Supplementary material for the manuscript entitled

Investigation on the physicochemical properties of trans-4-stilbenecarboxaldehyde-

derived hydrazones and their copper(II) complexes

Lenka V. Tamayoa, Jeferson G. Da Silvab, Matheus C. Quintãoa, Helio A. Duartea, Sonia

R.W. Louroc, Heloisa Beraldoa*

a Departamento de Química, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte MG Brazil

b Departamento de Farmácia, Universidade Federal de Juiz de Fora, Campus Governador Valadares, 35010-177

Governador Valadares, MG, Brazil.

c Departamento de Física, Pontifícia Universidade Católica do Rio de Janeiro, 22653-900 Rio de Janeiro, RJ,

Brazil

1

Table of contents

Infrared spectra of hydrazones ligands (HL1-HL7)……………………………...2

1H NMR spectra of ligands HL1, HL2, HL4, HL5, HL6 and 13C NMR spectra of

ligands HL5 and HL6…………………...............................................................8

Infrared spectra of complexes (1-6)…………………………………. .. 16

X-ray crystallography results……………………………………………………23

Theoretical Calculations………………………………………………………...27

2

Infrared spectra of hydrazones ligands (HL1-HL6)

3

Fig. S1 IR spectrum of ligand HStpT (HL1) in KBr

4

Fig. S2 IR spectrum of ligand HStpClPh (HL2) in KBr

5

Fig. S3 IR spectrum of ligand HStpNO2Ph (HL4) in KBr

6

Fig. S4 IR spectrum of ligand HStAc (HL5) in KBr

7

Fig. S5 IR spectrum of ligand HStBz (HL6) in KBr

8

1H NMR spectra of ligands HL1, HL2, HL4, HL5, HL6, and 13C NMR spectra of ligands HL5, HL6

9

Fig. S6 1H NMR spectrum of ligand HStpT (HL1) in DMSO-d6 (400 MHz) at room temperature

10

Fig. S7 1H NMR spectrum of ligand HStpClPh (HL2) in DMSO-d6 (400 MHz) at room temperature

11

Fig. S8 1H NMR spectrum of ligand HStpNO2Ph (HL4) in DMSO-d6 (400 MHz) at room temperature

12

Fig. S9 1H NMR spectrum of ligand HStAc (HL5) in DMSO-d6 (400 MHz) at room temperature

13

Fig. S10 13C NMR spectrum of ligand HStAc (HL5) in DMSO-d6 (100 MHz) at room temperature

14

Fig. S11 1H NMR spectrum of ligand HStBz (HL6) in DMSO-d6 (400 MHz) at room temperature

15

Fig. S12 13C NMR spectrum of ligand HStBz (HL6) in DMSO-d6 (100 MHz) at room temperature

16

Infrared spectra of copper(II) complexes (1-6)

17

Fig. S13 IR spectrum of complex [Cu(HStpT)2Cl2] (1) in KBr

18

Fig. S14 IR spectrum of complex [Cu(HStpClPh)2Cl2] (2) in KBr

19

Fig. S15 IR spectrum of complex [Cu(HStpOHPh)2Cl2] (3) in KBr

20

Fig. S16 IR spectrum of complex [Cu(HStpNO2Ph)2Cl2] (4) in KBr

21

Fig. S17 IR spectrum of complex [Cu(HStAc)2Cl2] (5) in KBr

22

Fig. S18 IR spectrum of complex [Cu(HStBz)2Cl2] (6) in KBr

23

X-ray crystallography results

24

Table S19. Bond lengths [Å] and angles [°] for HStpT (HL1) and HStpNO2Ph∙DMSO

(HL4a)

Bond lengths (Å) HStpT (HL1) HStpNO2Ph ∙DMSO

(HL4a)

C(15)-N(1) 1.2817(17) 1.2764(16)

C(16)-O(1) 1.2262(17) 1.2172(15)

C(16)-N(2) 1.3670(17) 1.3591(15)

C(16)-C(17) 1.4885(18) 1.5024(16)

N(1)-N(2) 1.3706(14) 1.3755(13)

Angles (°)

O(1)-C(16)-N(2) 116.17(12) 123.01(11)

O(1)-C(16)-C(17) 118.66(11) 120.67(11)

N(2)-C(16)-C(17) 120.6 116.30(10)

C(15)-N(1)-N(2) 120.6 117.32(10)

C(16) -N(2)-N(1) 122.42(12) 116.27(9)

C(8)-C(7)-H(7) 122.59(12) 117.0

C(6)-C(7)-H(7) 114.99(12) 117.0

25

Table S20. Torsion angles [°] for HStpT (HL1)

C(2)-C(1)-C(6)-C(7) -178.86(12)

C(5)-C(6)-C(7)-C(8) -175.75(13)

C(1)-C(6)-C(7)-C(8) 4.3(2)

O(1)-C(16)-N(2)-N(1) 4.82(19)

C(17)-C(16)-N(2)-N(1) -175.49(11)

C(15)-N(1)-N(2)-C(16) -172.91(12)

Table S21. Torsion angles [°] for HStpNO2Ph∙DMSO (HL4a)

C(2)-C(1)-C(6)-C(7) 179.13 (12)

C(4)-C(5)-C(6)-C(7) -179.39 (11)

C(1)-C(6)-C(7)-C(8) -176.37 (12)

C(6)-C(7)-C(8)-C(9) -178.59 (11)

O(1)-C(16)-N(2)-N(1) -3.54 (19)

C(15)-N(1)-N(2)-C(16) 170.53 (11)

26

Table S22. Hydrogen bonds for HStpT (HL1) [Å and °]

_______________________________________________________________________

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

_______________________________________________________________________

N(2)-H(2A)...O(1)#1 0.88 2.51 3.3770(16) 168.4

_______________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 x,y+1,z

Table S23. Hydrogen bonds for HStpNO2Ph∙DMSO (HL4a) [Å and °]

______________________________________________________________________

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

_______________________________________________________________________

C(15)-H(15)...O(4) 0.95 2.52 3.2828(15) 137.0

C(21)-H(21)...O(1)#1 0.95 2.41 3.0936(15) 128.5

C(101)-H(10A)...N(1)#1 0.98 2.65 3.5873(18) 161.3

C(102)-H(10E)...O(1)#2 0.98 2.60 3.5591(18) 167.6

C(102)-H(10F)...O(2)#3 0.98 2.56 3.2502(17) 127.9

N(2)-H(2A)...O(4) 0.88 1.95 2.7811(13) 155.9

______________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 x,-y+3/2,z-1/2 #2 x,-y+1/2,z-1/2 #3 -x,y-1/2,-z+1/2

27

27

SUPPORTING INFORMATION FOR THEORETICAL CALCULATIONS

1. Calculated thermodynamic properties of the tautomers of complex (5)

Table S24. Relative Free energies in kcal.mol-1 and the electronic (Eelecrel), solvation (Gsolv)

and the thermal energies contributions.

