Supporting Information
Ab initio and DFT study of luminescent cyclometalated N-heterocyclic carbene organogold(ІІІ) complexes
Bao-Zhu Yanga, Qi Zhanga,Jing Zhonga*, Shuang Huangb and Hong-Xing Zhangb*
a School of Petrochemical Engineering, Changzhou University,
Changzhou 213100, Jiangsu, PRC
b State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, PRC
Table S1.Partial Molecular Orbital Compositions in the Lowest-Energy Excited-State for2, 3 in CH2Cl2Solution by TD-DFT Calculations
2MO / E (eV) / Au / C^N^C / NHC / bond type
L + 2 / -1.4044 / 28.3dx2-y2 / 47.6 / 23.4 / d(Au)+π*(C^N^C)+σ*(NHC)
L + 1 / -1.8980 / 98.7 / π*(C^N^C)
L / -2.5745 / 11.2P / 86.4 / P(Au) + π*(C^N^C)
HOMO−LUMO Energy Gap
H / -6.2421 / 95.9 / π(C^N^C)
H − 1 / -6.9341 / 98.9 / π(C^N^C)
H − 2 / -6.9991 / 9.0P / 77.6 / 13.5 / P(Au) + π(C^N^C) + π(NHC)
3
MO / E (eV) / Au / C^N^C / NHC / bond type
L + 2 / -1.4901 / 28.9dx2-y2 / 47.2 / 23.9 / d(Au)+π*(C^N^C)+σ*(NHC)
L + 1 / -1.9845 / 99.4 / π*(C^N^C)
L / -2.6387 / 11.3P / 86.3 / P(Au) + π*(C^N^C)
HOMO−LUMO Energy Gap
H / -6.4187 / 95.3 / π(C^N^C)
H − 1 / -6.9969 / 8.9P / 65.2 / 26.0 / P(Au) + π(C^N^C) + π(NHC)
H − 2 / -7.1863 / 8.0dxz / 89.4 / d(Au) + π(C^N^C)
Excitation energies and oscillator strengths for 1 calculated by TD-DFT
method in CH2Cl2.
Excitation energies and oscillator strengths:
Excited State 1: Singlet-A 3.2656 eV 379.67 nm f=0.0559
94 -> 98 -0.10592
95 -> 96 0.67706
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1149.22754542
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited State 2: Singlet-A 3.5854 eV 345.81 nm f=0.0014
94 -> 96 0.68862
Excited State 3: Singlet-A 3.9607 eV 313.03 nm f=0.1539
92 -> 97 0.11662
93 -> 96 0.67349
Excited State 4: Singlet-A 4.0223 eV 308.25 nm f=0.0000
95 -> 98 0.69240
Excited State 5: Singlet-A 4.1207 eV 300.88 nm f=0.0555
91 -> 96 -0.19892
92 -> 96 0.64507
Excited State 6: Singlet-A 4.1493 eV 298.81 nm f=0.0683
91 -> 96 -0.43132
92 -> 96 -0.21511
93 -> 97 0.13920
95 -> 97 0.46413
Excited State 7: Singlet-A 4.2100 eV 294.50 nm f=0.0002
90 -> 97 0.11107
94 -> 97 0.69301
Excited State 8: Singlet-A 4.3879 eV 282.56 nm f=0.1393
91 -> 96 0.47585
95 -> 97 0.43694
Excited State 9: Singlet-A 4.4474 eV 278.78 nm f=0.0494
92 -> 97 -0.39393
94 -> 98 0.54549
Excited State 10: Singlet-A 4.5673 eV 271.46 nm f=0.0111
90 -> 96 0.54356
93 -> 97 -0.13683
93 -> 98 -0.39936
Excited State 11: Singlet-A 4.5917 eV 270.02 nm f=0.0073
90 -> 96 0.29504
91 -> 96 0.11675
93 -> 97 0.57771
93 -> 98 0.18295
Excited State 12: Singlet-A 4.5941 eV 269.88 nm f=0.0021
90 -> 96 0.30802
93 -> 97 -0.29751
93 -> 98 0.53703
Excited State 13: Singlet-A 4.7009 eV 263.75 nm f=0.0006
92 -> 98 0.69242
Excited State 14: Singlet-A 4.7862 eV 259.04 nm f=0.3801
90 -> 98 -0.19374
91 -> 97 0.20257
91 -> 98 0.12013
92 -> 97 0.50841
94 -> 98 0.29876
95 -> 99 -0.12118
Excited State 15: Singlet-A 4.8182 eV 257.33 nm f=0.0301
90 -> 98 0.10122
91 -> 97 0.58391
92 -> 97 -0.12452
94 -> 98 -0.14854
95 -> 99 -0.21847
