package. Thermogravimetric (TG) analysis was also carried out to study

15

thermal stability of compound. The HOMO-LUMO study to find the band gap of compound has

16

been extended to calculate ionization potential, electron affinity, global hardness, electron

17

chemical potential and global electrophilicity to study the chemical behavior of compound. A

18

good agreement between observed and calculated wavenumbers has been obtained. The

19

correlations between the statistical thermodynamics and temperature show that increase in

20

temperature increases heat capacities, entropies and enthalpies.

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Keywords: FTIR, FT-RAMAN, UV-Vis, TGA, HOMO-LUMO, Fukui Functions

22 23

1. Introduction Organophosphonates are versatile substrates that constitute core unit of several natural

24

products [1] and bioactive compounds [2]. Due to the diverse applications of phosphonates in

25

industrial, medicinal and agricultural purposes, their synthesis has been a focus of interest for

26

organic and medicinal chemists [3].

27

In particular, α- hydroxyphosphonates represents an elite class of organic compounds due to their

28

broad range of pharmacological properties such as antifungal [4], antiviral [5], anticancer [6],

29

rennin inhibitory [7], HIV protease [8]. These medicinally privileged scaffolds are also applied 1

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as enzyme inhibitors [9], metabolic probes [10], peptide mimetics [11], as flame retardants [12]

2

and additives [13]. Furthermore biphosphonates are popular drugs which are for the treatment of

3

bone related disorders [14].

4

Additionally, they act as pioneer materials for the synthesis of 1,2-diketones [15], and also

5

applied as ligands in asymmetric synthesis [16]. Organophosphonates also find utility as key

6

intermediates in construction of numerous natural and synthetic products including un-natural

7

aminoacids [17]. Because of diverse applications of α-hydroxyphosphonates, the compound was

8

synthesized for its detailed experimental and theoretical studies.

9

In this paper, we have prepared diethyl (hydroxy(phenyl) methyl) phosphonate (Fig. 1) using

10

our previously reported method [18]. It is well known that B3LYP functional in DFT provides an

11

outstanding understanding between accuracy and computational efficiency of vibrational spectra

12

[19-22]. The optimized geometrical parameters (bond lengths, bond angles) electronic and

13

vibrational frequencies, fukui functions, atomic charges, and statistical thermodynamic

14

parameters of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate are studied with 6-

15

311G(d,p) basis set using DFT and also HF method[23]. All the vibrational frequency modes

16

were assigned with the help of VEDA (Vibrational energy distribution analysis) [24] and a very

17

good agreement between observed and calculated wave numbers have been obtained. NBO and

18

atomic charges analysis was performed to provide information’s about various intramolecular

19

interactions and electronegativity in the compound respectively. The electronic absorption

20

spectrum was simulated at TD-DFT/6-311G(d,p) level of theory.

CHO

EtO +

MeO 21

1

Bi(NO3)3..5H2O OEt (10 mol%) P OEt neat, rt 2

OH OEt P

MeO

OEt

O 3

22 23 24

Fig.1. Synthesis of diethyl (hydroxy(4-methoxyphenyl)methyl)phosphonate 2. Synthesis of diethyl (hydroxy(4-methoxyphenyl) methyl)phosphonate :

25

A mixture of benzaldehyde 1 (1 mmol), triethylphosphite 2 (1 mmol) and Bi(NO3)3.5H2O

26

(10 mol%) was stirred at room temperature for 5 h under solvent-free condition. After 2

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completion of reaction as monitored by TLC, reaction mixture was cooled to get the crude

2

product. This crude product was isolated and purified by recrystallization from ethanol to afford

3

diethyl (hydroxy(phenyl) methyl) phosphonate in 90% yield.

4

3. Experimental details

5

Shimadzu IR-Tracer having spectral resolution of 1cm-1 was used to record the FTIR

6

spectrum of the compound in the spectral range of 4000-400 cm-1 and the FT-Raman Spectra of

7

the compound has been recorded in the spectral range of 4000-50 cm-1 using BRUKER: RFS 27.

8

Shimadzu UV-2600 Double beam spectrophotometer in the range 190-1400 nm and Shimadzu

9

DTG-60 thermal analyzer were used for UV-Vis spectra and TGA of the molecule respectively.

10

4. Computational details

11

DFT is an advantageous method that is extensively used in computational chemistry as it

12

gives accurate prediction of ground and excited state properties. All the computational

13

calculations were carried out by using Gaussian 09 program [25]. The optimized structure of the

14

compound is obtained by using HF method and is then again reoptimized by DFT using Becke’s

15

three-parameter hybrid functional(B3) [26,27] for the exchange part and the Lee-Yang-Parr

16

(LYP) correlation function [28], using 6-311G(d,p) basis set. For the calculations of vibrational

17

frequencies, atomic charges, Fukui functions, thermodynamic parameters and other molecular

18

properties, the reoptimized structural parameters have been used. The vibrational frequency

19

assignments were made accurately by using VEDA program. To get visual animation and to

20

carry out verification of the normal modes assignment, Gauss view program [29] has been used.

