Theoretical Study on the Two-Dimensionalsecond-Order Nonlinear Optical Properties: a Series

Theoretical Study on the Two-DimensionalSecond-Order Nonlinear Optical Properties: a Series of Charge-TransferCovalently Bonded Organoimido Derived Hexamolybdate Complexes

Y. L. Si1,2, C. G. Liu1,E. B. Wang1,*, Z. M. Su1,*

1.KeyLaboratoryofPolyoxometalateScienceof MinistryofEducation,Faculty of Chemistry, Northeast Normal University,Changchun 130024, People’s Republic of China

2. College of Resource and Environmental Science, Jilin Agricultural University, Changchun, Jilin 130118, P. R. China

Supporting Information

Table S1 The electronic transitions of complexes in set I.

compound / Ege (eV) / foc / symmetry / composition / major assignment
Ia / 2.29 / 1.11 / B1 / 25a2→34b2(42.4%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Phenyl
32b2→27a2(38.8%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Phenyl
Ib / 1.97 / 0.60 / B1 / 25a2→34b2(30.4%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Tetrazine + a
32b2→27a2(25.6%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Tetrazine + a
2.18 / 0.69 / B1 / 30b2→27a2(73.0%) / Mo6  MoN + Pyrimidine + CC + Tetrazine + a
Ic / 2.13 / 1.04 / B1 / 25a2→33b2 (42.4%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyrimidine + a
32b2→26a2(37.5%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyrimidine + a
Id / 2.21 / 0.54 / B1 / 25a2→36b2(28.3%) / MoN + Pyrimidine + CC + a  Mo6
25a2→35b2(17.9%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
32b2→27a2(15.7%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
32b2→29a2(14.9%) / MoN + Pyrimidine + CC + a  Mo6
30b2→26a2(11.8%) / Mo6 Pyridazine
2.24 / 0.42 / B1 / 25a2→36b2(45.3%) / MoN + Pyrimidine + CC + a  Mo6
25a2→35b2(13.9%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
32b2→27a2(12.3%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
32b2→29a2(11.4%) / MoN + Pyrimidine + CC + a  Mo6
Ie / 2.22 / 0.56 / B1 / 25a2→36b2(25.4%) / MoN + Pyrimidine + CC + a  Mo6
32b2→29a2(18.9%) / MoN + Pyrimidine + CC + a  Mo6
25a2→35b2 (18.3%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
32b2→27a2(16.1%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
2.24 / 0.44 / B1 / 25a2→36b2(40.8%) / MoN + Pyrimidine + CC + a  Mo6
32b2→29a2(15.0%) / MoN + Pyrimidine + CC + a  Mo6
25a2→35b2 (14.3%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridazine + a
If / 2.15 / 0.77 / B1 / 32b2→26a2(33.8%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + pyridine + a