95 ->100 0.16325
Excited State 16: Singlet-A 4.8949 eV 253.29 nm f=0.0258
91 -> 98 0.68674
Excited State 17: Singlet-A 5.0915 eV 243.51 nm f=0.1915
91 -> 97 0.21729
95 -> 99 0.62976
95 ->100 0.13389
Excited State 18: Singlet-A 5.2151 eV 237.74 nm f=0.0006
90 -> 97 0.69112
94 -> 97 -0.11408
Excited State 19: Singlet-A 5.2233 eV 237.37 nm f=0.0394
94 -> 99 0.66803
94 ->100 -0.15691
Excited State 20: Singlet-A 5.2747 eV 235.05 nm f=0.5011
90 -> 98 -0.21178
91 -> 97 -0.18010
95 ->100 0.60805
Excited State 21: Singlet-A 5.3027 eV 233.81 nm f=0.2394
90 -> 98 0.59885
92 -> 97 0.13155
94 -> 98 0.10312
95 ->100 0.21878
Excited State 22: Singlet-A 5.4239 eV 228.59 nm f=0.1232
94 -> 99 0.14459
94 ->100 0.65573
95 ->102 -0.12236
Excited State 23: Singlet-A 5.5811 eV 222.15 nm f=0.0092
87 -> 96 0.11651
88 -> 96 -0.39622
93 -> 99 0.14929
95 ->101 0.54085
Excited State 24: Singlet-A 5.6172 eV 220.72 nm f=0.0506
88 -> 96 0.13988
93 -> 99 0.60839
93 ->100 0.29166
Excited State 25: Singlet-A 5.6675 eV 218.76 nm f=0.0539
89 -> 96 0.39309
91 ->101 0.12994
92 -> 99 0.24180
93 -> 97 -0.10122
93 ->102 -0.10309
95 ->102 0.42154
Excited State 26: Singlet-A 5.6853 eV 218.08 nm f=0.0010
88 -> 96 0.43741
89 -> 97 0.36087
93 ->100 -0.17978
95 ->101 0.32843
Excited State 27: Singlet-A 5.7567 eV 215.38 nm f=0.0021
90 ->102 0.12213
94 ->102 0.68073
Excited State 28: Singlet-A 5.7753 eV 214.68 nm f=0.0014
87 -> 96 0.67689
88 -> 96 0.18774
Excited State 29: Singlet-A 5.7802 eV 214.50 nm f=0.0206
92 -> 99 0.56446
92 ->100 0.15083
95 ->102 -0.35092
Excited State 30: Singlet-A 5.7888 eV 214.18 nm f=0.2319
88 -> 97 -0.15537
89 -> 96 0.48209
91 -> 99 0.12727
91 ->101 -0.11575
92 -> 99 -0.25222
92 ->101 0.12001
95 ->102 -0.25214
Excited State 31: Singlet-A 5.8468 eV 212.05 nm f=0.0002
90 ->101 0.10039
94 ->101 0.67499
Excited State 32: Singlet-A 5.8713 eV 211.17 nm f=0.0033
85 -> 96 -0.17235
86 -> 96 0.65524
89 -> 98 -0.12637
Excited State 33: Singlet-A 5.9038 eV 210.01 nm f=0.0064
91 -> 99 0.58870
91 ->100 0.23138
91 ->101 0.10702
92 ->100 -0.20651
Excited State 34: Singlet-A 5.9354 eV 208.89 nm f=0.3156
89 -> 97 0.16794
91 ->102 -0.10646
93 -> 99 -0.25318
93 ->100 0.57572
93 ->101 -0.13791
Excited State 35: Singlet-A 5.9606 eV 208.01 nm f=0.0006
91 -> 99 0.19983
91 ->100 0.17993
92 ->100 0.59937
93 ->102 0.11089
95 ->102 0.17085
Excited State 36: Singlet-A 6.1100 eV 202.92 nm f=0.1224
91 ->102 -0.18020
92 ->102 -0.27554
93 ->101 0.53301
95 ->104 -0.22790
Excited State 37: Singlet-A 6.1506 eV 201.58 nm f=0.0078
85 -> 96 0.67099
86 -> 96 0.17787
Excited State 38: Singlet-A 6.1556 eV 201.42 nm f=0.0073
90 -> 99 0.40803
91 -> 99 -0.15919
91 ->100 0.45435
91 ->101 -0.12176
92 ->101 0.19385
Excited State 39: Singlet-A 6.1744 eV 200.80 nm f=0.1311
85 -> 98 -0.14534
88 -> 97 -0.10361
90 -> 99 0.50080
91 -> 99 0.14075
91 ->100 -0.34100
92 ->101 -0.10950
93 ->102 0.11443
Excited State 40: Singlet-A 6.2014 eV 199.93 nm f=0.0015
78 -> 98 -0.10255
86 -> 96 0.12515
89 -> 98 0.67509