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Supplementary Information
Nickel(II) complexes of ONS donor Schiff base ligands: Synthesis, combined DFT-experimental characterization, redox, thermal and in vitro biological investigation
R. C. MAURYA*, B. A. MALIK, J. M. MIR, P. K. VISHWAKARMA, D. K. RAJAK and N. JAIN
Thermodynamic studies based on TGA spectra
In the present studies of the metal complexes, non-isothermal mode for TGA/DTA techniques is
selected representatively for complex [Ni(dha-mtsc)(H2O)] (3). From Broido graphical method
(mathematical aspect given in supplemental data for clarity) and Broido plots [S1] (figure S11)
the activation energy and order at a particular step were calculated and the results are given in
table S3. The overall thermodynamic and kinetic evaluation results are given in table S4. From
the thermal behavior of the complex, it is quite evident that the change in activation energies and
decrease in the order of the decomposition against the pyrolytic steps determine the order of
stability that the metal oxide attains on getting fully decomposed. The structural rigidity of the
remaining compound gets increased after the expulsion of one or more species, as compared with
the precedent complex. It is known that the order has no intrinsic meaning, but is rather a
mathematical smoothing parameter. No regular trend is observed in the values of either Ea,
because of the fact that TS increases from one step to another.
A. Broido has suggested a simple and sensitive graphical method for the treatment of TGA data.
According to this method the weight at any time t (W t) is related to the fraction of initial
molecular weight as shown below,
Y= NN 0
=W t−W a
W 0−W a. . . (1)
where Wo is the initial weight of the materials and Wa is the weight of residue at the end of
decomposition:
1
For isolated pyrolysis,
dydt
=−K yn . . . (2)
If, K= A e−E/RT . . . (3)
and if T is linear fraction of time t, therefore:
T=T 0+β t . . . (4)
dydn
=−Aβ
e E /RT . dt . . . (5)
where β=dTt , the heating rate
Eq. (v) is integrated as:
(i) ∫Y
1 dydn
=¿ Aβ ∫
T0
T
e−E /RT . dt ¿ . . . (6)
For the first order kinetics (n= 1) in which complex degrades usually:
(ii) ∫Y
1 dyy
=¿−lny=ln ( 1y)¿ . . . (7)
On integrating and taking log of both sides of Eq. (vi), following equation is obtained.
ln [ ln( 1y )]=( E
R Tm+1 )lnT +Constant . . . (8)
Thus a plot of ln [ ln( 1y )] v/s 1/T yields straight line, whose slope is directly related to Ea:
-Ea = Slope × 2.303×R . . . (9)
where Ea is the activation energy and R is the gas constant. Application of this method is used to
determine the kinetic parameter for the complexes. Activation energies against Step (I), Step (II)
and Step (III) were also analyzed.
2
The order ‘n’ is calculated by the application of Horowitz-Metzger equation [S2] as given below
Cs = n1
(1−n) . . . (10)
Cs = W t−W a
W 0−W a, . . . (11)
where Cs is the mass fraction of the substance.
References
S1. A. Broido. J. Polym. Sci., Part A-2, 7, 1761 (1969).
S2. H.H. Horowitz, G. Metzger. Anal. Chem., 35, 1464 (1963).
Figure S1. Keto-enol and thione-thiol tautomerisation of Schiff bases.
3
Figure S2. IR spectra of Schiff base ligand (H2dha-mtsc) (III).
4
Figure S3. IR spectra of [Ni(dha-mtsc)(H2O)] (3).
5
Figure S4. IR spectra of [Ni(dha-mtsc)(H2O)] (3). (a) Experimental (b) Theoretical.
6
Figure S5. Electronic spectra of [Ni(dha-mtsc)(H2O)] (3) (A) in solution form (B) in solid form.
7
Figure S6. Electronic spectra of [Ni(dha-ptsc)(H2O)] (1); (A) in solution (B) in solid form.
8
Figure S7. 1H NMR spectrum of (H2dha-mtsc) (III).
9
Figure S8. 1H NMR spectrum of [Ni(dha-mtsc)(H2O)] (3).
10
Figure S9. 13C NMR spectrum of (H2dha-mtsc) (III).
11
Figure S10. 13C NMR spectrum of [Ni(dha-mtsc)(H2O)] (3).
12
13
Figure S11. Broido plots of [Ni(dha-mtsc)(H2O)] (3).