21

The electronic properties such as absorption wavelengths, excitation energies and oscillator

22

strengths were calculated using time-dependent DFT (TD-DFT) [30-32].

23

5. Results and discussion

24

5.1 Geometric structure

25

The optimized structure of the title compound is shown in Fig. 2 and bond lengths and

26

bond angles calculated by DFT method using 6-311G(d,p) basis set for the optimized structure

27

are shown in Table 1 and Table 2 respectively. The minimum energies of the optimized structure

28

of the title molecule calculated by the HF/6-311G(d,p) and B3LYP/6-311G(d,p) are

29

‒ 1180.80289381 𝑎.𝑢. and ‒ 1186.49677314 𝑎.𝑢. . The energy difference is about ‒ 5.69 𝑎.𝑢.

3

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1 2

Fig. 2 Optimized structure of diethyl (hydroxy(4-methoxyphenyl)methyl)phosphonate

3 4 5 6

Table 1 Calculated Bond lengths (Å) of the molecule with DFT theory employing 6-311G(d,p) basis set. Atom no.

7 8 9 10 11 12 13 14 15 16 17

C1-C2 C1-C6 C1-H19 C2-C3 C2-O11 C3-C4 C5-C6 C5-C7 C6-H22 C7-O8 C7-P9 C7-H23 O8-H24

B3LYP/6311G(d,p) 1.3989 1.3869 1.0834 1.3975 1.3644 1.394 1.3988 1.5102 1.0815 1.4227 1.8547 1.0993 0.9675

Atom no. P9-O10 P9-O13 P9-O16 O11-C12 C12-H25 O13-C14 C14-C15 C14-H28 C15-H32 O16-C17 C17-C18 C17-H33 C17-H34

B3LYP/6311G(d,p) 1.4896 1.6126 1.6072 1.4196 1.0889 1.4555 1.5175 1.0909 1.0918 1.4527 1.5141 1.0932 1.0928

Table 2 Calculated Bond angles (˚) of the molecule with DFT theory employing 6-311G(d,p) basis set. 4

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Structural parameters C2-C1-C6 C2-C1-H19 C6-C1-H19 C1-C2-C3 C1-C2-O11 C3-C2-O11 C2-C3-C4 C2-C3-H20 C5-C7-P9 C5-C7-H23 O8-C7-P9 O8-C7-H23 P9-C7-H23 C7-O8-H24 C7-P9-O10 C7-P9-O13 C7-P9-O16 O10-P9-O13 O10-P9-O16 O13-P9-O16

B3LYP/6311G(d,p) 120.4228 118.3861 121.1901 119.3387 115.9268 124.7336 119.6683 121.1116 115.83 108.9427 106.3317 110.6791 104.3221 106.9692 110.0433 110.5039 101.5842 113.8629 117.7669 102.2043

Structural parameters O11-C12-H27 H25-C12-H26 P9-O13-C14 O13-C14-C15 O13-C14-H28 H28-C14-H29 C14-C15-H30 C14-C15-H31 C14-C15-H32 H30-C15-H31 P9-O16-C17 O16-C17-C18 O16-C17-H33 C18-C17-H34 H33-C17-H34 C17-C18-H35 C17-C18-H36 C17-C18-H37 H35-C18-H36 H35-C18-H37

B3LYP/6311G(d,p) 111.5686 109.1957 122.196 111.3421 104.6187 109.0155 109.6153 110.9788 110.7641 108.3715 121.3813 107.9487 108.5733 111.4864 108.9449 109.7996 110.7172 110.7575 108.4103 108.4319

2 3

5.2 Atomic charges

4

The Vibrational spectrum is largely influenced by the distribution of charge on the

5

molecule. The total atomic charges of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate

6

obtained by Mulliken [33] and NBO methods using HF/6-311G(d,p) and B3LYP/6-311G(d,p)

7

level of theory are shown in Fig. 3. The total atomic charge values are obtained by Mulliken

8

population analysis and natural charges are obtained by natural bond orbital analysis The

9

Mulliken population analysis is used to obtain atomic charge distribution which is based on the

10

linear combination of atomic orbitals and therefore the wave function of the molecule. Positive

11

Mulliken charge values are exhibited by all the atoms of hydrogen. The hydrogen atom charges

12

range in case of HF/6-311G(d,p) is 0.087 to 0.281 where in case of B3LYP /6-311G(d,p) it

13

varies from 0.097 to 0.264. The charges changes with basis set due to polarization, for example,

14

the charge of O11 atom is -0.348949 for B3LYP/6-311G(d,p), -0.466111 for HF/6-311G(d,p) as

15

given in Table3. From Table 3 it can be concluded that the oxygen atoms exhibit a substational

16

negative charge, which are donor atoms. Only C2, P9 and Hydrogen atoms exhibit a positive

17

charge, which are acceptor atoms. 5

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P9

1.5

HF DFT

1.0

Mulliken

0.5 C2 C4

0.0

Charge/e

_

C1

-0.5

C3

C5

C6

C17

C14

O11

H19

H21

H20

C7

C12 C15

H23 H22

H 25 H24

H26

H27

H29 H28

H31 H30

H33 H32

H35 H34

H37 H36

C18

O8 O10

O13

O16

2.5 2.0 1.5

NBO

1.0 0.5 0.0 -0.5 -1.0

Atom

1 2 3

Fig. 3 Mulliken’s plot and NBO plot of with HF and DFT theory using B3LYP/6-311G(d,p) basis set.