Energy Isomers

5a 5b 5c 5d 5e

B3LYP/cc-pVDZ

ΔEelecrel -7.51 -11.61 -6.22 0.00 -2.04

ΔGsolv(PCM) 9.46 12.36 6.71 0.00 2.15

ΔGtherm 0.98 0.14 0.18 0.00 -0.11

ΔGrel 2.93 0.75 0.49 0.00 0.11

B3LYP/cc-pVTZ//B3LYP/cc-pVDZ

ΔEelecrel -7.46 16.98 -6.53 0.00 -1.71

ΔGrel 2.97 29.48 0.37 0.00 0.34

PBE/cc-pVDZ//B3LYP/cc-pVDZ

ΔEelecrel -5.28 -10.30 -4.50 0.00 -0.87

ΔGrel 5.16 2.20 2.40 0.00 1.17

PBE/cc-pVTZ//B3LYP/cc-pVDZ

ΔEelecrel -5.41 -10.68 -4.64 0.00 -0.56

ΔGrel 5.02 1.82 2.25 0.00 1.48

28

28

2. OPTIMIZED B3LYP/cc-pVDZ GEOMETRIES of the tautomers of complex

(5)

COMPOUND 5a

75

scf done: -4245.615527

C 9.533046 4.837655 0.667403

C 9.310129 3.574371 0.080232

C 10.392337 2.951092 -0.579652

C 11.640060 3.568729 -0.644848

C 11.843921 4.824037 -0.055051

C 10.783516 5.455940 0.601624

C 7.974025 2.977364 0.185804

C 7.579077 1.778892 -0.302255

C 6.242378 1.190248 -0.190108

C 6.007981 -0.077622 -0.763323

C 4.764571 -0.699398 -0.681847

C 3.690242 -0.070374 -0.019231

C 3.910160 1.215829 0.522104

C 5.154991 1.825938 0.451771

C 2.335046 -0.633248 0.096342

N 1.921511 -1.851372 0.205400

N 2.834761 -2.865056 0.288046

C 2.414487 -4.152678 0.370726

C 3.480116 -5.194414 0.563082

O 1.216208 -4.479805 0.283914

Cu -0.345035 -3.181166 0.101218

Cl -0.486435 -2.976768 2.425897

N -2.138459 -2.110096 -0.099795

N -3.233395 -2.894962 -0.331671

C -3.105102 -4.264182 -0.347108

C -4.339309 -5.021072 -0.761661

C -2.253285 -0.823475 -0.016299

C -3.434835 0.041043 -0.057574

C -4.730104 -0.335247 0.369582

C -5.783226 0.569738 0.335003

C -5.603614 1.890597 -0.134705

C -4.304361 2.265360 -0.542084

C -3.243232 1.369759 -0.491192

C -6.678244 2.882387 -0.203752

C -7.973583 2.689264 0.137316

C -9.057974 3.674965 0.074901

C -8.883118 4.998554 -0.386244

C -9.954141 5.889718 -0.419348

C -11.227779 5.486905 0.005874

C -11.419119 4.180038 0.464623

C -10.346668 3.286321 0.497553

O -2.049952 -4.815576 -0.035479

Cl -0.087783 -3.139917 -2.224731

H 3.822979 -2.662341 0.432569

H -4.076085 -2.460683 -0.701076

H -1.291838 -0.312621 0.084438

H -4.914496 -1.327591 0.781960

H -6.760870 0.241596 0.689904

H -2.247490 1.695466 -0.800160

H -4.129936 3.283976 -0.895866

29

29

H -6.363737 3.863508 -0.571528

H -8.282981 1.705618 0.504279

H 1.518713 0.096985 0.122922

H 3.085225 1.735568 1.014918

H 5.280414 2.814597 0.895626

H 4.627480 -1.658530 -1.183727

H 6.820538 -0.581364 -1.291842

H 8.302445 1.157694 -0.838694

H 7.247673 3.594778 0.723513

H 12.823531 5.303847 -0.108863

H 12.462858 3.068290 -1.160456

H 8.708431 5.336916 1.182817

H 10.929709 6.434309 1.064912

H 10.259609 1.973974 -1.047657

H -10.502466 2.265976 0.857279

H -12.406970 3.854432 0.798138

H -9.796602 6.908672 -0.780036

H -12.063640 6.189261 -0.021922

H -7.901714 5.336391 -0.723705

H 3.394808 -5.940100 -0.240992

H 4.494192 -4.774014 0.565573

H 3.298040 -5.710954 1.517871

H -5.230969 -4.384773 -0.839921

H -4.148204 -5.492013 -1.738892

H -4.522234 -5.824167 -0.033822

COMPOUND 5b

75

scf done: -4245.617443

Cu -0.007848 0.288597 0.112393

O 0.123663 2.675026 0.092175

O -0.116950 -2.096523 0.206075

Cl -0.058142 0.239934 -2.247444

Cl 0.042362 0.348309 2.477112

C 1.302597 2.992577 0.239886

C 1.747708 4.405033 0.515984

H 2.817978 4.563372 0.326508

H 1.155547 5.090375 -0.105342

H 1.536695 4.638062 1.572341

N 2.317596 2.064094 0.162227

H 3.267045 2.331997 0.411410

N 2.015808 0.735203 0.069478

C 2.943965 -0.161455 -0.033338

H 2.549344 -1.181965 -0.013954

C 4.398704 -0.031991 -0.137397

C 5.172263 -1.129639 0.305964

C 6.557452 -1.111728 0.236866

C 7.245007 -0.002428 -0.307050

C 6.467263 1.074854 -0.784075

C 5.078253 1.069486 -0.700881

H 4.529468 1.910511 -1.125720

H 6.968414 1.933637 -1.236169

H 7.111729 -1.977585 0.601103

H 4.667371 -2.005506 0.719378

C 8.702787 0.078825 -0.413979

H 9.071090 0.991433 -0.891695

H 9.218178 -1.753959 0.500077

C 9.592066 -0.845696 0.017278

30

30

C 11.053647 -0.777655 -0.084592

C 11.815643 -1.846070 0.433355

C 13.210401 -1.839533 0.365574

C 13.877962 -0.761328 -0.223374

C 13.136564 0.308821 -0.743330

C 11.744512 0.302959 -0.676249

H 11.190202 1.147542 -1.089255

H 13.650381 1.154777 -1.205437

H 14.968640 -0.751996 -0.278619

H 13.777192 -2.679195 0.773986