25a2→34b2(26.9%) / MoN + Pyrimidine + CC + a  Mo6 + Pyrimidine + CC + pyridine + a
Ig / 2.15 / 0.70 / B1 / 25a2→34b2(35.0%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridine + a
32b2→26a2(33.4%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Pyridine + a
Ih / 2.29 / 0.59 / B1 / 25a2→36b2(24.1%) / MoN + Pyrimidine + CC + a  Mo6 + Pyridine
25a2→34b2(19.5%) / MoN + Pyrimidine + CC + a  Mo6 + Pyrimidine + CC +Pyridine + a
32b2→28a2(19.0%) / MoN + Pyrimidine + CC + a  Pyridine
32b2→27a2(17.7%) / MoN + Pyrimidine + CC + a  Mo6 + Pyrimidine + CC +Pyridine + a
Ii / 2.22 / 0.66 / B1 / 25a2→34b2(26.9%) / MoN + Pyrimidine + CC + a  Mo6 + Pyrimidine + CC + pyridine + a
25a2→35b2(25.5%) / MoN + Pyrimidine + CC + a  Mo6
32b2→27a2(23.8%) / MoN + Pyrimidine + CC + a  Mo6 + Pyrimidine + CC + pyridine + a
Ij / 2.32 / 1.12 / B1 / 25a2→33b2(35.5%) / MoN + Pyrimidine + CC + Thiophene + a  MoN + Pyrimidine + CC + Thiophene + a
32b2→26a2(33.2%) / MoN + Pyrimidine + CC + Thiophene + a  MoN + Pyrimidine + CC + Thiophene + a
Ik / 2.42 / 1.27 / B1 / 25a2→33b2(34.5%) / MoN + Pyrimidine + CC + Furan + a  MoN + Pyrimidine + CC + Furan + a
32b2→26a2(32.8%) / MoN + Pyrimidine + CC + Furan + a  MoN + Pyrimidine + CC + Furan + a
Il / 2.43 / 0.76 / B1 / 24a2→33b2(28.0%) / Mo6 MoN + Pyrimidine + CC + Pyrrole
25a2→33b2(22.6%) / MoN + Pyrimidine + CC + Pyrrole + a  MoN + Pyrimidine + CC + Pyrrole
32b2→26a2(21.6%) / MoN + Pyrimidine + CC + Pyrrole + a  MoN + Pyrimidine + CC + Pyrrole
2.49 / 0.86 / B1 / 25a2→33b2(22.3%) / MoN + Pyrimidine + CC + Pyrrole + a  MoN + Pyrimidine + CC + Pyrrole
32b2→26a2(21.7%) / MoN + Pyrimidine + CC + Pyrrole + a  MoN + Pyrimidine + CC + Pyrrole
31b2→26a2(20.0%) / Mo6 MoN + Pyrimidine + CC + Pyrrole
Im / 2.37 / 0.99 / B1 / 25a2→33b2(30.5%) / MoN + Pyrimidine + CC + * + a MoN + Pyrimidine + CC + * + a
32b2→26a2(28.5%) / MoN + Pyrimidine + CC + * + a MoN + Pyrimidine + CC + * + a
24a2→33b2(17.7%) / Mo6 MoN + Pyrimidine + CC + * + a
31b2→26a2(15.4%) / Mo6 MoN + Pyrimidine + CC + * + a
In / 2.27 / 1.02 / B1 / 25a2→33b2(36.3%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→26a2(33.0%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
Io / 2.29 / 1.08 / B1 / 25a2→33b2 (39.95) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→26a2(35.9%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
Ip / 2.21 / 1.04 / B1 / 25a2→33b2(42.6%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Thiadiazole + a
32b2→26a2(36.7%) / MoN + Pyrimidine + CC + a  MoN + Pyrimidine + CC + Thiadiazole + a