4 5 6

Table 3: MULLIKEN AND NBO CHARGES USING HF AND DFT THEORY Atom NO. C1 C2 C3 C4 C5 C6 C7 O8 P9 O10 O11 C12 O13 C14 C15 O16 C17 C18 H19 H20 H21

Mulliken 6-311G(d,p) HF DFT -0.111804 -0.098164 0.268298 0.178030 -0.151989 -0.139976 -0.053781 -0.044146 -0.188263 -0.153167 -0.029169 -0.032570 -0.055925 -0.143920 -0.491099 -0.401304 1.563692 1.209705 -0.755438 -0.596881 -0.466111 -0.348949 -0.027857 -0.132085 -0.678656 -0.527390 0.072757 -0.034802 -0.249340 -0.301512 -0.679200 -0.536657 0.087768 -0.014947 -0.243746 -0.299225 0.107297 0.100939 0.106322 0.101690 0.097854 0.097963 6

NBO 6-311G(d,p) HF DFT -0.24377 -0.23621 0.39195 0.32842 -0.30039 -0.28965 -0.13640 -0.17572 -0.11156 -0.09363 -0.13633 -0.18034 -0.12985 -0.16702 -0.76964 -0.73621 2.51156 2.28932 -1.19694 -1.08487 -0.59709 -0.52501 -0.08502 -0.19704 -0.93003 -0.84937 0.09129 -0.00314 -0.52003 -0.60007 -0.92474 -0.84970 0.08405 -0.00711 -0.50643 -0.58315 0.19976 0.21297 0.19277 0.20684 0.19011 0.20853

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H22 H23 H24 H25 H26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37

0.117612 0.144312 0.281298 0.111975 0.088182 0.087062 0.098717 0.127004 0.090828 0.106166 0.105446 0.114923 0.107678 0.092114 0.101800 0.103276

0.109670 0.167022 0.264557 0.128608 0.110066 0.109300 0.119887 0.141483 0.105892 0.118931 0.124055 0.136038 0.132224 0.109857 0.119044 0.120732

0.20494 0.16963 0.47742 0.15654 0.13430 0.13369 0.14261 0.16182 0.17251 0.17889 0.17690 0.14939 0.14400 0.17377 0.17465 0.17566

0.22201 0.19800 0.47670 0.18470 0.16302 0.16277 0.17374 0.18667 0.20088 0.20529 0.20337 0.17642 0.17529 0.20244 0.19980 0.20107

1 2

5.3 Vibrational analysis

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The vibrational analysis of the compound diethyl (hydroxy(4-methoxyphenyl) methyl)

4

phosphonate(C12H19O5P) was carried out with DFT (B3LYP) level. DFT (B3LYP) is an efficient

5

method to carry the vibrational analysis of the compound [34].Positive values of all the 105

6

modes of vibrations of present compound confirmed that geometries are located at true local

7

minima of potential energy surface. Out of 105 modes of vibrations only those are given for

8

which experimental modes are observed.

9

The calculated wavenumbers are usually higher than the corresponding experimental

10

ones, due to the combination of electron correlation effects and insufficient basis set deficiencies.

11

Therefore, in order to improve the calculated values, the discrepancy between experimental and

12

theory is removed by computing anharmonic corrections explicitly, by introducing scalar field ,

13

by direct scaling of the calculated wavenumbers with a proper scaling factor [35, 36]. It is well

14

known that different scaling factors reproduce theoretical wavenumbers in good agreement with

15

the experimental wavenumbers. In the present study, the computed wavenumbers have been

16

scaled by 0.967. The assignments of the wavenumbers have been done with the help of VEDA

17

by using PED (potential energy distribution). The complete detail of the PED analyses can be

18

found elsewhere [37, 38]. The calculated wavenumbers (scaled), observed and assignments of IR

19

band, Raman are given in Table 4 and comparison between calculated and observed

20

wavenumbers (IR and Raman) are given in figures 4 and 5.The vibrational modes of the

21

C12H19O5P molecule are discussed as under: 7

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5.3.1. C-H vibrations

2

Normally above 3250-2950 cm-1, the aromatic C-H stretching vibrations occurs.

3

Substituent’s nature does not affect the bands in this region. In the present work, the

4

experimental C-H stretching vibration of compound were observed in the range 3109-2973 cm-1

5

and the computed scaled wavenumbers in the range 3107-2982 cm-1. Figure 4 and 5 represent the

6

observed and calculated FTIR and FT-Raman spectra respectively. A close agreement between

7

observed and calculated spectra can be seen from these figures.