H 11.299598 -2.691936 0.894900

N -2.027763 -0.174775 0.178332

N -2.309657 -1.498933 0.362147

C -1.282978 -2.414142 0.435083

C -1.698847 -3.811764 0.812737

H -1.433510 -3.982018 1.868780

H -1.131452 -4.527345 0.202565

H -2.775690 -3.987678 0.686140

H -3.242015 -1.759811 0.675115

C -2.971508 0.704393 0.066032

C -4.427417 0.551942 0.036987

H -4.691583 2.566262 0.792009

C -5.196552 1.659093 0.452946

C -6.585003 1.606308 0.450967

C -7.277110 0.457867 0.007536

C -6.503151 -0.633243 -0.448818

H -6.991285 -1.529087 -0.834349

C -5.114845 -0.592498 -0.431738

H -4.567766 -1.444458 -0.836549

C -8.740829 0.463704 0.030542

H -9.182624 1.400546 0.382533

H -9.107412 -1.495724 -0.667689

C -9.554745 -0.557004 -0.326124

C -11.021298 -0.563585 -0.305069

C -11.695067 -1.743283 -0.685635

H -13.587045 -2.738280 -0.982659

C -13.089734 -1.812693 -0.684228

C -13.845878 -0.700302 -0.302296

H -14.936876 -0.749667 -0.300190

C -13.192931 0.480760 0.077209

H -13.776381 1.354785 0.375356

C -11.800999 0.550774 0.076458

H -11.316850 1.482632 0.373908

H -11.109495 -2.616311 -0.985281

H -2.591007 1.728823 0.009207

H -7.155035 2.473027 0.793162

COMPOUND 5c

75

scf done: -4245.617844

C -11.727266 0.987408 0.236707

C -11.131163 -0.292754 0.271548

C -11.981630 -1.417095 0.326192

C -13.370525 -1.273571 0.343855

C -13.943574 0.001337 0.307805

C -13.113519 1.129794 0.254370

C -9.680824 -0.511034 0.253838

C -8.716825 0.436432 0.186076

31

31

C -7.271269 0.205741 0.168316

C -6.677378 -1.072494 0.280362

C -5.298583 -1.223520 0.259287

C -4.438192 -0.112968 0.095240

C -5.024994 1.168001 0.004922

C -6.407691 1.316122 0.047189

C -2.999634 -0.386308 0.105177

N -2.008411 0.269167 -0.411364

N -2.231495 1.384418 -1.174136

C -1.170160 2.138385 -1.621216

C -1.530616 3.228643 -2.598321

Cu 0.000681 -0.326069 -0.181653

O -0.021692 1.922951 -1.240921

N 2.090524 -0.222753 0.105245

N 2.366978 0.465152 1.261676

C 1.317379 0.953502 1.970262

O 0.155506 0.835075 1.537053

C 3.039847 -0.698292 -0.635181

C 4.493922 -0.605845 -0.505981

C 5.189951 0.478057 0.079238

C 6.577406 0.486917 0.135350

C 7.340836 -0.586166 -0.378879

C 6.640561 -1.653543 -0.983142

C 5.253393 -1.657129 -1.061292

C 8.802676 -0.639950 -0.330299

C 9.623189 0.290518 0.210695

C 11.087863 0.246359 0.269449

C 11.856893 -0.820525 -0.245972

C 13.247705 -0.804160 -0.158830

C 13.909742 0.274724 0.443680

C 13.164164 1.339227 0.959369

C 11.770573 1.323580 0.872673

C 1.617665 1.632367 3.272295

Cl 0.102809 -1.314605 -2.268839

Cl -0.441900 -2.380065 1.296499

H 2.692799 1.778988 3.436601

H 1.104931 2.604603 3.289568

H 1.204789 1.020519 4.089366

H 3.304640 0.448320 1.656933

H 11.365158 -1.672425 -0.718851

H 13.823046 -1.639763 -0.563656

H 14.999846 0.282441 0.509392

H 13.668825 2.185225 1.431226

H 11.193235 2.158554 1.277962

H 9.183210 1.184830 0.662936

H 9.236947 -1.535881 -0.783374

H 7.203307 -2.489191 -1.405050

H 4.741581 -2.491456 -1.545584

H 4.653101 1.352732 0.448457

H 7.073603 1.349792 0.580830

H 2.647169 -1.278134 -1.476928

H -1.273228 2.888785 -3.614756

H -0.925493 4.117714 -2.375728

H -2.597526 3.490345 -2.574096

H -3.149048 1.502886 -1.598440

H -4.406357 2.063787 -0.051390

H -4.866525 -2.221291 0.362416

H -7.300585 -1.959846 0.398131

32

32

H -6.836098 2.319110 -0.011874

H -9.007220 1.489885 0.132713

H -2.665227 -1.300190 0.610512

H -9.384913 -1.563929 0.297392

H -11.102861 1.881660 0.196351

H -13.553042 2.129409 0.226765

H -15.029324 0.118273 0.321610

H -14.006839 -2.160386 0.385965

H -11.540313 -2.416665 0.354646

COMPOUND 5d

75

scf done: -4245.618634

C 9.334120 3.842137 -1.211642

C 8.547137 3.564414 -0.074125

C 8.845589 4.253669 1.122143

C 9.886105 5.179526 1.171559

C 10.657528 5.443773 0.031236

C 10.376624 4.769888 -1.161251

C 7.465348 2.581016 -0.193265

C 6.607355 2.194786 0.779351

C 5.526579 1.215903 0.647918

C 5.268149 0.485651 -0.534196

C 4.214049 -0.416176 -0.610699

C 3.367175 -0.639589 0.499798

C 3.651663 0.051122 1.696085

C 4.695395 0.966246 1.762107

C 2.246501 -1.583726 0.525869

N 1.445425 -1.975613 -0.412480

N 1.542524 -1.454920 -1.673648

C 0.672623 -1.869811 -2.648220

C 0.790747 -1.160698 -3.970609

Cu 0.027629 -3.603769 -0.207193