14
Figure S12. Inhibition zones shown by Schiff bases and their complexes at 100 and 200 conc. µg/mL aginst E. coli.
15
Figure S13. HOMO-LOMO structure with energy level diagram of (H2dha-mtsc) (III).
16
Figure S14. HOMO-LOMO structure with energy level diagram of [Ni(dha-mtsc)(H2O)] (3).
17
Figure S15. Structure of with color range (a) Mulliken atomic charges (b) NBO atomic charges of [Ni(dha-mtsc)(H2O)] (3).
18
Figure S16. Molecular electrostatic potential MESP (a) [H2dha-mtsc] and (b) [Ni(dha-mtsc)(H2O)] (3) with color range along with scale.
19
Figure S17. (a) 1H NMR (b) 13C NMR spectrum of [Ni(dha-mtsc)(H2O)] (3).
20
Table S1. Characterization data of synthesized Schiff bases.
S.No Ligand(Empirical Formula) (M. W.)
Color Yield (%)
Elemental Analysis (Observed/Calculated) %
C H N S M.P.0C
I H2dha-ptsc(C15H15N3O3S)(317.08) White 65
56.67(56.77)
4.61(4.76)
13.01(13.24)
9.92(10.10)
200
II H2dha-tsc(C9H11N3O3S)(241.27)
Creamy white 60
44.52(44.80)
4.45(4.60)
17.32(17.42)
13.0(13.29)
190
III H2dha-mtsc(C10H13N3O3S)(255.07)
Light yellow 63
47.13(47.05)
5.02(5.13)
15.87(16.46)
11.87(12.56)
195
IV H2dha-psc(C15H15N3O4)(301.11)
Creamy white 62
59.51(59.79)
4.97(5.02)
13.76(13.95)
- 198
Table S2. Analytical data, colors, yields (%) and decomposition temperatures (DT) of the synthesized complexes.
Complex (empirical formulae) (molecular weight)
Color M
(Ohm-1
cm2/mole)
μeff
(B.M)Yield ( %)
DT 0C
Elemental Analysis, Observed/Calculated) %
C H N S Ni
[Ni(dha-ptsc)(H2O)] C15H15N3NiO4S (392.06)
Light brown 15.4 0.59 62 270
45.72(45.95)
3.76(3.86)
10.50(10.72)
8.02(8.18)
14.82(14.97)
[Ni(dha-tsc)(H2O)] C9H11N3NiO4S (315.96)
Light brown 14.2 0.44 61 280
34.01(34.21)
3.35(3.51)
13.10(13.30)
10.02(10.15)
18.30(18.58)
[Ni(dha-mtsc)(H2O)] C10H13N3NiO4S (329.00)
Reddish brown 14.3 0.61 64 290
36.24(36.40)
3.65(3.97)
12.52(12.73)
9.67(9.72)
17.65(17.79)
[Ni(dha-psc)(H2O)] C15H15N3NiO5 (375.04)
Deep brown 15.6 0.66 65 290
47.99(47.92)
4.22(4.02)
11.02(11.18)
- 15.39(15.61)
21
Table S3. Stepwise thermal behavior and thermodynamic parameters of [Ni(dha-mtsc)(H2O)].
Step I
Temp. C Temp K 1/K X 103 Residue % Wt Cs =Wt – Wa
Wo- Wa
Order 1/ Cs
180 453 2.207 84.537 1.791 0.838 1.1933190 463 2.159 83.628 1.772 0.829 1.2062200 473 2.114 82.719 1.748 0.817 1.2239210 483 2.070 81.810 1.733 0.810 1.2345220 493 2.028 81.790 1.733 0.810 1.2346230 503 1.988 79.992 1.695 0.791 1.2642240 513 1.949 78.174 1.656 0.774 1.2919250 523 1.912 76.356 1.617 0.753 1.3280
Step II
Temp. C Temp K 1/K X 103 Residue % Wt Cs =Wt – Wa
Wo- Wa
Order 1/ Cs
375 648 1.543 60.903 1.290 0.592 4 1.6891385 658 1.519 59.994 1.271 0.582 4 1.7161395 668 1.497 59.634 1.263 0.578 4 1.7280405 678 1.479 59.085 1.252 0.573 3 1.7442415 688 1.474 58.630 1.242 0.568 3 1.7593423 698 1.436 57.627 1.221 0.558 3 1.7917435 708 1.432 56.358 1.194 0.544 3 1.8355445 718 1.392 56.176 1.190 0.542 3 1.8422
Step III
Temp. C Temp K 1/K X 103 Residue % Wt Cs =Wt – Wa
Wo- Wa
Order 1/ Cs
765 1038 0.963 32.724 0.693 0.298 1 3.355775 1048 0.954 31.815 0.674 0.288 1 3.472785 1058 0.945 29.997 0.635 0.269 1 3.717795 1168 0.856 29.088 0.616 0.260 1 3.846805 1078 0.927 27.270 0.577 0.241 ½ 4.419815 1088 0.919 24.543 0.520 0.213 ½ 4.694825 1098 0.190 23.634 0.500 0.203 ½ 4.926835 1108 0.902 22.725 0.481 0.193 ½ 5.181
22
Table S4. Overall TGA based thermodynamic and decomposition kinetic parameters of 3.