8

5.3.2. C˗O vibrations

9

The C-O stretching vibration occurs as a strongest band in the region 1000˗1300 cm-1. For

10

title molecule C-O stretching vibrations observed in the FTIR spectrum at 1222, 1058 and 1020

11

cm-1 and in FT-RAMAN spectrum at 1224, 1057 and 1023 cm-1 corresponds to the calculated

12

bands at 1235, 1034 and 1024 cm-1 with 51, 72 and 82% contribution. As shown in the Table 4. ,

13

the DFT/6-311G(d,p) values and the experimental one are in good agreement.

14

5.3.3 C˗C vibrations

15

The C-C stretching modes of the phenyl group are expected in the range from 1650-1200

16

cm-1 [39]. Therefore, the strong vibrational frequency bands at 1611, 1541, 1300 and 1194 cm-1

17

are assigned to C˗C stretching vibrations in FTIR spectrum and the strong vibrational frequency

18

bands at 1606, 1585 and 1198 cm-1 corresponds to FT-RAMAN spectrum which coincides well

19

with the calculated vibrational bands at 1603, 1565, 1308 and 1206 cm-1 with significant

20

contribution of TED. The medium intensity band experimentally at 834 and 837 cm-1 are also

21

attributed to C˗C stretching and matches well with the calculated frequency value at 832 cm-1.

22

5.3.4 P˗C vibrations

23

The P-C stretching modes appear in the region of 754-634 cm-1 medium-weak in IR,

24

strong in RAMAN. In FTIR spectrum frequency bands at 754 and 662 cm-1 and the bands of FT-

25

RAMAN spectrum at 757 and 660 cm-1. The computed theoretical wavenumber of P-C

26

stretching vibrations at 759 and 654 cm-1 by 6-311G(d,p) coincides very well with the

27

experimental value and the PED corresponds is 59% and 38% as shown in Table 4.

8

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Experiment

Theory

4000

3500

3000

2500

2000

1500

-1 Wavenumbers (cm )

1000

500

0

1 2 3

Fig. 4 Experimental and calculated FTIR spectra of diethyl (hydroxy(4methoxyphenyl)methyl)phosphonate

Experiment

Theory

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )

4 5 6 7 8 9

Fig. 5 Experimental and calculated FT-Raman spectra of diethyl (hydroxy(4methoxyphenyl)methyl)phosphonate Table 4 The experimental IR, Raman and calculated wavenumbers (cm-1) with potential energy distribution (PED %). 9

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1

Calculated frequencies DFT/6311G(d,p) 3107 3080 3070 3027 3015 2982 1603

2 3 4 5

Experimental frequencies FTIR

Experimental frequencies FT-RAMAN

3109 3080 3051 3038 3018 2982 1611

3078 3058 3017 2973 1606

1565 1495 1474 1456 1435 1429 1361 1308

1541 1508 1474 1458 1435 1418 1368 1300

1585

1280 1254 1235 1206

1279 1248 1222 1194

1281

1164 1098 1035 1024 950 832 795 759 654 630 585

1168 1098 1058 1020 959 834 794 754 662 638 593

1174 1098

1455 1369

1224 1198

1023 973 837 791 757 660 638 596

Assignments and TED(≥15%, given in parenthesis) ν CH(92) ν CH(92) ν CH(91) ν CH(92) ν CH(95) ν CH(97) ν CC(57)+ β HCC(18) ν CC(70) β HCC(55) β HCH(85) β HCH(88) β HCH(79) β HCH(86) β HOC(74) ν CC(46)+ β HCC(16) β HCC(90) β HCO(54) ν OC(51) ν CC(15)+ β HCC(32) β HCO(78) β HCC(70) ν OC(72) ν OC(82) τ HCCH(92) ν CC(56) β HCC(70) ν PC(59) ν PC(47) β CCC(80) β COC(50)

ν – stretching, β – bending, γ˗ out-of-plane deformation, τ ˗ torsion 5.4 Natural bond orbital analysis

6

The NBO program as implemented in the Gaussian 09 package at the DFT/B3LYP level was

7

used for natural bond orbital analysis to understand intra-molecular delocalization or

10

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hyperconjugation. It is an efficient method to get information about second order interactions

2

between filled and vacant orbitals.

3

Delocalization of electron density between occupied Lewis-type (bond or lone pair) NBO

4

orbitals and formally unoccupied (antibond or Rydberg) non-Lewis NBO orbitals corresponds to

5

a stabilizing donor-acceptor interaction. For each donor NBO (i) and acceptor NBO (j), the

6

stabilization energy E(2) associated with delocalization ("2e-stabilization") is estimated. For each

7

donor NBO (i) and acceptor NBO (j), the stabilization energy E(2) associated with i

8

→ j delocalization, given by equation: 2

𝐹(𝑖,𝑗) 𝐸(2) = ∆𝐸𝑖𝑗 = 𝑞𝑖 𝐸𝑗 ‒ 𝐸𝑖

9

10

where qi is the donor orbital occupancy, Ei, Ej are diagonal elements (orbital energies)