Cl -1.639069 -5.212016 -0.241984

N -1.468811 -2.153269 0.389277

N -1.575986 -1.960260 1.739002

C -0.683483 -2.564034 2.585555

O 0.176827 -3.343089 2.164961

C -2.298742 -1.583719 -0.424651

C -3.462233 -0.729782 -0.167384

C -4.303672 -0.821988 0.961913

C -5.401171 0.023342 1.096577

C -5.709484 1.001157 0.126292

C -4.879385 1.069122 -1.016281

C -3.795019 0.216596 -1.163507

C -6.865952 1.872457 0.343926

C -7.260747 2.892668 -0.452723

C -8.412381 3.777819 -0.249510

C -8.637197 4.814015 -1.180231

C -9.714222 5.691593 -1.040295

C -10.595424 5.552563 0.036293

C -10.388482 4.527166 0.969616

C -9.313502 3.650967 0.830771

C -0.830870 -2.216070 4.042565

Cl 1.768647 -5.089055 -0.573321

O -0.148603 -2.767142 -2.438230

H -2.201867 -1.239500 2.090502

H 2.130892 -0.639999 -1.832098

33

33

H 2.007770 -2.032757 1.494037

H 4.089109 -0.988602 -1.530897

H 5.906802 0.613501 -1.408950

H 3.033572 -0.127801 2.578667

H 4.882204 1.500011 2.696725

H 6.693606 2.640262 1.774769

H 7.369880 2.138118 -1.189610

H -2.050720 -1.771928 -1.473128

H -3.178842 0.283541 -2.062805

H -5.091124 1.789097 -1.807717

H -4.141822 -1.588036 1.721637

H -6.043234 -0.076378 1.974496

H -7.435094 1.652127 1.252015

H -6.677980 3.115475 -1.352061

H -11.439574 6.236132 0.149633

H -11.073363 4.410674 1.812556

H -7.952281 4.928045 -2.024388

H -9.865520 6.485987 -1.774554

H -9.175798 2.859170 1.569261

H 9.119378 3.318953 -2.147068

H 10.971021 4.966956 -2.056207

H 10.099511 5.701142 2.107282

H 11.471864 6.170156 0.075330

H 8.260073 4.065393 2.023730

H 0.077717 -1.688835 4.372289

H -1.707838 -1.589189 4.251203

H -0.901438 -3.149116 4.620382

H 1.677675 -0.516874 -4.037154

H 0.820380 -1.912974 -4.771553

H -0.111226 -0.547005 -4.122355

COMPOUND 5e

75

scf done: -4245.618454

C -5.426115 7.005560 0.133196

C -6.002295 5.727059 -0.021293

C -7.405048 5.645848 -0.166117

C -8.191139 6.796641 -0.155548

C -7.601707 8.059130 -0.000902

C -6.214473 8.158107 0.143593

C -5.118671 4.556490 -0.026618

C -5.485632 3.260941 -0.162440

C -4.591327 2.101994 -0.175060

C -3.184396 2.193614 -0.068295

C -2.390157 1.057034 -0.103707

C -2.955697 -0.234151 -0.217196

C -4.358815 -0.331015 -0.337701

C -5.149864 0.813640 -0.320586

C -2.023951 -1.362635 -0.280744

N -2.170419 -2.610113 0.030005

N -3.337329 -3.053785 0.589021

C -3.504033 -4.395514 0.829387

C -4.755001 -4.768748 1.579843

Cu -0.701507 -4.149191 -0.303785

Cl 0.659384 -6.016059 -0.370034

N 1.159714 -2.539227 -0.084833

N 1.485622 -2.504972 1.240912

C 0.748465 -3.248183 2.111882

34

34

O -0.251369 -3.892164 1.748652

C 1.843887 -1.870514 -0.953399

C 2.976612 -0.947911 -0.804952

C 3.204770 -0.126191 0.323184

C 4.288387 0.742711 0.366997

C 5.202948 0.831464 -0.706539

C 4.957381 0.024368 -1.838919

C 3.864625 -0.832976 -1.893857

C 6.366871 1.720220 -0.712415

C 6.757299 2.541532 0.289530

C 7.918477 3.437999 0.292160

C 8.802695 3.571612 -0.801153

C 9.888822 4.442724 -0.738479

C 10.124128 5.204043 0.414890

C 9.258825 5.084474 1.506643

C 8.170187 4.212042 1.444507

C 1.198796 -3.243796 3.544644

O -2.675903 -5.221641 0.443858

Cl -1.035843 -3.993042 -2.590507

H -5.476099 -3.943438 1.651735

H -5.224433 -5.626916 1.079041

H -4.472767 -5.086910 2.596140

H -3.974390 -2.377625 1.004047

H -1.017135 -1.133029 -0.638838

H -4.842985 -1.294614 -0.498232

H -6.231809 0.712391 -0.430849

H -2.702466 3.167080 0.030682

H -1.304758 1.159924 -0.037144

H -6.545374 3.016105 -0.279438

H -4.057327 4.795447 0.092956

H -4.342068 7.089753 0.245427

H -5.743540 9.136228 0.264500

H -8.222223 8.957810 0.006178

H -9.274118 6.710679 -0.269398

H -7.888162 4.674916 -0.289434

H 1.506960 -2.062868 -1.978705

H 2.503592 -0.117966 1.159004

H 4.415902 1.370739 1.249612

H 5.637355 0.082106 -2.691975

H 3.695687 -1.435405 -2.789184

H 6.954684 1.687216 -1.634521

H 6.169725 2.566190 1.212630

H 8.640729 2.990557 -1.710750

H 10.559537 4.530448 -1.596181

H 10.976618 5.885242 0.459059

H 9.431421 5.672708 2.410711

H 7.497233 4.123727 2.301368

H 2.356688 -2.082036 1.557242

H 1.486641 -4.268892 3.824395

H 0.351914 -2.949731 4.181758

H 2.044407 -2.567128 3.724090

35

35

3. VIBRATIONAL ANALYSIS based on B3LYP/cc-pVDZ calculations.

(HARMONIC FREQUENCIES in CM-1).