Table S2 The electronic transitions of complexes in set II.

compound / Ege (eV) / foc / symmetry / composition / major assignment
IIa / 1.96 / 0.84 / B1 / 25a2→33b2 (28.6%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
32b2→26a2 (26.5%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
30b2→26a2 (22.8%) / Mo6 MoN + Pyrimidine + NN + Phenyl + a
24a2→33b2 (18.3%) / Mo6  MoN + Pyrimidine + NN + Phenyl + a
2.14 / 0.88 / B1 / 30b2→26a2 (64.9%) / Mo6  MoN + Pyrimidine + NN + Phenyl + a
25a2→33b2 (14.5%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
32b2→26a2 (13.3%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
2.27 / 0.72 / A1 / 25a2→26a2 (32.2%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
32b2→33b2 (29.9%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Phenyl + a
30b2→33b2 (25.7%) / Mo6 MoN + Pyrimidine + NN + Phenyl + a
IIb / 2.05 / 1.51 / B1 / 25a2→34b2 (32.1%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Tetrazine + a
30b2→27a2 (29.8%) / Mo6  MoN + Pyrimidine + NN + Tetrazine + a
32b2→27a2 (28.1%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Tetrazine + a
IIc / 2.07 / 1.06 / B1 / 30b2→26a2 (49.0%) / Mo6  MoN + Pyrimidine + NN + Pyrimidine + a
25a2→33b2 (23.2%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyrimidine + a
32b2→26a2 (20.6%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyrimidine + a
IId / 2.10 / 1.25 / B1 / 30b2→26a2 (44.4%) / Mo6  MoN + Pyrimidine + NN + Pyridazine + a
25a2→33b2 (25.7%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridazine + a
32b2→26a2 (22.8%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridazine + a
IIe / 2.02 / 0.80 / B1 / 30b2→26a2 (52.1%) / Mo6  MoN + Pyrimidine + NN + Pyridazine + a
25a2→33b2 (19.5%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridazine + a
32b2→26a2 (17.4%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridazine + a
IIf / 2.11 / 0.98 / B1 / 30b2→26a2 (59.4%) / Mo6 MoN + Pyrimidine + NN + Pyridine + a
25a2→33b2 (18.5%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridine + a
32b2→26a2 (16.9%) / MoN + Pyrimidine + NN + a  MoN + Pyrimidine + NN + Pyridine + a
IIg / 1.95 / 1.32 / B1 / 25a2→33b2 (39.3%) / MoN + Pyrimidine + CC + Thiophene + a  MoN + Pyrimidine + CC + Thiophene + a
32b2→26a2 (37.4%) / MoN + Pyrimidine + CC + Thiophene + a  MoN + Pyrimidine + CC + Thiophene + a
30b2→26a2 (18.1%) / Mo6  MoN + Pyrimidine + CC + Thiophene + a
IIh / 1.90 / 1.14 / B1 / 25a2→33b2 (34.3%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→26a2 (32.6%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
30b2→26a2 (29.8%) / Mo6  MoN + Pyrimidine + CC + Thiazole + a
2.09 / 0.80 / B1 / 30b2→26a2 (66.8%) / Mo6  MoN + Pyrimidine + CC + Thiazole + a
25a2→33b2 (13.9%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→26a2 (13.1%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
2.22 / 0.93 / A1 / 25a2→26a2 (35.6%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→33b2 (33.7%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
30b2→33b2 (20.3%) / Mo6  MoN + Pyrimidine + CC + Thiazole + a
IIi / 1.96 / 1.11 / B1 / 25a2→33b2 (35.6%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
32b2→26a2 (33.2%) / MoN + Pyrimidine + CC + Thiazole + a  MoN + Pyrimidine + CC + Thiazole + a
30b2→26a2 (27.0%) / Mo6  MoN + Pyrimidine + CC + Thiazole + a
IIj / 2.13 / 1.19 / B1 / 30b2→26a2(50.2%) / Mo6 MoN + Pyrimidine + CC + Thiadiazole + a
25a2→33b2(22.5%) / MoN + Pyrimidine + CC + Thiadiazole + a MoN + Pyrimidine + CC + Thiadiazole + a
32b2→26a2(20.5%) / MoN + Pyrimidine + CC + Thiadiazole + a MoN + Pyrimidine + CC + Thiadiazole + a
2.30 / 0.95 / A1 / 25a2→26a2(37.8%) / MoN + Pyrimidine + CC + Thiadiazole + a MoN + Pyrimidine + CC + Thiadiazole + a
32b2→33b2(34.7%) / MoN + Pyrimidine + CC + Thiadiazole + a MoN + Pyrimidine + CC + Thiadiazole + a
30b2→33b2(18.3%) / Mo6 MoN + Pyrimidine + CC + Thiadiazole + a

Table S3 The electronic transitions of complexes in set III.