11

and F(i,j) is the off-diagonal NBO Fock matrix element. Larger the E(2) value, the more

12

intensive is the interaction between electron donors and electron acceptors i.e. the more donating

13

tendency from electron donors to electron acceptors and the extent of electron delocalization is

14

greater. The intramolecular interaction are formed by the orbital overlap between bonding σ (C-

15

C) and antibonding σ* (C-C) orbital, which results in intramolecular charge transfer (ICT). In

16

this compound, the interaction between the C2-C3 (NBO 412) and the C4-C5 antibonding (NBO

17

417) having the strongest stabilization, 264.65 KJ/mol as in Table 5. The intramolecular

18

hyperconjugative interaction of σ (C2-C3)→ σ* (C1-C6) leading to a stabilization of 230.16

19

kJ/mol. The most important interaction energy is the electron donating from the LP(2) O11 atom

20

to σ* (C2-C3) which leads to a strong stabilization of 30.32 KJ/mol and interaction between

21

LP(2) O13 atom to π* (P9-O10) leads to less stabilization energy of 1.04KJ/mol. In the case of

22

P-O bond, σ (P9-O13) bonding conjugation with σ* (O13-C14) and σ (P9-O16) conjugation with

23

σ* (O16-C17) leads to stabilization energy of 24.95KJ/mol and 33.93KJ/mol respectively. As in

24

the case of O-H bond, σ (O8-H24) conjugation with σ * (C5-C7) leads to less stabilization energy

25

of 2.60KJ/mol, which shows that σ (O-H) bond do not have the stability to cause any change in

26

the ring.

27

pharmaceutical and biological properties of C12H19O5P.

28 29 30

Table 5 Second-order perturbation theory analysis of Fock matrix in NBO basis for diethyl (hydroxy(4-methoxyphenyl)methyl)phosphonate

Hence the charge transfer interactions explained above are responsible for the

11

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1 2 3 4 5 6 7

Donor (i)

ED(i)(e)

Acceptor (j)

ED(j)(e)

σ (C1-C2) σ (C1-C2) σ (C1-C6) σ (C1-C6) σ (C1-C6) σ (C1-H19) σ (C2-C3) σ (C2-C3) σ (C4-C5) σ (C4-C5) σ (C4-H21) σ (C6-H22) σ (O8-H24) π (P9-010) σ (P9-O13) σ (C12-H25) σ (C15-H30) σ (C18-H35) σ (C2-C3) σ (C2-C3) σ (C4-C5) σ (C7-P9) LP (2) O(11) LP(2)O(13) π (P9-O13) σ (P9-O16) π (P9-O16) σ (P9-O13) σ (P9-O16)

1.97188 1.97188 1.97378 1.69699 1.69699 1.97646 1.65986 1.65986 1.67866 1.67866 1.97793 1.97745 1.98784 1.98759 1.98088 1.99056 1.97972 1.98083 0.39617 0.39617 0.36608 0.14921 1.84195 1.89993 0.17343 0.17115 0.17115 0.17343 0.17115

σ* (C2-C3) σ* (O11-C12) σ* (C2-O11) σ* (C2-C3) σ * (C4-C5) σ* (C2-C3) σ* (C1-C6) σ* (C4-C5) σ* (C1-C6) σ* (C2-C3) σ* (C5-C6) σ *(C1-C2) σ * (C5-C7) π* (P9-O13) σ * (P9-O16) σ* (C2-O11) σ* (O13-C14) σ* (O16-C17) σ* (C1-C6) σ* (C4-C5) σ* (C7-P9) σ* (P9-O13) σ* (C2-C3) π * (P9-O10) π * (P9-O10) σ* (C7-O8) π * (P9-O10) σ* (O13-C14) σ* (O16-C17)

0.03023 0.00949 0.03257 0.39617 0.36608 0.03023 0.31840 0.36608 0.31840 0.39617 0.02583 0.02442 0.03467 0.17343 0.17115 0.03257 0.03099 0.03165 0.31840 0.36608 0.14921 0.17343 0.39617 0.07734 0.07734 0.01714 0.07734 0.03099 0.03165

E(2) (KJ/mol)a 4.47 3.52 3.34 22.52 18.31 4.34 16.55 22.42 21.61 17.43 4.53 4.02 2.60 2.47 3.72 4.19 4.97 4.54 230.16 264.65 4.28 6.61 30.32 1.04 2.68 5.04 3.64 24.95 33.93

E(j) - E(i) (a.u)b 1.25 0.98 1.06 0.27 0.29 1.07 0.30 0.30 0.29 0.28 1.09 1.07 1.13 1.17 1.06 0.90 0.75 0.75 0.01 0.01 0.16 0.03 0.34 0.70 0.13 0.04 0.13 0.02 0.01

F(i,j) (a.u)c 0.067 0.053 0.053 0.072 0.066 0.061 0.063 0.073 0.071 0.063 0.063 0.059 0.049 0.050 0.058 0.055 0.055 0.052 0.082 0.081 0.046 0.030 0.097 0.024 0.047 0.042 0.055 0.063 0.059

aE(2)

means energy of hyperconjugative interactions Energy difference between donor and acceptor i and j NBO orbitals c F(i,j) is the Fock matrix element between i and j NBO orbitals. b