Compound 5a

Frequencies -- 7.2268 14.9110 17.9274

Frequencies -- 21.3205 22.6377 27.5925

Frequencies -- 28.6480 33.5014 39.4024

Frequencies -- 43.9513 47.9138 50.7797

Frequencies -- 51.9476 54.9056 59.9014

Frequencies -- 67.7614 72.0404 74.5323

Frequencies -- 79.6376 88.9812 93.9423

Frequencies -- 101.0022 107.4825 115.0867

Frequencies -- 129.5760 141.4275 142.3390

Frequencies -- 167.9350 171.6387 174.1116

Frequencies -- 181.9923 188.5565 198.7126

Frequencies -- 208.1894 221.3621 225.8694

Frequencies -- 234.6190 242.4631 255.7412

Frequencies -- 260.3589 276.5648 283.5466

Frequencies -- 301.3712 304.5551 329.0800

Frequencies -- 339.4123 349.4421 413.2494

Frequencies -- 414.6737 414.9083 416.3233

Frequencies -- 439.0851 454.8034 472.3150

Frequencies -- 475.7622 485.6278 489.9154

Frequencies -- 497.3499 500.5798 504.2788

Frequencies -- 530.6287 543.0834 549.5095

Frequencies -- 593.7563 604.4805 611.2271

Frequencies -- 611.7450 628.1877 628.7108

Frequencies -- 628.9039 639.9298 640.9002

Frequencies -- 646.5889 648.9715 650.0469

Frequencies -- 706.6005 707.2207 719.6427

Frequencies -- 722.2321 744.6214 745.7502

Frequencies -- 778.5350 779.6367 814.8906

Frequencies -- 820.3730 843.7677 846.0765

Frequencies -- 853.3611 855.1642 856.0343

Frequencies -- 857.9470 859.3244 860.7515

Frequencies -- 886.1451 887.6745 906.2776

Frequencies -- 906.8888 925.8102 927.7909

Frequencies -- 946.8187 948.7386 991.4893

Frequencies -- 992.6978 993.8108 995.3632

Frequencies -- 997.2035 1001.6520 1005.1096

Frequencies -- 1006.2139 1008.4631 1008.5670

Frequencies -- 1009.5123 1009.8934 1018.1709

Frequencies -- 1019.8890 1022.2108 1023.3271

Frequencies -- 1031.7939 1037.6847 1039.8496

Frequencies -- 1043.5456 1048.6562 1048.6716

Frequencies -- 1093.8680 1100.6830 1100.9062

Frequencies -- 1116.0052 1144.9798 1146.1625

Frequencies -- 1165.5787 1166.1679 1191.5131

Frequencies -- 1191.8523 1196.3415 1196.8496

Frequencies -- 1218.2822 1219.6818 1229.3166

Frequencies -- 1236.9314 1250.9519 1253.4406

Frequencies -- 1265.0172 1289.5821 1299.7290

Frequencies -- 1302.2421 1325.9298 1327.5222

Frequencies -- 1333.3238 1336.7869 1348.6240

Frequencies -- 1350.9223 1356.7755 1357.7054

Frequencies -- 1371.1155 1373.9947 1376.1257

Frequencies -- 1379.2299 1406.0368 1414.4639

Frequencies -- 1428.4267 1430.3313 1444.9244

36

36

Frequencies -- 1448.5594 1452.5081 1453.9225

Frequencies -- 1475.0802 1475.1344 1517.9707

Frequencies -- 1520.4041 1522.3917 1536.4596

Frequencies -- 1539.4280 1548.2514 1590.8891

Frequencies -- 1591.8929 1619.2727 1619.5363

Frequencies -- 1635.2106 1638.3135 1648.8076

Frequencies -- 1649.4138 1666.1119 1679.9266

Frequencies -- 1684.1433 1688.6009 1688.6722

Frequencies -- 1721.4663 3056.0151 3058.8191

Frequencies -- 3133.6658 3135.8431 3154.4462

Frequencies -- 3154.8300 3156.3250 3156.4021

Frequencies -- 3158.8316 3163.0255 3163.3288

Frequencies -- 3171.6741 3172.6344 3178.3151

Frequencies -- 3179.2935 3180.3912 3181.7959

Frequencies -- 3182.9217 3183.4949 3187.2098

Frequencies -- 3188.3411 3195.3125 3196.7026

Frequencies -- 3197.0822 3198.5545 3201.7570

Frequencies -- 3203.3964 3203.9429 3204.8366

Frequencies -- 3213.5565 3521.9454 3552.4989

COMPOUND 5b

Frequencies -- 4.8653 5.9254 14.0903

Frequencies -- 17.5882 21.7777 23.1570

Frequencies -- 27.7043 29.9613 39.2895

Frequencies -- 41.6948 52.2740 52.7261

Frequencies -- 53.8047 57.8709 59.0922

Frequencies -- 72.9700 76.7792 79.1055

Frequencies -- 85.6613 93.6712 101.3638

Frequencies -- 103.1823 103.7226 112.2356

Frequencies -- 117.2560 146.5464 150.3529

Frequencies -- 151.4167 168.0601 169.7190

Frequencies -- 176.2238 179.9528 190.9467

Frequencies -- 199.4419 213.5176 223.1056

Frequencies -- 236.8707 250.9037 260.9476

Frequencies -- 265.8142 269.4992 279.7401

Frequencies -- 296.2553 308.6545 328.8156

Frequencies -- 348.0271 350.8249 411.8807

Frequencies -- 413.5698 414.1493 414.9779

Frequencies -- 435.6097 441.6393 475.4890

Frequencies -- 478.0018 488.0275 488.6883

Frequencies -- 500.1047 503.4587 506.5698

Frequencies -- 515.5749 541.5806 542.0897

Frequencies -- 591.8407 594.7282 609.6528