StepStep analysis (C)
Cs = (Wt –Wa) / (Wo –Wa)Order
(n) Ea (KJ)Ti Tmax Tf
I 180 210 250 0.838 28.57
II 375 405 445 0.592 4 7.10
III 765 805 835 0.298 1 57.87
Table S5. Selected geometrical optimization parameters of the representative complex.
S.No
Bond Connectivity
Length
Bond Connectivity
Angle Bond Connectivity Dihedral Angle
1 N(1)-C(2) 1.341 C(2)-N(1)-H(13) 115.014 N(13)-N(1)-C(2)-C(3) 177.6772 N(1)-N(13) 1.412 C(2)-N(1)-Ni(16) 126.006 N(13)-N(1)-C(2)-C(12) -4.0573 N(1)-N(16) 1.876 N(13)-N(1)-
Ni(16)118.866 Ni(16)-N(1)-C(2)-C(3) -6.272
4 C(2)-C(3) 1.464 N(1)-C(2)-C(3) 122.426 Ni(16))-N(1)-C(2)-C(12)
171.994
5 C(2)-C(12) 1.517 N(1)-C(2)-C(12) 117.686 C(2)-N(1)-N(13)-C(14) -177.2896 C(3)-C(4) 1.463 C(3)-C(2)-C(12) 119.866 Ni (16)-N(1)-N(13)
C(14)6.358
7 C(3)-C(6) 1.423 C(2)-C(3)-C(4) 118.703 C(2)-N(1)-Ni(16)-O(11) -5.0858 C(4)-O(5) 1.238 C(2)-C(3)-C(6) 123.134 C(2)-N(1)-Ni(16)-S(15) -3.6629 C(4)-O(10) 1.455 C(4)-C(3)-C(6) 118.138 C(2)-N(1)-Ni(16)-O(30) -22.17310 C(6)-C(7) 1.446 C(3)-C(4)-O(5) 129.669 N(13)-N(1)-Ni(16)-
O(11)170.828
11 C(6)-O(11) 1.321 C(3)-C(4)-O(10) 116.278 N(13)-N(1)-Ni(16)-S(15) -7.47312 C(7)-C(8) 1.708 O(5)-C(4)-O(10) 114.047 N(13)-N(1)-Ni(16)-
O(30)153.741
13 C(7)-H(19) 1.082 C(3)-C(6)-C(7) 120.923 N(1)-C(2)-C(3)-C(4) -164.60914 C(8)-C(9) 1.498 C(3)-C(6)-O(11) 123.124 N(1)-C(2)-C(3)-C(6) 13.52215 C(8)-O(10) 1.377 C(7)-C(6)-O(11) 115.949 C(12)-C(2)-C(3)-C(4) 17.16216 C(9)-H(20) 1.093 C(6)-C(7)-C(8) 120.429 C(12)-C(2)-C(3)-C(6) -164.70717 C(9)-H(21) 1.097 C(6)-C(7)-H(19) 118.416 N(1)-C(2)-C(12)-H(23) -154.94818 C(9)-H(22) 1.097 C(8)-C(7)-H(19) 121.152 N(1)-C(2)-C(12)-H(24) 86.21919 O(11)-
Ni(16)1.849 C(7)-C(8)-C(9) 127.244 N(1)-C(2)-C(12)-H(25) -31.696
20 C(12)-H(23) 1.088 C(7)-C(8)-O(10) 120.188 C(3)-C(2)-C(12)-H(23) 23.36421 C(12)-H(24) 1.097 C(9)-C(8)-O(10) 112.566 C(3)-C(2)-C(12)-H(24) -95.469
23
22 C(12)-H(25) 1.090 C(8)-C(9)-H(20) 110.936 C(3)-C(2)-C(12)-H(25) 146.61523 N(13)-C(14) 1.321 C(8)-C(9)-H(21) 110.285 C(2)-C(3)-C(4)-O(5) 9.27024 C(14)-S(15) 1.813 C(8)-C(9)-H(22) 110.209 C(2)-C(3)-C(4)-O(10) -171.13425 C(14)-N(17) 1.372 H(20)-C(9)-H(21) 109.109 C(6)-C(3)-C(4)-O(5) -168.95526 S(15)-Ni(16) 2.245 H(20)-C(9)-H(22) 109.015 C(6)-C(3)-C(4)-O(10) 10.04127 Ni(16)-