compound / Ege (eV) / foc / symmetry / composition / major assignment
IIIa / 1.44 / 0.56 / B1 / 31b2→27a2 (60.8%) / Mo6  CC + Phenyl + Nitryl
26a2→34b2 (18.6%) / MoN + Pyrimidine + CC  CC + Phenyl + Nitryl
33b2→27a2 (16.5%) / MoN + Pyrimidine + CC  CC + Phenyl + Nitryl
2.33 / 0.53 / B1 / 26a2→36b2 (28.3%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Nitryl
23a2→34b2 (22.9%) / CC + Phenyl  CC + Phenyl + Nitryl
33b2→29a2 (22.5%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Nitryl
1.51 / 0.51 / A1 / 31b2→34b2 (32.5%) / Mo6  CC + Phenyl + Nitryl
26a2→27a2 (31.4%) / MoN + Pyrimidine + CC  CC + Phenyl + Nitryl
33b2→34b2 (28.0%) / MoN + Pyrimidine + CC  CC + Phenyl + Nitryl
IIIb / 1.46 / 1.11 / B1 / 26a2→34b2(36.7%) / MoN + Pyrimidine + CC  CC + Tetrazine + Nitryl
33b2→27a2(31.4%) / MoN + Pyrimidine + CC  CC + Tetrazine + Nitryl
31b2→27a2(26.8%) / Mo6  CC + Tetrazine + Nitryl
IIIc / B1 / 31b2→27a2(51.9%) / Mo6  CC + Pyrimidine(2) + Nitryl
26a2→34b2(23.9%) / MoN + Pyrimidine + CC  CC + Pyrimidine(2) + Nitryl
33b2→27a2(20.5%) / MoN + Pyrimidine + CC  CC + Pyrimidine(2) + Nitryl
A1 / 26a2→27a2(34.9%) / MoN + Pyrimidine + CC  CC + Pyrimidine(2) + Nitryl
33b2→34b2(30.3%) / MoN + Pyrimidine + CC  CC + Pyrimidine(2) + Nitryl
31b2→34b2(27.4%) / Mo6  CC + Pyrimidine(2) + Nitryl
IIId / 1.36 / 0.58 / B1 / 31b2→27a2 (47.6%) / Mo6  CC + Pyridazine + Nitryl
26a2→34b2 (24.5%) / MoN + Pyrimidine + CC  CC + Pyridazine + Nitryl
33b2→27a2 (21.0%) / MoN + Pyrimidine + CC  CC + Pyridazine + Nitryl
IIIe / 1.37 / 0.62 / B1 / 31b2→27a2 (50.4%) / Mo6  CC + Pyridazine + Nitryl
26a2→34b2(24.0%) / MoN + Pyrimidine + CC  CC + Pyridazine + Nitryl
33b2→27a2 (20.8%) / MoN + Pyrimidine + CC  CC + Pyridazine + Nitryl
IIIf / 1.42 / 0.59 / B1 / 31b2→27a2 (58.3%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2 (20.2%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2 (17.7%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
1.50 / 0.51 / A1 / 26a2→27a2 (32.7%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
31b2→34b2 (30.8%) / Mo6  CC + Pyridine + Nitryl
33b2→34b2 (28.8%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IIIg / 1.42 / 0.59 / B1 / 31b2→27a2 (56.7%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2 (21.1%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2 (18.4%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
1.50 / 0.53 / A1 / 26a2→27a2 (33.0%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
31b2→34b2 (30.0%) / Mo6  CC + Pyridine + Nitryl
33b2→34b2 (29.0%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IIIh / 1.43 / 0.75 / B1 / 31b2→27a2 (46.9%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2(25.8%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2(22.6%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
1.52 / 0.60 / A1 / 26a2→27a2 (35.6%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→34b2 (31.5%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
31b2→34b2 (23.7%) / Mo6  CC + Pyridine + Nitryl
IIIi / 1.43 / 0.75 / B1 / 31b2→27a2 (47.7%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2 (25.3%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2 (22.3%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IIIj / 1.52 / 0.50 / B1 / 31b2→27a2 (58.1%) / Mo6  CC + Thiophene + Nitryl