5.5 UV-Vis spectral analysis

8

Most of the absorption spectroscopy of the organic molecules is based on transitions π˗ π*

9

and σ˗ σ* in the UV-Vis region [40, 41]. The UV-Vis absorption spectrum of C12H19O5P

10

molecule has been recorded in the spectral range 190-800 nm. Fig. 6 shows the experimentally

11

absorption spectrum of the compound. The most intense UV bands at 200, 272 and 292 nm

12

observed in the Fig. 6 are due to excitation from HOMO (ground state) to LUMO (excited state)

13

are in good agreement with the calculated results obtained from TD-DFT [42-44] method as 12

ACCEPTED MANUSCRIPT 1

shown in Table 6 along with their oscillator strength and assignments. The calculated absorption

2

spectrum shows that the maximum absorption wavelength corresponds to the electronic

3

transition from the HOMO˗0→LUMO+2 with 90% and from HOMO˗0→LUMO+3 with 81%

4

contribution.

292 nm

0.18

Absorbance (arb. units)

0.16 0.14 0.12 0.10 0.08 0.06 0.04

200 nm

0.02 0.00 200

300

400

500

600

700

800

Wavelength(nm)

5 6

Fig. 6 Experimental UV-Vis of diethyl (hydroxy(4-methoxyphenyl)methyl)phosphonate

7 8 9 10

Table 6 Theoretical and experimental electronic absorption spectra values of using TD-DFT/6311G(d,p) method and their assignments. Wavelength 𝛌(𝐧𝐦)

Energy(eV) Oscillator strength(f) Experiment Theory Theory Theory 195.8 6.33 0.0162 200

292

204.2

6.07

0.0054

223.9

5.54

0.2405

251.2

4.94

0.0258

11 13

Assignments [53] HOMO - 0→LUMO+3( + 81%) HOMO - 0→LUMO+2( + 90%) HOMO - 0→LUMO+1( + 78%) HOMO - 0→LUMO+0 ( + 78%)

ACCEPTED MANUSCRIPT 1

5.6. Thermodynamic properties

2

The studies of the thermodynamical properties of compounds are very important to

3

understand the chemical processes and thermodynamic properties of molecule. Using HF and

4

DFT method, the thermodynamic parameters such as thermal energy, vibrational energy, zero

5

point vibrational energy, heat capacity, entropy, rotational constants, and dipole moment have

6

been computed as shown in Table 7. The rotational constant values are observed to be nearly

7

same and dipole moment calculated differs slightly using both the methods as dipole moment

8

reflects the molecular charge distribution and is given as a vector in three dimensions. On the

9

basis of vibrational analysis and statistical thermodynamics, the standard

thermodynamic

10

parameters like heat capacity, entropy and enthalpy for the title compound at B3LYP/6-

11

311G(d,p) level were calculated within the temperature range from 100 to 700 K and are shown

12

in Table 8. From the correlation graphs of heat capacity, entropy and enthalpy (Fig. 7), it is

13

concluded that the increase in molecular vibrational intensities with temperature causes the

14

variation in thermodynamic properties with temperature [45]. The quadratic formulas were used

15

to fit the correlation equations between heat capacity, entropy, enthalpy changes and

16

temperatures, and R is the corresponding fitting factors (R2) for these thermodynamic properties

17

and the corresponding fitting equations are as follows: 0

‒5 2

2

𝑇 (𝑅 = 0.99956)

18

𝐶𝑝,𝑚 = 9.10792 + 0.24437𝑇 ‒ 8.82098 × 10

19

𝑆𝑚 = 61.90966 + 0.33564𝑇 ‒ 1.14079 × 10

‒4 2

2

20

𝐻𝑚 = 189.71622 + 0.01863𝑇 + 9.02393 × 10

0

‒5 2

2

0

14

𝑇 (𝑅 = 0.9992) 𝑇 (𝑅 = 0.99987)

ACCEPTED MANUSCRIPT

250

Polynomial Fitting 2

Thermodynamic variables

R = 0.99987 200 2

R = 0.9992 150 2

R = 0.99956 100 0 -1 -1 C p,m(cal mol K ) 0 -1 -1 S m(cal mol K ) 0 -1 H m(kcal mol )

50

0 0

100

200

300

400

500

600

700

800

Temperature (K)

1 2

Fig. 7 Correlation graph between thermodynamic variables with temperature.