Frequencies -- 611.8314 624.4631 625.8439

Frequencies -- 628.3958 628.4851 641.3231

Frequencies -- 641.6943 649.6606 650.7146

Frequencies -- 706.0465 706.5003 723.4723

Frequencies -- 727.6750 744.7058 745.0991

Frequencies -- 779.1682 779.3587 814.7758

Frequencies -- 818.8291 845.4270 845.9266

Frequencies -- 852.1365 854.5354 855.9074

Frequencies -- 856.8438 859.6142 860.3868

Frequencies -- 886.4197 888.3160 908.4101

Frequencies -- 909.0479 933.4306 934.3300

Frequencies -- 947.1158 947.7393 993.1019

Frequencies -- 993.2534 994.0680 994.5610

Frequencies -- 996.1712 997.6172 999.5609

Frequencies -- 1002.8626 1007.1735 1008.5562

37

37

Frequencies -- 1008.6847 1008.8021 1019.1470

Frequencies -- 1019.4537 1021.5917 1022.2421

Frequencies -- 1029.0656 1030.0048 1039.0850

Frequencies -- 1039.2781 1048.4109 1048.9716

Frequencies -- 1100.6013 1101.3869 1118.7897

Frequencies -- 1120.1280 1147.0626 1147.7599

Frequencies -- 1165.8603 1166.0976 1191.3471

Frequencies -- 1192.3261 1196.8637 1197.2269

Frequencies -- 1219.0549 1219.4933 1231.7684

Frequencies -- 1236.2985 1251.8901 1253.1283

Frequencies -- 1260.7016 1262.2496 1301.4130

Frequencies -- 1302.8045 1327.5334 1328.1616

Frequencies -- 1336.2076 1337.3054 1349.4522

Frequencies -- 1352.0644 1357.8069 1357.9382

Frequencies -- 1373.1095 1373.8983 1375.4704

Frequencies -- 1375.5541 1413.7395 1415.2178

Frequencies -- 1427.6548 1428.2752 1446.8824

Frequencies -- 1448.3763 1452.1634 1452.7923

Frequencies -- 1475.2001 1475.2988 1514.9997

Frequencies -- 1515.4753 1520.7534 1521.5199

Frequencies -- 1539.8903 1539.9114 1590.0852

Frequencies -- 1590.7089 1619.1828 1619.5725

Frequencies -- 1635.4924 1635.9560 1648.9119

Frequencies -- 1648.9449 1680.1541 1681.2908

Frequencies -- 1688.0009 1688.6314 1723.4619

Frequencies -- 1723.4951 3054.0894 3054.7657

Frequencies -- 3131.9534 3132.5688 3155.4413

Frequencies -- 3155.8330 3159.4057 3159.8230

Frequencies -- 3164.2408 3164.9449 3172.2142

Frequencies -- 3172.2897 3173.5615 3175.2082

Frequencies -- 3179.0677 3179.1743 3181.7733

Frequencies -- 3184.9880 3186.8296 3188.2018

Frequencies -- 3188.2606 3196.9440 3197.2773

Frequencies -- 3197.3250 3198.0314 3204.7657

Frequencies -- 3204.9239 3207.4551 3210.0593

Frequencies -- 3213.2101 3550.0356 3550.5970

COMPOUND 5c

Frequencies -- 5.3616 5.7007 14.8305

Frequencies -- 18.0027 20.6677 25.1199

Frequencies -- 26.9698 31.3192 37.5155

Frequencies -- 42.4745 47.3188 54.1897

Frequencies -- 56.7238 63.9986 65.6117

Frequencies -- 66.8626 75.6775 79.0670

Frequencies -- 85.5049 91.0052 92.5072

Frequencies -- 100.6718 106.4069 111.8739

Frequencies -- 120.6829 131.2367 148.8625

Frequencies -- 159.1959 161.4802 168.4027

Frequencies -- 175.4346 182.3490 184.3138

Frequencies -- 199.5012 207.2260 222.1383

Frequencies -- 234.7142 247.3072 261.1520

Frequencies -- 262.7115 283.6831 287.8893

Frequencies -- 291.9390 309.6204 331.9604

Frequencies -- 346.1148 348.4535 412.1365

Frequencies -- 413.9856 414.2446 416.1557

Frequencies -- 434.3791 446.8058 474.4654

Frequencies -- 475.4172 487.9394 488.5460

Frequencies -- 498.3508 503.9030 508.5908

38

38

Frequencies -- 512.4442 539.5343 539.6905

Frequencies -- 591.6311 592.3908 608.4773

Frequencies -- 614.1664 621.9482 628.2550

Frequencies -- 628.3812 631.8930 641.4390

Frequencies -- 643.8854 648.9871 656.6227

Frequencies -- 706.3567 706.5006 723.5151

Frequencies -- 726.7447 745.9323 746.5823

Frequencies -- 779.7272 779.8048 814.6600

Frequencies -- 821.3284 846.6579 846.8252

Frequencies -- 852.5006 856.8669 857.0188

Frequencies -- 857.9853 861.3962 862.8788

Frequencies -- 886.5509 888.3733 911.5013

Frequencies -- 912.3040 947.1396 947.7361

Frequencies -- 959.1881 966.5027 993.0873

Frequencies -- 993.7421 994.9349 997.5511

Frequencies -- 997.8497 1003.2528 1003.3902

Frequencies -- 1008.3178 1008.6656 1009.9419

Frequencies -- 1010.0359 1013.4543 1019.5999

Frequencies -- 1020.0176 1021.8280 1022.2708

Frequencies -- 1027.4507 1037.3571 1038.5679

Frequencies -- 1042.7870 1048.0562 1048.6719

Frequencies -- 1099.9566 1100.3850 1101.3137

Frequencies -- 1116.1211 1146.4154 1146.9113

Frequencies -- 1166.0610 1166.7414 1190.9305

