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1
Theoretical study on the photophysical properties of chiral
mononuclear and dinuclear zinc complexes
Yanling Sia and Guochun Yang*b
aCollege of Resource and Environmental Science, Jilin Agricultural University, Changchun,
130118 Jilin, China
bInstitute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University,
Changchun, 130024 Jilin, China
AUTHOR EMAIL ADDRESS:[email protected];
Contents
1. The calculated IR spectra of complexes 1 and 2 at B3LYP/6-31G(d,p) level along
with the experimental data S2
2. Computed absorption energy (nm) using different functionals at 6-31+G(d) basis
set level for mononuclear zinc complex 1 S3
3. Computed HOMO and LUMO energy level and corresponding energy gaps
(Eg=LUMO-HOMO) in eV using different functionals at 6-31+G(d) basis set level for
mononuclear zinc complex 1 S3
4. The calculated excitation energies, oscillator strengths and rotational strengths for
complex 1 in the gas phase at the B3LYP/ 6-31+G(d) level S3
5. Molecular orbitals involved into the main CD transition S5
6. The molecular structure of compound 4 S6
7. Comparison CD spectra between complex 1 and compound 4 S7
8. Cartesian coordinates of 1 at the B3LYP/6-31G(d,p) level of theory S7
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9. Cartesian coordinates of 2 at the B3LYP/6-31G(d,p) level of theory S8
10. Cartesian coordinates of 3 at the B3LYP/6-31G(d,p) level of theory S11
1000 1100 1200 1300 1400 1500 1600 1700 1800
1547
1667
a.u
.
Wavenumber/cm-1
Complex 1
1628
1000 1100 1200 1300 1400 1500 1600 1700 1800
a.u
.
Wavenumber/cm-1
Complex 2
1619~1626
Figure S1. The calculated IR spectra of complexes 1 and 2 at B3LYP/6-31G(d,p)
level along with the experimental data (labeled as blue). The experimental data can be
found in Ref 18.
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Table S1. Computed absorption energy (nm) using different functionals at 6-31+G(d)
basis set level for mononuclear zinc complex 1
Table S2. Computed HOMO and LUMO energy level and corresponding energy gaps
(Eg=LUMO-HOMO) in eV using different functionals at 6-31+G(d) basis set level for
mononuclear zinc complex 1
Table S3. The calculated excitation energies, oscillator strengths and rotational
strengths for complex 1 in the gas phase at the B3LYP/ 6-31+G(d) level.
states eV λa
fb
Rlengthc Rvelocity
c
1 2.9003 427.49 0.0056 0.5106 0.1039
2 2.9571 419.28 0.1232 -59.4728 -60.9718
3 3.0473 406.87 0.0010 2.4885 1.4143
4 3.0860 401.76 0.0487 -47.4616 -41.0091
5 3.1598 392.38 0.0194 -11.3030 -13.1671
6 3.3787 366.95 0.0054 12.6094 14.3427
7 3.5139 352.84 0.0002 -0.3813 -0.1140
8 3.5715 347.15 0.0131 5.8548 5.2827
9 3.6646 338.33 0.0004 0.2383 0.2715
10 3.7158 333.67 0.0001 0.2388 0.2309
11 3.7876 327.34 0.0169 -22.2068 -26.1104
12 3.8394 322.93 0.0010 -3.9545 -2.7195
13 3.8711 320.28 0.0466 -26.7261 -21.7800