26a2→34b2(19.2%) / MoN + Pyrimidine + CC  CC + Thiophene + Nitryl
33b2→27a2(17.0%) / MoN + Pyrimidine + CC  CC + Thiophene + Nitryl
2.32 / 0.51 / B1 / 26a2→36b2 (31.2%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiophene + Nitryl
33b2→29a2 (25.5%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiophene + Nitryl
1.60 / 0.57 / A1 / 26a2→27a2 (30.8%) / MoN + Pyrimidine + CC  CC + Thiophene + Nitryl
31b2→34b2 (30.4%) / Mo6  CC + Thiophene + Nitryl
33b2→34b2 (27.5%) / MoN + Pyrimidine + CC  CC + Thiophene + Nitryl
IIIk / 1.56 / 0.50 / B1 / 31b2→27a2(56.9%) / Mo6  CC + Furan + Nitryl
26a2→34b2(19.6%) / MoN + Pyrimidine + CC  CC + Furan + Nitryl
33b2→27a2(17.2%) / MoN + Pyrimidine + CC  CC + Furan + Nitryl
1.64 / 0.52 / A1 / 31b2→34b2(31.4%) / Mo6  CC + Furan + Nitryl
26a2→27a2(29.4%) / MoN + Pyrimidine + CC  CC + Furan + Nitryl
33b2→34b2(26.0%) / MoN + Pyrimidine + CC  CC + Furan + Nitryl
IIIl / 2.36 / 0.46 / B1 / 26a2→36b2(27.3%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Pyrrole + Nitryl
61b1→69a1(26.4%) / Mo6 +MoN + Pyrimidine  Mo6
33b2→29a2(23.0%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Pyrrole + Nitryl
1.63 / 0.40 / A1 / 31b2→34b2(44.1%) / Mo6  CC + Pyrrole + Nitryl
26a2→27a2(23.7%) / MoN + Pyrimidine + CC  CC + Pyrrole + Nitryl
33b2→34b2(20.9%) / MoN + Pyrimidine + CC  CC + Pyrrole + Nitryl
IIIm / 1.29 / 0.47 / B1 / 26a2→34b2(42.0%) / MoN + Pyrimidine + CC  CC + * + Nitryl
33b2→27a2(37.9%) / MoN + Pyrimidine + CC  CC + * + Nitryl
31b2→27a2(13.7%) / Mo6  CC + * + Nitryl
2.34 / 0.43 / B1 / 61b1→69a1(36.2%) / Mo6 +MoN + Pyrimidine  Mo6
26a2→36b2(21.0%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + * + Nitryl
33b2→29a2(18.4%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + * + Nitryl
IIIn / 2.25 / 0.56 / B1 / 26a2→36b2(37.7%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiazole + Nitryl
33b2→29a2(30.3%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiazole + Nitryl
1.55 / 0.55 / A1 / 26a2→27a2(32.3%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
33b2→34b2(28.5%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
31b2→34b2(28.2%) / Mo6  CC + Thiazole + Nitryl
IIIo / 1.42 / 0.51 / B1 / 31b2→27a2(49.9%) / Mo6  CC + Thiazole + Nitryl
26a2→34b2(23.7%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
33b2→27a2(20.9%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
1.50 / 0.56 / A1 / 26a2→27a2(33.7%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
33b2→34b2(29.9%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
31b2→34b2(26.2%) / Mo6  CC + Thiazole + Nitryl
IIIp / 2.18 / 1.57 / B1 / 26a2→35b2(36.1%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiadiazole + Nitryl
33b2→28a2(30.7%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Thiadiazole + Nitryl
23a2→34b2(10.7%) / Pyrimidine + CC + Thiadiazole  CC + Thiadiazole + Nitryl
1.36 / 0.42 / A1 / 26a2→27a2(32.0%) / MoN + Pyrimidine + CC  CC + Thiadiazole + Nitryl
31b2→34b2(31.6%) / Mo6 CC + Thiadiazole + Nitryl
33b2→34b2(28.1%) / MoN + Pyrimidine + CC  CC + Thiadiazole + Nitryl