3 4 5 6

Table 7 Calculated thermodynamic parameters with HF and DFT theory using B3LYP function and 6-311G(d,p) basis set. Thermodynamic Parameters (298K) SCF energy Total energy (Thermal), Etotal(Kcal mol-1) Vibrational energy, Evib(Kcal mol-1) Zero point vibrational energy, E0(Kcal mol-1) Heat Capacity, Cv(Cal/Mol-Kelvin) Entropy, S (Cal/Mol-Kelvin)

HF/6-311G(d,p) -1180.80289381 216.014 214.236 203.93876 68.597 149.299

B3LYP/6-311G(d,p) -1186.49677314 203.143 201.366 190.46356 73.324 152.103

Rotational Constants (GHZ) A B C

0.52642 0.23697 0.19810

0.52166 0.23568 0.19697

Dipole moment (Debye) 𝝁𝒙 𝝁𝒚 𝝁𝒛 𝝁𝒕𝒐𝒕𝒂𝒍

0.9140 2.7110 2.4311 3.7544

-0.9313 2.7683 -2.3610 3.7556

7 15

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Table 8 Thermodynamic properties at different temperatures at the DFT/6-311G(d,p) level for diethyl (hydroxy(4-methoxyphenyl)methyl)phosphonate

4 T(K)

C0p.m(cal mol-1K-1)

S0m(cal mol-1K-1)

H0m(kcal mol-1)

50 100 150 200 250 298.15 300 350 400 450 500 550 600 650 700

21.410 33.458 44.033 53.842 63.679 73.324 73.695 83.628 93.149 102.034 110.185 117.598 124.321 130.423 135.974

75.199 95.199 111.614 126.203 139.713 152.103 152.570 164.985 177.045 188.770 200.159 211.203 221.901 232.256 242.275

191.139 192.517 194.460 196.908 199.845 203.143 203.279 207.213 211.635 216.517 221.826 227.524 233.574 239.945 246.607

5 6

5.7HOMO-LUMO analysis

7

The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular

8

orbital (LUMO) are named as the frontier orbitals. The HOMO and LUMO energies are very

9

useful for physicists and chemists and they are very important terms in quantum chemistry [46].

10

HOMO-LUMO gap is generally the lowest energy electronic excitation that is possible in a

11

molecule. The pictorial representation and the energy difference for the title molecule are shown

12

in Fig. 8.

13

The HOMO is at - 5.955 eV and is delocalized over the molecule whereas the LUMO to

14

be found at - 0.310 eV with large anti-bonding character which shows that the eventual charge

15

transfer occurs within the molecule, and the frontier orbital energy gap is5.64 eV. The frontier

16

molecular orbital energy gap explains the eventual charge transfer interaction within the

17

molecule and helps to understand the chemical reactivity of the molecule. Both the HOMO and

18

LUMO orbitals are the main orbital that take part in chemical stability. The HOMO and LUMO

19

energies, the energy gap (∆E) , the ionization potential (I) , the electron affinity (A) , global

20

hardness(ɳ) chemical potential (μ) , global electrophilicity(ω) for molecule have been calculated

21

at the same levels and the results are given in Table 9. 16

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Fig. 8 HOMO-LUMO diagrams of diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate Table 9 HOMO-LUMO and other related molecular properties Molecular parameters (eV) ELUMO EHOMO ELUMO- EHOMO Ionization potential (I) Electron affinity (A) Global hardness (ɳ) Chemical potential (μ) Global Electrophilicity (ω)

B3LYP/6-311G(d,p) -0.310 -5.955 5.64 5.955 0.310 2.822 -3.132 1.737 17

ACCEPTED MANUSCRIPT 1

5.8 Thermo gravimetric analysis

2

Thermo gravimetric analysis (TGA) is one such important instrumental technique to

3

observe thermal changes with respect to increase in temperature [47]. The synthesized compound

4

was subjected to thermogravimetric analysis to evaluate their thermal stability. The sample

5

weighing 5.145 mg was taken for the analysis and the thermogram is illustrated in Fig.9 The

6

thermo gravimetric (TG) identified the thermal stability of C12H19O5P and differential thermal

7

analysis (DTA) were carried out simultaneously by using Shimadzu DTG-60 thermal analyser in

8

a nitrogen free atmosphere from 32oC to 350oC at a heating rate of 15oC/min. There is sudden

9

and significant weight loss as the temperature is increased above 150oC. From the TGA curve, it

10

is clear that the molecule is stable up to 172oC and after that the slow decomposition of complex

11

takes place. At 173oC, the weight loss begins and ends at 238oC, where maximum weight loss

12

takes place. The Sharp endothermic peaks are of the DTA curve of the compound which are

13

shown at 126oC, 214oCand 299oC and exothermic peak at around 235oC (Fig.9).