14 3.8992 317.98 0.0040 0.0529 1.8211
Functional Band 1 Band 2 Band 3
B3LYP 239.9 347.2 419.3
PBE 232.8 369.2 401.4
B3PW91 238.4 344.4 417.8
M05-2X 242.9 363.9
CAM-B3LYP 246.8 372.6
BH&HLYP 244.0 358.1
Functional HOMO LUMO Eg
B3LYP -6.459 -3.032 3.427
PBE -6.498 -3.060 3.438
B3PW91 -6.507 -2.717 3.790
M05-2X -7.773 -2.104 5.669
CAM-B3LYP -7.775 -1.892 5.884
BH&HLYP -7.461 -1.968 5.492
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15 3.9409 314.61 0.0037 -8.1575 -8.5485
16 3.9875 310.93 0.0131 10.1909 7.8055
17 4.1412 299.39 0.0101 -5.5742 -1.6960
18 4.3043 288.04 0.0007 -1.2049 -0.8501
19 4.3255 286.64 0.0014 -3.4449 -1.1650
20 4.5407 273.05 0.1520 -14.4576 4.4432
21 4.5945 269.85 0.0948 34.8227 34.7013
22 4.6622 265.93 0.0008 -4.9438 -4.7589
23 4.6790 264.98 0.0032 0.2308 -1.2424
24 4.6917 264.26 0.0002 -0.1533 -0.2788
25 5.0752 244.29 0.0020 1.9969 -4.3714
26 5.1684 239.89 0.3805 -225.0606 -205.0255
27 5.2132 237.83 0.0035 -4.6167 -6.4992
28 5.2297 237.08 0.0077 -6.5689 -5.7706
29 5.2678 235.36 0.0042 0.2946 0.6942
30 5.3042 233.75 0.0002 -0.0895 0.1247
31 5.3087 233.55 0.0002 -0.0480 -0.1083
32 5.3241 232.88 0.0051 0.3061 -0.7233
33 5.3832 230.32 0.0032 -0.3437 -0.2800
34 5.4035 229.45 0.0013 0.0629 -0.0093
35 5.4582 227.15 0.0076 -8.7747 -10.6935
36 5.4680 226.75 0.0101 -5.7417 -6.5834
37 5.4727 226.55 0.0038 2.8387 3.3007
38 5.4965 225.57 0.0013 -0.7563 0.1216
39 5.5067 225.15 0.0001 -0.2299 -0.3281
40 5.5289 224.25 0.0021 1.4398 1.5179
41 5.5546 223.21 0.0049 23.5266 24.2051
42 5.5702 222.59 0.0007 1.6058 1.6436
43 5.5929 221.68 0.0026 -2.1897 -2.3749
44 5.6045 221.22 0.0014 -0.8341 -0.8890
45 5.6130 220.89 0.0041 -2.4643 -2.0632
46 5.6305 220.20 0.0011 -1.9267 -1.7494
47 5.6398 219.84 0.0070 25.7576 27.3871
48 5.6536 219.30 0.0036 7.1604 7.7447
49 5.6575 219.15 0.0112 -2.9795 -2.8835
50 5.6652 218.85 0.0044 2.9180 1.7481
51 5.6946 217.72 0.0016 -3.9528 -3.6661
52 5.7084 217.19 0.0814 35.8333 30.7213
53 5.7232 216.63 0.0815 30.2500 34.3067
54 5.7382 216.07 0.0314 9.7996 11.1542
55 5.7718 214.81 0.0044 -0.9770 0.0617
56 5.7751 214.69 0.0059 0.6554 -1.1485
57 5.7994 213.79 0.0058 -0.9826 -0.9801
58 5.8038 213.63 0.0007 3.2887 3.1704
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59 5.8290 212.70 0.0242 19.3129 20.6102
60 5.8318 212.60 0.0025 -1.2870 -0.5173
61 5.8387 212.35 0.0276 23.3183 16.4617
62 5.8452 212.11 0.0019 4.5713 4.8316
63 5.8575 211.67 0.0066 -1.7986 -3.2802
64 5.8904 210.49 0.0108 22.0554 25.4331
65 5.8997 210.15 0.0228 2.0512 4.6038
66 5.9078 209.87 0.0010 2.0253 1.1158
67 5.9136 209.66 0.0051 -0.3029 -0.7825
68 5.9207 209.41 0.0083 -13.8268 -14.5651
69 5.9347 208.92 0.0073 9.9214 8.4624
70 5.9389 208.76 0.0046 21.1518 22.3819 aλ in nm.
b Oscillator Strengths.
c R values (in 10
-40 esu
2cm
2) using the velocity-gauge
representation and length-gauge representation of the electric dipole operator.