Frequencies -- 1191.6033 1196.1439 1196.7706

Frequencies -- 1218.7287 1219.4949 1231.9317

Frequencies -- 1236.7033 1252.4730 1253.4179

Frequencies -- 1263.0878 1283.4466 1300.4058

Frequencies -- 1303.1185 1326.8082 1327.5502

Frequencies -- 1337.1238 1337.2517 1349.6868

Frequencies -- 1350.7460 1357.7612 1358.1271

Frequencies -- 1373.4624 1373.8646 1375.3757

Frequencies -- 1377.5249 1402.9461 1413.2436

Frequencies -- 1426.9860 1427.5305 1445.9136

Frequencies -- 1447.0785 1451.1870 1452.7621

Frequencies -- 1475.1008 1475.2548 1515.8471

Frequencies -- 1519.8692 1520.1691 1531.4489

Frequencies -- 1538.7473 1543.6229 1588.5489

Frequencies -- 1590.5714 1618.9845 1619.2318

Frequencies -- 1632.9055 1635.2082 1647.3347

Frequencies -- 1648.4535 1656.2091 1674.8341

Frequencies -- 1686.7334 1688.1015 1690.2020

Frequencies -- 1728.3149 3052.4550 3060.0702

Frequencies -- 3130.0342 3136.7042 3137.3862

Frequencies -- 3153.6891 3156.3433 3157.6905

Frequencies -- 3162.4042 3164.7243 3165.2938

Frequencies -- 3166.5905 3172.4203 3172.7287

Frequencies -- 3178.9941 3179.5216 3182.9671

Frequencies -- 3185.3242 3186.9694 3187.9802

Frequencies -- 3188.5140 3196.4596 3197.2727

Frequencies -- 3198.2913 3198.6843 3204.5020

Frequencies -- 3205.0263 3205.9049 3214.0051

Frequencies -- 3214.4416 3545.1095 3554.3255

COMPOUND 5d

Frequencies -- 5.1279 13.8194 17.9233

Frequencies -- 20.0852 20.9508 23.9799

Frequencies -- 24.9670 27.4859 35.8079

39

39

Frequencies -- 38.2250 43.5346 50.6651

Frequencies -- 53.8812 56.7708 59.6742

Frequencies -- 68.2969 68.8057 76.9717

Frequencies -- 79.4661 91.4477 95.0157

Frequencies -- 102.4341 106.6743 118.2915

Frequencies -- 123.6355 135.9959 138.3223

Frequencies -- 149.2816 158.0851 167.9791

Frequencies -- 170.9195 177.1877 188.3577

Frequencies -- 199.2374 202.5243 230.6757

Frequencies -- 238.8217 253.7042 259.9217

Frequencies -- 266.5003 271.3586 275.8470

Frequencies -- 296.2913 310.5024 328.8183

Frequencies -- 343.3163 349.2913 413.7025

Frequencies -- 414.8618 415.2597 415.9143

Frequencies -- 433.8712 437.7174 473.8133

Frequencies -- 477.2471 488.3083 490.3714

Frequencies -- 499.7021 502.2460 503.4627

Frequencies -- 514.1354 541.8714 543.4473

Frequencies -- 596.4833 600.2421 604.9238

Frequencies -- 609.3934 628.3272 628.6761

Frequencies -- 634.3997 636.1261 640.0547

Frequencies -- 641.0853 648.0137 650.0946

Frequencies -- 706.0256 706.6142 717.6485

Frequencies -- 722.1640 745.2939 745.9173

Frequencies -- 778.9399 779.5315 816.1952

Frequencies -- 819.6336 845.9861 846.4908

Frequencies -- 854.4917 855.4793 856.3894

Frequencies -- 857.0256 860.8904 861.0336

Frequencies -- 886.3144 888.3303 909.6646

Frequencies -- 911.4694 946.4581 946.5819

Frequencies -- 956.0123 956.9302 992.7653

Frequencies -- 993.0628 994.5939 995.5599

Frequencies -- 999.5835 999.6975 1002.3563

Frequencies -- 1003.1128 1008.0099 1008.1131

Frequencies -- 1008.6361 1008.7622 1019.0006

Frequencies -- 1019.2718 1021.5606 1022.9376

Frequencies -- 1031.8546 1032.8917 1041.0544

Frequencies -- 1041.5937 1048.2490 1048.5016

Frequencies -- 1100.4216 1100.8372 1106.2998

Frequencies -- 1111.8980 1145.7425 1147.6593

Frequencies -- 1165.4575 1167.0345 1190.7747

Frequencies -- 1191.4687 1196.6865 1197.6298

Frequencies -- 1218.3044 1219.3710 1230.9458

Frequencies -- 1236.0173 1251.9764 1252.2754

Frequencies -- 1265.8145 1268.9308 1300.1538

Frequencies -- 1302.0888 1326.3008 1328.2710

Frequencies -- 1336.7608 1337.0642 1350.5299

Frequencies -- 1351.0079 1357.4342 1357.7368

Frequencies -- 1372.4191 1373.0861 1375.2088

Frequencies -- 1375.7832 1406.7688 1412.5057

Frequencies -- 1429.0255 1429.4297 1443.6392

Frequencies -- 1446.7461 1450.7961 1452.5827

Frequencies -- 1475.1333 1475.4105 1518.5161

Frequencies -- 1519.0898 1521.3136 1523.6635

Frequencies -- 1539.6043 1540.2406 1589.7150

Frequencies -- 1590.8170 1619.0631 1619.2823

Frequencies -- 1635.6969 1635.9676 1648.7579

Frequencies -- 1648.8732 1676.0840 1677.0839

40

40

Frequencies -- 1687.6004 1688.2845 1705.1047

Frequencies -- 1705.9524 3056.4801 3056.9938

Frequencies -- 3133.7285 3134.1923 3155.2168