10 235C

172C

DTA TGA

5 0

5

299C

4

-10

3

-15

Weight loss(mg)

DTA(V)

-5

2 -20 126C

238C

-25

1

214C

-30 0

100

200

300

400

TemperatureC

14 15 16

Fig. 9 DTA and Thermo gravimetric analysis (TGA) of diethyl (hydroxy(4-methoxyphenyl)

methyl) phosphonate

17 18

ACCEPTED MANUSCRIPT 1

5.9 Fukui Functions

2

DFT is a powerful tool for the study of reactivity and selectivity in a molecule [48]. The

3

most basic and commonly used local reactivity parameter is the Fukui function. The Fukui

4

function for a given molecule has been defined as the derivative of electron density with respect

5

to the change of number of electrons, keeping the positions of nuclei unchanged [49, 50]. Fukui

6

function gives us information regarding electrophilic/nucleophilic power of a given atomic site in

7

a molecule. In practice a convenient way of calculating the Fukui functions at atomic resolution

8

is to use the condensed Fukui functions [51]. The condensed Fukui functions on the jth atom site

9

can be expressed as: ‒

10

f j = qj(N) ‒ qj(N ‒ 1)

11

f

12

1 0 f j = [qj(N + 1) ‒ qj(N ‒ 1)] 2

+ j

= qj(N + 1) ‒ qj(N)

13

Where, fj+ for nucleophilic attack, fj- for electrophilic attack and fj0 for free radical. In these

14

equations, qj is the atomic charge at the jth atomic site in the neutral (N), anionic (N+1) or

15

cationic (N-1) chemical species. In the present study, the values of fukui function were

16

calculated from NBO charges. Morrel et al. [52] have proposed a new dual descriptor ∆f(r) for

17

the calculation of nucleophilicity and electrophilicity and is defined as the difference between the

18

nucleophilic and electrophilic Fukui function and is given by the equation:

19

∆f(r) = f

+ j

‒

‒ fj

20

If ∆ f(r) > 0, then the site is prone for nucleophilic attack, if ∆f(r) < 0, then the sites for

21

electrophilic attack. The condensed Fukui functions (f+j), (f-j) and dual descriptor ∆f(r) are given

22

in

23

C2,C5,O8,O10,O11,O13,O16,H22,H23 are prone to nucleophilic attack as they have ∆f(r) > 0

24

whereas C1, C3, C4,C6,C7,P9,C14, C15, H21,H24 are prone for electrophilic attack as they have

25

∆f(r) < 0.

26 27 28

Table 10 Fukui indices for nucleophilic and electrophilic attacks on atoms calculated from Natural population analysis at DFT/6-311G(d,p)

Table

10.

In

Atom C1 C2 C3

the

present

f+ 0.08425 0.08792 0.05139

work

f0.161 0.00117 0.1042 19

it

has

been

∆f(r) -0.07675 0.08675 -0.05281

observed

that

ACCEPTED MANUSCRIPT

C4 C5 C6 C7 O8 P9 O10 O11 C12 O13 C14 C15 O16 C17 C18 H19 H20 H21 H22 H23 H24 H25 H26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37

0.04531 0.16116 0.01052 -0.02471 0.03376 0.01104 0.07119 0.12775 -0.02059 0.00546 -0.00324 -0.0021 -0.00299 -0.00106 -0.00238 0.03319 0.03102 0.03281 0.03232 0.05095 0.01927 0.0333 0.03196 0.03106 0.01629 0.00946 0.02208 -0.00701 -0.00683 0.01161 0.00513 0.01773 -0.00374 0.00675

0.17316 0.00025 0.0944 -0.00431 0.00613 0.01481 0.03003 0.0183 -0.00826 -0.00554 -0.00063 0.00342 -0.00837 0.00345 -0.0002 0.0368 0.03281 0.03465 0.03057 0.04817 0.02326 0.02811 0.01424 0.01496 0.02649 0.01705 0.03705 0.00082 -0.00376 0.0291 0.0136 0.02193 -0.00218 0.01332

-0.12785 0.16091 -0.08388 -0.0204 0.02763 -0.00377 0.04116 0.10945 -0.01233 0.011 -0.00261 -0.00552 0.00538 -0.00451 -0.00218 -0.00361 -0.00179 -0.00184 0.00175 0.00278 -0.00399 0.00519 0.01772 0.0161 -0.0102 -0.00759 -0.01497 -0.00783 -0.00307 -0.01749 -0.00847 -0.0042 -0.00156 -0.00657

1 2 3

6. Conclusions Diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate has been synthesized and

4

characterized by

FTIR, FT-Raman and UV-Vis. The structural geometrical parameters,

5

vibrational, electronic, HOMO-LUMO, Fukui analysis, and the thermodynamic properties of the

6

molecule were performed on the basis of DFT calculations at B3LYP/6-311G(d,p) basis set. A

7

good agreement between observed and calculated wavenumbers and all observed wavenumbers

8

have been assigned. The title compound is chemically stable up to 1720C. Using NBO analysis,

9

the stability of the molecule arising from the hyper-conjugative interaction and charge

10

delocalization has been studied. Fukui function analysis helps in identifying the nucleophilic and 20

ACCEPTED MANUSCRIPT 1

electrophilic behaviour of a specific site within a molecule. The correlations between the

2

statistical thermodynamics and temperature are obtained and show that increase in temperature

3

causes the increase in heat capacities, entropies and enthalpies.

4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

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Diethyl (hydroxy(4-methoxyphenyl) methyl) phosphonate has been synthesized.

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Structural, vibrational, electronic, thermal and Fukui analysis.

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Hartree- Fock (HF) and Density Functional Theory (DFT) with 6-311G(d,p) basis set.