H(30)1.927 H(21)-C(9)-H(22) 107.199 C(2)-C(3)-C(6)-C(7) 173.980
28 N(17)-C(18) 1.463 C(4)-O(10)-C(8) 123.329 C(2)-C(3)-C(6)-O(11) -5.27429 N(17)-H(26) 1.013 C(6)-O(11)-
Ni(16)127.509 C(4)-C(3)-C(6)-C(7) -7.879
30 C(18)-H(27) 1.098 C(2)-C(12)-H(23) 111.258 C(4)-C(3)-C(6)-O(11) 172.86731 C(18)-H(28) 1.094 C(2)-C(12)-H(24) 110.437 C(3)-C(4)-O(10)-C(8) -6.78332 C(18)-H(29) 1.096 C(2)-C(12)-H(25) 109.169 O(5)-C(4)-O(10)-C(8) 172.37133 O(30)-H(31) 0.970 H(23)-C(12)-
H(24)107.130 C(3)-C(6)-C(7)-C(8) 1.661
34 O(30)-H(32) 0.977 H(23)-C(12)-H(25)
111.322 C(3)-C(6)-C(7)-H(19) -177.707
35 H(24)-C(12)-H(25)
107.411 O(11)-C(6)-C(7)-C(8) -179.034
36 N(1)-N(13)-C(14) 115.507 O(11)-C(6)-C(7)-H(19) 1.59837 N(13)-C(14)-
S(15)123.188 C(3)-C(6)-O(11)-Ni(16) -9.823
38 N(13)-C(14)-N(17)
117.782 C(7)-C(6)-O(11)-Ni(16) 170.888
39 S(15)-C(14)-N(17)
119.026 C(6)-C(7)-C(8)-C(9) -178.523
40 C(14)-S(15)-Ni(16)
91.369 C(2)-C(3)-C(6)-O(11) -5.274
41 N(1)-Ni(16)-O(11)
95.725 H(19)-C(7)-C(8)-C(9) 0.826
42 N(1)-Ni(16)-S(15)
90.246 H(19)-C(7)-C(8)-O(10) -178.549
43 N(1)-Ni(16)-O(30)
177.111 C(7)-C(8)-C(9)-H(20) 0.166
44 O(11)-Ni(16)-S(15)
173.793 C(7)-C(8)-C(9)-H(21) -120.838
45 O(11)-Ni(16)-O(30)
81.515 C(7)-C(8)-C(9)-H(22) 121.000
46 S(15)-Ni(16)-O(30)
92.488 O(10)-C(8)-C(9)-H(20) 179.581
47 C(14)-N(17)- 125.176 O(10)-C(8)-C(9)-H(21) 58.577
24
C(18)48 C(14)-N(17)-
H(26)115.252 O(10)-C(8)-C(9)-H(22) -59.585
49 C(18)- N(17)-H(26)
119.482 C(7)-C(8)-O(10)-C(4) 0.650
50 N(17)-C(18)-H(27)
111.882 C(9)-C(8)-O(10)-C(4) -178.811
51 N(17)-C(18)-H(28)
108.581 C(6)-O(11)-Ni(16)-N(1) 13.332
52 N(17)-C(18)-H(29)
111.136 C(6)-O(11)-Ni(16)-S(15) 177.418
53 H(27)-C(18)-H(28)
108.610 C(6)-O(11)-Ni(16)-O(30)
-167.526
54 H(27)-C(18)-H(29)
108.053 N(1)-N(13)-C(14)-S(15) -0.444
55 H(28)-C(18)-H(29)
108.495 N(1)-N(13)-C(14)-N(17) 178.888
56 Ni(16)-O(30)-H(31)
129.143 N(13)-C(14)-S(15)-Ni(16)
-4.097
57 Ni(16)-O(30)-H(32)
108.712 N(17)-C(14)-S(15)-Ni(16)
176.579
58 H(31)-O(30)-H(32)
116.834 N(13)-C(14)-N(17)-C(18)
-178.321
59 N(13)-C(14)-N(17)-H(26)
-1.817
60 S(15)-C(14)-N(17)-C(18)
1.040
61 S(15)-C(14)-N(17)-H(26)
177.544
62 C(14)-S(15)-Ni(16)-N(1) 5.35363 C(14)-S(15)-Ni(16)-
O(11)-158.815
64 C(14)-S(15)-Ni(16)-O(30)
