supporting information · 2018. 4. 9. · s9 x-ray diffraction analysis the crystal of 2a (c 94 h...

$: Supporting Information · 2018. 4. 9. · S9 X-ray Diffraction Analysis The crystal of 2a (C 94 H 62 N 16 OSMgBr 8, M = 2127.16) used for study was triclinic, space group P-1, at$
Supporting Information

Optical Readout of Controlled Monomer-Dimer Self-Assembly

P. A. Tarakanov,*ab

E. N. Tarakanova,a P. V. Dorovatovskii,

c Y. V. Zubavichus,

c V. N. Khrustalev,

d

S. A. Trashin,ae

K. De Wael,e M. E. Neganova,

a D. V. Mischenko,

b J. L. Sessler,

f P. A. Stuzhin,

g

V. E. Pushkarev*ah

and L. G. Tomilovaah

a Institute of Physiologically Active Compounds, Russian Academy of Sciences, 1 Severny Proezd, 142432

Chernogolovka, Moscow Region, Russian Federation. E-mails: [email protected];

[email protected] b Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician Semenov Avenue,

142432 Chernogolovka, Moscow Region, Russian Federation c National Research Centre “Kurchatov Institute”, 1 Akad. Kurchatov Sq., Moscow 123182, Russia

d Inorganic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6

Miklukho-Maklay St., Moscow 117198, Russian Federation e AXES Research Group, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020

Antwerpen, Belgium f Department of Chemistry, Shanghai University, Shanghai 200444, China

g Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, 153000

Ivanovo, Russia h Department of Chemistry, M.V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow,

Russian Federation

Table of Contents

General Information S2

Synthesis S2

NMR Spectra S3

X-ray Diffraction Analysis S9

Studies of the Extent of Dissociation S11

Studies of the Influence of Fluoride Ion Concentration on the Dimer-Monomer Equilibria S12

Electrochemistry S19

In Vitro and in Vivo Toxicity Tests S21

References S21

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2018

S2

General Information

UV-vis spectra were recorded on a Hitachi U-2900 spectrophotometer using quartz cuvettes (10 × 10 mm)

with the samples dissolved in pyridine, DMSO, o-DCB, unless otherwise specified. 1H and

13C NMR spectra

were recorded on Bruker Avance 500 (500 and 125 MHz, respectively) with the samples dissolved in

pyridine-d5 or DMSO-d6. Chemical shifts are given in parts per million (ppm) relative to TMS. Matrix-

assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra were acquired on a VISION-

2000 mass spectrometer with α-cyano-4-hydroxycinnamic acid (CHCA) as the matrix. Size exclusion column

chromatography was carried out using Bio-Beads S-X1 resin (BIORAD) eluted with pyridine. All other

reagents and solvents were obtained or distilled according to standard procedures. All reactions were

controlled by TLC and UV-vis until complete disappearance of the starting materials, unless otherwise

specified.

Electrochemical measurements were carried out in pyridine using a conventional three-electrode cell and

Autolab/PGSTAT101 (Metrohm Autolab B.V., the Netherlands). A double junction Ag/AgCl reference

electrode (Metrohm, Switzerland) was filled with 2 M LiCl in ethanol as the reference (inner) electrolyte and

0.1 M [TBA][BF4] in pyridine as the bridge electrolyte. Before making any measurements, a platinum disk

working electrode (2 mm in diameter, BASi, USA) was regenerated by polishing with an abrasive paper (grit

400), washed with ultrapure water and drying. Blank voltammograms were recorded in pure pyridine

containing 0.1 M [TBA][BF4] and then approximately 1 mM of a sample was introduced into the cell. After a

series of measurements, ferrocene was added as internal reference, and additional voltammograms were

recorded. Before the measurements the solutions were purged with N2 for at least 30 min. All measurements

were performed at room temperature (22 ± 2°C).

Synthesis

General procedure for the preparation of complexes 2a,b. Mg metal (50 mg) was boiled in isoamyl

alcohol (50 mL) in the presence of a catalytic amount of I2 until complete dissolution was observed (ca. 3 h).