Table S4 The electronic transitions of complexes in set IV.

compound / Ege (eV) / foc / symmetry / composition / major assignment
IVa / 1.55 / 0.84 / B1 / 31b2→27a2(50.5%) / Mo6 NN + Phenyl + Nitryl
26a2→34b2(23.2%) / MoN + Pyrimidine + NN  NN + Phenyl + Nitryl
33b2→27a2(20.5%) / MoN + Pyrimidine + NN  NN + Phenyl + Nitryl
IVb / 1.62 / 1.43 / B1 / 26a2→34b2(35.4%) / MoN + Pyrimidine + NN  MoN + Pyrimidine + CC + Tetrazine + Nitryl
33b2→27a2(31.4%) / MoN + Pyrimidine + NN  MoN + Pyrimidine + CC + Tetrazine + Nitryl
31b2→27a2(24.1%) / Mo6  MoN + Pyrimidine + CC + Tetrazine + Nitryl
IVc / 1.59 / 0.93 / B1 / 31b2→27a2(45.5%) / Mo6 MoN + Pyrimidine + CC + Pyrimidine(2) + Nitryl
26a2→34b2(25.1%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Pyrimidine(2) + Nitryl
33b2→27a2(22.1%) / MoN + Pyrimidine + CC  MoN + Pyrimidine + CC + Pyrimidine(2) + Nitryl
IVd / 1.50 / 0.80 / B1 / 31b2→27a2 (46.1%) / Mo6 NN + Pyridazine + Nitryl
26a2→34b2 (25.4%) / MoN + Pyrimidine + NN  NN + Pyridazine + Nitryl
33b2→27a2 (22.1%) / MoN + Pyrimidine + NN  NN + Pyridazine + Nitryl
IVe / B1 / 31b2→27a2 (50.4%) / Mo6 NN + Pyridazine + Nitryl
26a2→34b2(24.0%) / MoN + Pyrimidine + NN  NN + Pyridazine + Nitryl
33b2→27a2 (20.8%) / MoN + Pyrimidine + NN  NN + Pyridazine + Nitryl
IVf / 1.57 / 0.69 / B1 / 31b2→27a2(60.1%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2(18.2%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2 (16.1%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IVg / 1.56 / 0.90 / B1 / 31b2→27a2(47.1%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2(24.7%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2(21.9%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IVh / 1.55 / 1.06 / B1 / 31b2→27a2 (37.8%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2(29.5%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2(26.1%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IVi / 1.54 / 1.03 / B1 / 31b2→27a2 (40.2%) / Mo6  CC + Pyridine + Nitryl
26a2→34b2(28.2%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
33b2→27a2(25.2%) / MoN + Pyrimidine + CC  CC + Pyridine + Nitryl
IVj / 1.65 / 1.23 / B1 / 26a2→34b2 (31.2%) / MoN + Pyrimidine + CC + Thiophene + NitrylMoN + Pyrimidine + CC + Thiophene + Nitryl
33b2→27a2 (30.5%) / MoN + Pyrimidine + CC + Thiophene + NitrylMoN + Pyrimidine + CC + Thiophene + Nitryl
31b2→27a2(28.9%) / Mo6  MoN + Pyrimidine + CC + Thiophene + Nitryl
IVk / 1.71 / 1.23 / B1 / 26a2→34b2 (31.7%) / MoN + Pyrimidine + CC + Furan  Pyrimidine + CC + Furan + Nitryl
31b2→27a2 (30.6%) / Mo6 MoN +Pyrimidine + CC + Furan + Nitryl
33b2→27a2(29.3%) / MoN + Pyrimidine + CC + Furan  MoN +Pyrimidine + CC + Furan + Nitryl
IVl / 1.72 / 0.97 / B1 / 31b2→27a2 (38.9%) / Mo6 Pyrimidine + CC + Pyrrole + Nitryl
26a2→34b2 (27.1%) / MoN + Pyrimidine + CC + Pyrrole + Nitryl  Pyrimidine + CC + Pyrrole + Nitryl
33b2→27a2 (24.9%) / MoN + Pyrimidine + CC + Pyrrole + Nitryl  Pyrimidine + CC + Pyrrole + Nitryl
IVm / 2.13 / 0.71 / B1 / 33b2→28a2 (29.7%) / MoN + Pyrimidine + CC + * MoN + Pyrimidine + CC + * + Nitryl
26a2→36b2 (28.8%) / MoN + Pyrimidine + CC + * Mo6 + CC + * + Nitryl
62b1→70a1 (10.8%) / Mo6 + MoN + Pyrimidine + CC  Mo6
IVn / 1.65 / 1.09 / B1 / 31b2→27a2 (32.3%) / Mo6 MoN + Pyrimidine + CC + Thiazole + Nitryl
26a2→34b2 (30.6%) / MoN + Pyrimidine + CC + ThiazoleMoN + Pyrimidine + CC + Thiazole + Nitryl
33b2→27a2 (28.3%) / MoN + Pyrimidine + CC + ThiazoleMoN + Pyrimidine + CC + Thiazole + Nitryl
IVo / 1.59 / 1.02 / B1 / 31b2→27a2 (32.1%) / Mo6  CC + Thiazole + Nitryl
26a2→34b2 (31.3%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
33b2→27a2 (28.7%) / MoN + Pyrimidine + CC  CC + Thiazole + Nitryl
IVp / 1.53 / 0.54 / B1 / 31b2→27a2 (48.0%) / Mo6 Pyrimidine + CC + Thiadiazole + Nitryl
26a2→34b2 (22.4%) / MoN + Pyrimidine + CC + Thiadiazole  Pyrimidine + CC + Thiadiazole + Nitryl
33b2→27a2 (20.0%) / MoN + Pyrimidine + CC + Thiadiazole  Pyrimidine + CC + Thiadiazole + Nitryl

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