-173.716
65 N(1)-Ni(16)-O(30)-H(31)
-139.869
66 N(1)-Ni(16)-O(30)-H(32)
13.028
67 O(11)-Ni(16)-O(30)-H(31)
-157.063
68 O(11)-Ni(16)-O(30)-H(32)
-4.165
25
69 S(15)-Ni(16)-O(30)-H(31)
21.326
70 S(15)-Ni(16)-O(30)-H(32)
174.224
71 C(14)-N(17)-C(18)-H(27)
65.375
72 C(14)-N(17)-C(18)-H(28)
-174.768
73 C(14)-N(17)-C(18)-H(29)
-55.509
74 H(26)-N(17)-C(18)-H(27)
-110.992
75 H(26)-N(17)-C(18)-H(28)
8.865
Table S6. Representation data of Mulliken atomic charges and NBO analysis of [Ni(dha-mtsc)](H2O)] (3).
S. No.
Atom with the Numerical Assignment
NBO Partial Charges
Mulliken Partial Charges
S. No.
Atom with the Numerical Assignment
NBO Partial Charges
Mulliken Partial Charges
1 1 N -0.308554 -0.34199 17 17 N -0.331951
-0.64121
2 2 C 0.314189 0.35411 18 18 C -0.555487 -0.41500
3 3 C -0.077093 -0.30903 19 19 H 0.247162 0.23870
4 4 C 0.120588 0.78907 20 20 H 0.217664 0.22944
5 5 O -0.251456 -0.60106 21 21 H 0.240130 0.24700
6 6 C 0.411602 0.46695 22 22 H 0.238543 0.24651
7 7 C -0.450977 -0.36033 23 23 H 0.235609 0.24414
8 8 C 0.377162 0.43331 24 24 H 0.244951 0.25489
9 9 C -0.716364 -0.67125 25 25 H 0.245026 0.25184
10 10 O -0.286916
-0.56785 26 26 H 0.317705 0.42409
11 11 O -0.518215
-0.69053 27 27 H 0.233969 0.21410
12 12 C -0.699172 -0.67302 28 28 H 0.203703 0.21954
13 13 N -0.075244
-0.42876 29 29 H 0.237404 0.21887
26
14 14 C -0.123080 0.33898 30 30 O -0.702186
-0.90898
15 15 S -0.053078 -0.18729 31 31 H 0.433109 0.54288
16 16 Ni 0.387685 0.53039 32 32 H 0.443573 0.55148
27
Equation S1. The absolute electronegativity (cabs) and absolute hardness (h) are related to IA
and EA [62] as given below:
cabs = (IE + IA)/2 = (EHOMO + ELUMO) / 2
h = (IE - IA)/2 = (EHOMO - ELUMO) / 2
Equation S2.
Electrophilicity index (), Global softness (S) are given by
= 2/ 2h
S = 1/h
Equation S3.
Dipole moment (), Mean polarizability () and the total first static Hyperpolarizability (0) are given by
= (x2+y
2+z2)1/2
= 1/3(xx +yy +zz)
∆ α=[ ( α XX−α YY )2+(α YY−α ZZ )2+ (α ZZ−α XX )2
2 ]12
0 = (x2+y
2+z2 )1/2
and x = xxx + xyy + xzz
y = yyy + xxy +yzz
z = zzz +xxz + yyz
(or)
0 = [(xxx +xyy +xzz)2 +(yyy +yzz +yxx)2 +(zzz +zxx+zyy)2]1/2
28
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