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Figure S2. Molecular orbitals involved into the main CD transition for the studied
complexes 1 and 2.
Figure S3. The molecular structure of compound 4
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Figure S4. Comparison CD spectra between complex 1 and compound 4
Table S4. Cartesian coordinates of 1 at the B3LYP/6-31G(d,p) level of theory
Center
Number
Atomic
Number
Atomic
Type
Coordinates (Angstroms)
x y z
1 30 0 9.540376 3.987150 15.408798
2 8 0 10.319134 4.278353 17.248867
3 17 0 8.421361 5.910510 15.078263
4 7 0 9.419830 4.986825 19.567258
5 7 0 11.422282 3.994026 14.594854
6 17 0 8.530265 1.996524 15.418847
7 6 0 11.475796 4.735693 17.554104
8 6 0 12.580038 4.774632 16.628060
9 6 0 13.822829 5.224776 17.072080
10 1 0 14.644786 5.228946 16.357836
11 6 0 14.076554 5.679621 18.382403
12 6 0 13.008898 5.691442 19.262033
13 1 0 13.152628 6.060543 20.275682
14 6 0 11.720058 5.244719 18.885893
15 6 0 15.456287 6.143838 18.782700
16 1 0 15.470493 6.495908 19.817454
17 1 0 16.191516 5.335590 18.697332
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18 1 0 15.803660 6.965947 18.147043
19 6 0 12.473867 4.373009 15.232657
20 1 0 13.424411 4.416274 14.686433
21 6 0 10.649185 5.361399 19.811678
22 1 0 10.843155 5.809713 20.786021
23 6 0 11.614411 3.644760 13.152821
24 1 0 12.283764 4.401337 12.722701
25 6 0 10.268451 3.719789 12.427798
26 1 0 9.814159 4.707548 12.550256
27 1 0 10.413363 3.531562 11.360547
28 1 0 9.574438 2.966118 12.811095
29 6 0 12.292608 2.288251 13.006055
30 6 0 13.481675 2.182429 12.275423
31 1 0 13.915521 3.071542 11.823257
32 6 0 14.111619 0.946683 12.111476
33 1 0 15.031674 0.881285 11.537574
34 6 0 13.558603 -0.197130 12.685515
35 1 0 14.046191 -1.159920 12.562326
36 6 0 12.373419 -0.098591 13.418985
37 1 0 11.935948 -0.985609 13.867845
38 6 0 11.739699 1.132848 13.579004
39 1 0 10.816455 1.195538 14.149335
40 6 0 8.251393 5.225213 20.432212
41 1 0 8.636065 5.328206 21.453580
42 6 0 7.328983 4.000707 20.358083
43 1 0 7.852833 3.092269 20.669580
44 1 0 6.466675 4.153159 21.011269
45 1 0 6.956738 3.858823 19.338881
46 6 0 7.540681 6.519925 20.049888
47 6 0 7.279497 6.843575 18.711645
48 1 0 7.613910 6.207561 17.895682
49 6 0 6.594430 8.017247 18.397875
50 1 0 6.409459 8.256034 17.355378
51 6 0 6.158148 8.872721 19.411316
52 1 0 5.624650 9.785270 19.162431
53 6 0 6.414825 8.554092 20.745207
54 1 0 6.083321 9.216151 21.539818
55 6 0 7.107450 7.384582 21.061332
56 1 0 7.309443 7.142308 22.102501
57 1 0 9.300096 4.579776 18.625012
Table S5. Cartesian coordinates of 2 at the B3LYP/6-31G(d,p) level of theory
Center Atomic Atomic Coordinates (Angstroms)
