Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study
Table 8
Significant second-order interaction energies (, kcal/mol) between donor and acceptor NBOs of L1 and its Cu(II) and Zn(II) chloride complexes.
(kcal/mol)
Cu(L1)Cl2
Zn(L1)Cl2
(kcal/mol)
Donor(i) acceptor(j)
Gas-phase
DMSO
Donor(i) acceptor(j)
Gas-phase
DMSO
Donor(i) acceptor(j)
Gas-phase
DMSO
π(C6-(C8-C9)
22.85
23.77
π(C6-(C8-C9)
12.11 (12.21)
12.77 (12.90)
π(C6-(C7-C8)
17.82
16.94
π(C6-(C10-C11)
16.59
16.60
π(C6-(C10-C11)
8.15 (8.08)
8.13 (8.03)
π(C6-(C9-C10)
25.30
26.24
π(C8-(C6-C7)
17.00
16.69
π(C8-(C6-C7)
8.08 (8.02)
7.94 (7.91)
π(C7-(C6-C11)
22.81
23.24
π(C8-(C10-C11)
21.53
21.77
π(C8-(C10-C11)
10.56 (10.61)
10.71 (10.74)
π(C7-(C9-C10)
17.03
16.60
π(C10-(C6-C7)
21.19
21.28
π(C10-(C6-C7)
10.54 (10.59)
10.54 (10.60)
π(C9-(C6-C11)
17.79
17.12
π(C10-(C8-C9)
17.49
17.13
π(C10-(C8-C9)
8.63 (8.57)
8.36 (8.30)
π(C9-(C7-C8)
23.27
22.73
(C6-C7)
30.64
30.75
π(S25-()C24
(150.08)
—
3.05
10.62
11.68
11.15
(S25-()Cu29
(1.22)
(24.74)
—
34.19
LP(1)(C16-N21)
25.75
23.29
23.05 (23.93)
14.34 (14.73)
(C6-C11)
28.78
29.21
LP(1)(1)C24
—
130.14
(C6-C7)
16.04 (16.11)
16.10 (16.20)
(6)Zn29
23.71
31.05
LP(1)(C24-S25)
48.42
—
()Cu29
(27.57)
—
(9)Zn29
28.64
30.63
LP(2)(N22-C24)
13.92
11.69
(6)Cu29
12.23
16.4 (37.24)
LP(1)(1)C24
128.39
135.41
LP(3)(1)C24
—
212.55
(8)Cu29
10.74
18.42
(C16-N21)
22.05
20.45
LP(2)(C24-N26)
11.37
9.33
(9)Cu29
10.42
7.47
(7)Zn29
0.55
17.41
LP(1)(1)C24
—
137.34
LP(1)(C16-N21)
10.53 (10.40)
9.82
(7)Zn29
0.80
21.61
LP(1)(C24-S25)
46.09
—
LP(1)(C24-S25)
34.87
—
LP()(8)Zn29
17.49
1.20
LP(1)()C24
(58.01)
64.46 (64.40)
LP()(6)Zn29
69.54
50.55
LP()(6)Cu29
29.82
28.71
LP()(8)Zn29
51.69
10.44
LP()(7)Cu29
20.94
24.77
LP()(6)Zn29
4.59
66.42
LP(3)(1)C24
—
31.27
LP()(7)Zn29
6.22
36.18
LP(2)(1)C24
—
10.05 (76.21)
LP(2)(C24-N26)
10.71
—
LP()(6)Cu29
—
26.22
LP(2)(1)C24
—
38.26
LP()→(7)Cu29
—
12.37
LP(3)(1)C24
280.74
37.01
LP(1)(C24-S25)
32.81
—
LP(1)(1)C24
115.63
162.67
LP(1)(1)C24
(59.12)
84.10 (83.87)
to Figure 2 for atomic numbering. values in parentheses are obtained from NBO data for the beta spin orbitals.
