Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study
Table 1
ECDA and generalized CDA results for transition metal chloride complexes of L1 calculated using Gaussian output files for single-point calculations at B3LYP/6-311G(d,p)/(SDD for metal ions) level on geometries optimized at B3LYP/6-31++G(d,p)/(SDD for metal ions) level.
[Ni(L1)Cl2]
[Pd(L1)Cl2]
[Pt(L1)Cl2]
[Zn(L1)Cl2]
Gas-phase
Frag.1 Frag.2 donation (d)
0.26654
0.14418
0.21067
0.30532
0.26154
Frag.1 Frag.2 back donation (b)
−0.00296
0.04153
0.05289
−0.01265
0.00267
Net Frag.1 Frag.2 donation (d-b)
0.26950
0.10266
0.15778
0.31797
0.25887
Donation to back donation ratio, |d/b|
89.95478
3.47205
3.98336
24.13581
98.02661
CT() - CT()
0.60450
0.39720
0.46260
0.56460
0.41070
Benzene
Frag.1 Frag.2 donation (d)
0.28205
0.15715
0.21982
0.33276
0.29419
Frag.1 Frag.2 back donation (b)
−0.00731
0.03463
0.04368
−0.01384
0.00387
Net Frag.1 Frag.2 donation (d-b)
0.28936
0.12253
0.17615
0.34659
0.29032
Donation to back donation ratio, |d/b|
38.56248
4.53860
5.03318
24.05183
76.07706
CT() - CT()
0.69220
0.49480
0.55910
0.66880
0.46970
Ethanol
Frag.1 Frag.2 donation (d)
0.29623
0.16990
0.22919
0.35717
0.32350
Frag.1 Frag.2 back donation (b)
−0.00861
0.02929
0.03645
−0.01264
0.00671
Net Frag.1 Frag.2 donation (d-b)
0.30484
0.14061
0.19274
0.36981
0.31679
Donation to back donation ratio, |d/b|
34.41757
5.80025
6.28753
28.25720
48.20414
CT() - CT()
0.78610
0.61200
0.67540
0.78440
0.53030
DMSO
Frag.1 Frag.2 donation (d)
0.29691
0.17013
0.22975
0.35872
0.32508
Frag.1 Frag.2 back donation (b)
−0.00853
0.02883
0.03608
−0.01240
0.00691
Net Frag.1 Frag.2 donation (d-b)
0.30544
0.14130
0.19367
0.37112
0.31817
Donation to back donation ratio, |d/b|
34.82839
5.90087
6.36797
28.93394
47.05196
CT() - CT()
0.79060
0.61670
0.68310
0.79150
0.53290
. refers to fragment, where Frag.1 is L1 and Frag.2 is MCl2 [M = Ni(II), Pd(II), Pt(II), Cu(II), and Zn(II)]. overall results for alpha and beta electrons are reported for the Cu(II) chloride complex of L1.