Frequencies -- 3155.8388 3156.1248 3157.6982

Frequencies -- 3163.8048 3164.5186 3172.3551

Frequencies -- 3172.5955 3179.1814 3179.3529

Frequencies -- 3180.4570 3182.4333 3184.5557

Frequencies -- 3185.3288 3186.6907 3188.1879

Frequencies -- 3188.4072 3195.9013 3196.4671

Frequencies -- 3197.0193 3197.1610 3204.7593

Frequencies -- 3204.9877 3205.0336 3208.6434

Frequencies -- 3211.3734 3548.6244 3551.9997

COMPOUND 5e

Frequencies -- 3.0554 13.2434 17.9952

Frequencies -- 18.9841 22.1246 23.8295

Frequencies -- 28.3477 30.7518 35.3604

Frequencies -- 41.8274 48.0580 51.1672

Frequencies -- 53.1140 61.4039 63.0654

Frequencies -- 68.3639 70.6981 74.2870

Frequencies -- 81.2114 89.4962 93.8371

Frequencies -- 98.5463 102.2395 108.2186

Frequencies -- 129.7741 134.5352 137.7887

Frequencies -- 158.6084 168.3776 171.6521

Frequencies -- 179.1765 182.4994 183.7095

Frequencies -- 195.9506 206.7568 229.9206

Frequencies -- 236.6346 254.0295 259.8525

Frequencies -- 266.3243 270.5811 273.9028

Frequencies -- 295.2111 308.1583 322.6169

Frequencies -- 339.1392 345.8854 412.7321

Frequencies -- 414.2363 414.3079 416.1443

Frequencies -- 440.8700 442.3867 474.8878

Frequencies -- 475.2027 484.8391 487.9198

Frequencies -- 498.3139 502.8040 514.7554

Frequencies -- 528.3918 541.0471 545.6383

Frequencies -- 594.2683 604.9033 607.8471

Frequencies -- 609.2538 628.0586 628.2952

Frequencies -- 630.1986 638.1836 641.3636

Frequencies -- 642.7395 648.0282 649.4752

Frequencies -- 706.2337 706.7453 717.7521

Frequencies -- 726.1223 744.6334 745.3389

Frequencies -- 778.8779 779.3819 816.6095

Frequencies -- 817.0642 845.1926 845.4902

Frequencies -- 853.3067 855.6518 856.4565

Frequencies -- 856.9782 859.7652 860.7562

Frequencies -- 885.5613 888.3624 908.1594

Frequencies -- 908.4316 931.1736 943.6383

Frequencies -- 947.4296 948.6469 992.9649

Frequencies -- 993.2233 994.3937 994.8321

Frequencies -- 998.9380 999.6613 1002.6482

Frequencies -- 1006.0992 1007.1300 1007.4707

Frequencies -- 1008.5317 1008.6958 1018.8217

Frequencies -- 1018.9810 1021.6276 1022.8101

Frequencies -- 1032.0494 1033.8440 1040.7440

Frequencies -- 1041.6151 1048.4078 1048.4684

Frequencies -- 1094.2223 1100.7571 1100.8764

Frequencies -- 1112.6981 1146.4004 1147.9653

Frequencies -- 1165.0977 1166.3304 1191.4234

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Frequencies -- 1191.5129 1196.5287 1197.5646

Frequencies -- 1218.8970 1219.5062 1232.4750

Frequencies -- 1232.6042 1251.9762 1253.3963

Frequencies -- 1268.9954 1277.2031 1301.3766

Frequencies -- 1302.1515 1327.8960 1328.0384

Frequencies -- 1335.1458 1336.5282 1350.3829

Frequencies -- 1350.9083 1357.2797 1357.7101

Frequencies -- 1372.1500 1372.9064 1376.5114

Frequencies -- 1376.6998 1402.6728 1410.0842

Frequencies -- 1428.7381 1430.1318 1444.0459

Frequencies -- 1447.9487 1451.2982 1455.3447

Frequencies -- 1474.9798 1475.3598 1519.6700

Frequencies -- 1519.8455 1524.0079 1529.6415

Frequencies -- 1540.4395 1541.9149 1589.9453

Frequencies -- 1592.0882 1619.2731 1619.5269

Frequencies -- 1635.4576 1636.8001 1648.5047

Frequencies -- 1648.9974 1664.7474 1680.9538

Frequencies -- 1685.1110 1687.7966 1688.9240

Frequencies -- 1717.7319 3054.8934 3057.9408

Frequencies -- 3132.7149 3135.4308 3150.3945

Frequencies -- 3153.7082 3154.7427 3156.4406

Frequencies -- 3157.9387 3162.4100 3163.1573

Frequencies -- 3171.6742 3172.6923 3178.7605

Frequencies -- 3179.4341 3180.9096 3183.9253

Frequencies -- 3185.4741 3187.8222 3188.3244

Frequencies -- 3188.8126 3194.2246 3196.2862

Frequencies -- 3196.6683 3196.9833 3204.4578

Frequencies -- 3204.9248 3206.7956 3209.8738

Frequencies -- 3212.4442 3530.8933 3550.3941

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42

3. Calculated Infrared Spectra for the tautomers of complex (5)

Compound 5a.

Compound 5b.

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43

Compound 5c.

Compound 5d.

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44

Compound 5e.

5. Calculated UV-Vis spectra for the Compound 5 isomers.

Compound 5a.

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45

Compound 5b.

Compound 5c.

46

46

Compound 5d.

Compound 5e.