theoretical study on the photophysical properties of ...2 9. cartesian coordinates of 2 at the...

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

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

2



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.


3

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


4

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


5

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.


6

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


7

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


8

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


Center Atomic Atomic Coordinates (Angstroms)


9

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


10

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


11

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


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


12

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


13

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


theoretical study on the photophysical properties of ...2 9. cartesian coordinates of 2 at the...

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