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Number Number Type x y z
1 30 0 5.110552 17.381365 1.302036
2 30 0 7.540453 15.508834 1.932084
3 7 0 4.595386 19.401495 2.249419
4 7 0 6.526837 18.760105 0.498933
5 7 0 3.569440 17.751836 -0.374178
6 7 0 3.481793 16.449863 1.976157
7 7 0 6.588039 13.605952 2.224103
8 7 0 8.871544 14.502549 3.196363
9 6 0 3.476445 19.669518 2.936110
10 1 0 2.864501 18.806317 3.181130
11 6 0 3.120294 20.959825 3.315771
12 1 0 2.208159 21.132761 3.876610
13 6 0 3.961397 22.013171 2.952080
14 1 0 3.713109 23.036485 3.217965
15 6 0 5.125931 21.733806 2.242069
16 1 0 5.805451 22.527185 1.945631
17 6 0 5.416581 20.406070 1.915806
18 6 0 6.715061 20.010255 1.233119
19 1 0 7.013584 20.819208 0.547818
20 6 0 7.821734 19.823740 2.294415
21 1 0 8.772162 19.586207 1.809698
22 1 0 7.555472 18.996506 2.956769
23 1 0 7.943848 20.736688 2.886018
24 6 0 7.183589 18.610836 -0.602734
25 1 0 7.770400 19.458863 -0.985849
26 6 0 7.230931 17.419027 -1.420754
27 6 0 6.822063 16.133725 -0.941623
28 6 0 6.976641 15.047008 -1.827094
29 1 0 6.680538 14.063916 -1.474261
30 6 0 7.489908 15.196987 -3.110519
31 1 0 7.581388 14.323227 -3.746059
32 6 0 7.890053 16.462936 -3.569756
33 6 0 7.765538 17.551379 -2.717805
34 1 0 8.093949 18.524679 -3.072859
35 6 0 8.595979 15.622634 -5.692232
36 1 0 9.029460 16.033007 -6.606140
37 1 0 7.646302 15.127977 -5.938961
38 1 0 9.284571 14.875977 -5.273659
39 6 0 3.664599 18.536987 -1.462639
40 1 0 4.655494 18.919550 -1.684082
41 6 0 2.578034 18.854472 -2.268938
42 1 0 2.709371 19.495818 -3.134042
43 6 0 1.329636 18.329641 -1.932246
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44 1 0 0.451411 18.558515 -2.528722
45 6 0 1.230157 17.505079 -0.814142
46 1 0 0.277120 17.075482 -0.521636
47 6 0 2.373303 17.233666 -0.053359
48 6 0 2.305848 16.308628 1.152930
49 1 0 1.397447 16.594079 1.718870
50 6 0 2.081838 14.852918 0.665410
51 1 0 2.070544 14.183817 1.530581
52 1 0 2.895932 14.550326 -0.000460
53 1 0 1.134455 14.739809 0.127095
54 6 0 3.361774 15.993566 3.247473
55 1 0 2.369457 15.647749 3.558574
56 6 0 4.354112 15.966166 4.265882
57 6 0 5.740765 16.312223 4.089800
58 6 0 6.593588 16.275725 5.197382
59 1 0 7.626435 16.576388 5.044338
60 6 0 6.167186 15.875366 6.466778
61 1 0 6.842180 15.856037 7.315666
62 6 0 4.822154 15.511411 6.646711
63 6 0 3.941589 15.561854 5.578807
64 1 0 2.898591 15.294205 5.711940
65 6 0 3.133324 14.779576 8.171043
66 1 0 3.067619 14.520246 9.230246
67 1 0 2.814227 13.915109 7.571017
68 1 0 2.450166 15.615565 7.963955
69 6 0 5.414507 13.279156 1.658533
70 1 0 5.096000 13.936623 0.857657
71 6 0 4.661949 12.191207 2.082403
72 1 0 3.723230 11.955399 1.593701
73 6 0 5.132179 11.439978 3.159594
74 1 0 4.562417 10.595873 3.536737
75 6 0 6.339411 11.791978 3.754350
76 1 0 6.722194 11.237263 4.604534
77 6 0 7.055169 12.882935 3.251729
78 6 0 8.410540 13.273502 3.836073
79 1 0 8.264172 13.440427 4.914544
80 6 0 9.414259 12.117185 3.638097
81 1 0 9.051531 11.193283 4.096771
82 1 0 10.379131 12.358542 4.091731
83 1 0 9.572024 11.938253 2.570319
84 6 0 10.001817 15.019166 3.576264
85 1 0 10.536922 14.567083 4.423072
86 6 0 10.666692 16.132646 2.968557
87 6 0 10.197936 16.732803 1.748386
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88 6 0 11.039377 17.738449 1.175263
89 1 0 10.716396 18.171628 0.233956
90 6 0 12.205174 18.149025 1.778213
91 1 0 12.824922 18.921027 1.331009
92 6 0 12.638130 17.575266 2.997374
93 6 0 11.881144 16.575408 3.569945
94 1 0 12.196056 16.096049 4.491398
95 6 0 14.291003 17.538194 4.713619
96 1 0 15.215345 18.069785 4.947048
97 1 0 14.507475 16.464292 4.624018
98 1 0 13.574394 17.684810 5.533886
99 8 0 6.339541 15.945790 0.275907
100 8 0 8.410123 16.718928 -4.817618
101 8 0 6.240023 16.665484 2.877033
102 8 0 4.479429 15.124979 7.928374
103 8 0 9.099011 16.409011 1.144305
104 8 0 13.815340 18.081387 3.498568
Table S6. Cartesian coordinates of 3 at the B3LYP/6-31G(d,p) level of theory
Center
Number
Atomic
Number
Atomic
Type
Coordinates (Angstroms)
x y z
1 30 0 7.685192 10.503351 1.083230
2 30 0 5.170568 12.274176 1.870524
3 8 0 6.473673 11.030255 2.678024
4 8 0 6.412888 12.034576 0.195640
5 8 0 3.644955 11.466100 0.905855
6 7 0 6.032312 14.169841 2.368000
7 7 0 3.759217 13.073982 3.157069
8 7 0 8.172921 8.407101 1.833543
9 7 0 6.388514 9.247944 0.017384
10 7 0 9.313134 10.503012 -0.545800
11 7 0 9.217940 11.399885 1.990662
12 6 0 -1.578675 9.546718 4.117747
13 1 0 -2.493029 9.079725 4.470523
14 6 0 -1.114396 9.308157 2.839344
15 1 0 -1.659569 8.646062 2.170795
16 6 0 3.076366 15.420644 3.636832
17 1 0 2.085203 15.125397 3.991063
18 1 0 3.007615 15.636796 2.566477
19 1 0 3.360803 16.337593 4.160719
20 6 0 4.648238 12.209774 -5.105286
21 1 0 4.468863 13.191063 -5.537906
22 6 0 7.221807 14.588303 1.906279
23 1 0 7.603956 14.029842 1.059486
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24 6 0 9.261528 11.645052 3.320393
25 1 0 10.218632 12.010626 3.694233
26 6 0 5.921393 11.004807 4.977417
27 1 0 4.911717 10.747240 4.670018
28 6 0 5.746833 10.806913 -1.763901
29 6 0 0.821519 10.788309 3.211102
30 6 0 5.076405 12.137238 -3.758828
31 6 0 5.988668 12.010905 -1.045227
32 6 0 10.430241 11.717469 1.268134
33 1 0 11.317724 11.375311 1.833590
34 6 0 2.034039 11.409452 2.703635
35 6 0 8.248897 11.458640 4.291728
36 6 0 6.882071 11.155342 3.963450
37 6 0 2.538860 11.043219 1.411148
38 6 0 11.650889 10.273088 -2.044369
39 1 0 12.567406 10.178323 -2.619250
40 6 0 7.622809 6.095293 1.570313
41 1 0 6.961773 5.343163 1.150505
42 6 0 0.331869 10.986118 4.527918
43 1 0 0.893722 11.591004 5.231327
44 6 0 2.620766 12.496547 3.421893
45 1 0 2.016724 12.907021 4.237156
46 6 0 7.372108 7.451541 1.343063
47 6 0 7.552410 11.485509 6.714904
48 6 0 5.319308 10.865741 -3.148170
49 6 0 5.284322 13.319457 -2.988365
50 1 0 5.092173 14.282415 -3.455838
51 6 0 6.223105 11.183251 6.316849
52 1 0 5.454684 11.070735 7.076916
53 6 0 1.727541 10.171236 0.593832
54 1 0 2.101384 9.963412 -0.403740
55 6 0 9.168502 11.914220 8.498590
56 1 0 9.395247 12.041349 9.553647
57 6 0 4.723100 9.814017 -5.276951
58 1 0 4.601071 8.909923 -5.867161
59 6 0 4.104733 14.294225 3.881270
60 1 0 4.158912 14.090551 4.962022
61 6 0 5.781111 9.533007 -1.094756
62 1 0 5.203480 8.732127 -1.571211
63 6 0 10.191363 11.988771 7.536098
64 1 0 11.218738 12.163421 7.844335
65 6 0 6.139027 7.926805 0.591940
66 1 0 5.914853 7.199314 -0.204243
67 6 0 9.542699 6.734567 2.866693
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68 1 0 10.404214 6.496516 3.480982
69 6 0 9.899355 11.826199 6.190993
70 1 0 10.726803 11.861620 5.491205
71 6 0 5.147374 9.716047 -3.964795
72 1 0 5.371378 8.731083 -3.569576
73 6 0 5.725571 13.259274 -1.697762
74 1 0 5.888422 14.162560 -1.118092
75 6 0 11.658953 10.897923 -0.800876
76 1 0 12.577390 11.301688 -0.386299
77 6 0 10.466713 11.000190 -0.073638
78 6 0 9.229713 8.059656 2.581016
79 1 0 9.825992 8.885310 2.957885
80 6 0 6.137613 15.816302 4.091582
81 1 0 5.690318 16.268779 4.970626
82 6 0 -0.837496 10.389925 4.965638
83 1 0 -1.176346 10.565700 5.982907
84 6 0 10.445285 9.771276 -2.536718
85 1 0 10.386340 9.283024 -3.503567
86 6 0 5.485058 14.767535 3.436392
87 6 0 7.877594 11.658474 8.085312
88 1 0 7.074583 11.576495 8.814666
89 6 0 7.915206 15.643338 2.485061
90 1 0 8.870505 15.955748 2.078706
91 6 0 10.616987 13.238507 1.033085
92 1 0 10.555581 13.762772 1.990899
93 1 0 9.829958 13.618304 0.374707
94 1 0 11.586470 13.465430 0.576489
95 6 0 0.561226 9.638444 1.049162
96 1 0 -0.024526 8.980853 0.410267
97 6 0 8.723639 5.733572 2.342083
98 1 0 8.939313 4.686378 2.532753
99 6 0 8.583626 11.596055 5.718999
100 6 0 4.935065 7.987456 1.557142
101 1 0 4.033222 8.278818 1.012616
102 1 0 5.125875 8.732818 2.333008
103 1 0 4.764954 7.013375 2.026881
104 6 0 9.306616 9.908766 -1.752150
105 1 0 8.345466 9.535299 -2.089053
106 6 0 7.363598 16.260218 3.608657
117 1 0 7.885817 17.071853 4.106293
108 6 0 4.463263 11.069650 -5.859529
109 1 0 4.133943 11.136859 -6.891870
110 6 0 0.075318 9.907140 2.368507
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