The solution of the resulting Mg alkoxide was cooled to room temperature, 1,4-diazepine-2,3-dicarbonitrile

1a or 1b (1 mmol) was added, and the mixture was heated at reflux for 16 h. The course of the reaction was

monitored by UV-vis spectroscopy. Then, the reaction mixture was cooled to room temperature and the

solvent was evaporated under reduced pressure. The resulting dry residue was successively washed with 50%

aqueous acetic acid (4 × 50 mL), a 5% aqueous solution of sodium bicarbonate (2 × 50 mL), distilled water (4

× 50 mL) and finally with MeOH (50 mL) followed by drying in vacuo at 50 °C. The resulting solid was

subjected to gel permeation chromatography (Bio-Beads S-X1, pyridine). This yielded 2a and 2b in the form

of dark-green solids.

Tetrakis{5,7-bis[2’-(4-bromophenyl)ethenyl]-6H-1,4-diazepino}[2,3-b,g,l,q]porphyrazinato magnesium

(II) (2a). Yield 0.44 g (86%). UV-vis (DMSO) λmax/nm (log ε): 387 (4.77), 659 (4.59), 700 (4.41). 1H NMR

(500 MHz; DMSO-d6) δ/ppm: 8.20 (8H, d, 3J = 15.9 Hz, 2'-H), 7.7–7.65 (24H, br m, 1'-H; H

o-Ar), 7.47 (16H,

br s, Hm-Ar

), 6.11 (4H, br s, Heq

), 4.77 (4H, br s, Hax

). 13

C NMR (125 MHz; Py-d5) δ/ppm: 154.99, 149.19,

143.05, 137.46, 132.50, 131.68, 129.82, 37.75. MS (MALDI-TOF; HCCA): m/z 2050.87 [M+H]+, 4101.46

[M2+H]+; calculated for C92H57Br8MgN16: 2050.82.

Tetrakis{5,7-bis[2’-(4-methoxyphenyl)ethenyl]-6H-1,4-diazepino}[2,3-b,g,l,q]porphyrazinato

magnesium(II) (2b). Yield 0.39 g (94%). UV-vis (DMSO) λmax/nm (log ε): 386 (5.05), 661 (4.87), 698

(4.78). 1H NMR (500 MHz; pyridine-d5) δ/ppm: 8.49 (8H, d,

3J = 16.53 Hz, 2'-H), 8.13 (8H, d,

3J = 16.06 Hz,

1'-H), 7.69 (16H, d, 3J = 7.79 Hz, H

o-Ar), 6.89 (16H, d,

3J = 8.15 Hz, H

m-Ar), 6.67 (4H, br s, H

eq), 5.94 (4H, d,

2J = 12.64 Hz, H

ax), 3.81 (24H, s, -OMe).

13C NMR (125 MHz; Py-d5) δ/ppm: 161.12, 154.86, 143.05, 138.65,

130.15, 130.03, 128.95, 114.99, 55.62, 38.48. MS (MALDI-TOF/TOF; HCCA): m/z 1658.60 [M+H]+,

3317.07 [M2+H]+; calculated for C100H81MgN16O8: 1658.63.

Tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazinato magnesium(II) (2c)

was synthesized according to a previously published procedure.1

S3

NMR Spectra

9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

4.0

9

4.0

4

15

.98

7.9

68

.20

7.7

07

.66

7.6

57

.47

6.1

1

4.7

7

23.9

9

2'-H (d) 3J=15.9 Hz

1'-H; Ho-Ar

(br m) Hm-Ar (br s)

Hax (br s)Heq (br s)

H2O

*

Figure S1.

1H NMR spectrum of 2a (DMSO-d6, 293 K).

8 6 4 2F2 Chemical Shift (ppm)

2

3

4

5

6

7

8

F1

Ch

em

ica

l S

hift

(pp

m)

2'-H

1'-H;

Ho-Ar Hm-Ar

HaxHeq

H2O*

Figure S2.

1H-

1H COSY NMR spectrum of 2a (DMSO-d6, 293 K).

S4

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

Chemical Shift (ppm)

154

.99

149

.19

143

.05

137

.46

132

.50

131

.68

129

.82

37.7

5

***

Figure S3.

13C NMR spectrum of 2a (pyridine-d5, 293 K).

8 6 4 2 0F2 Chemical Shift (ppm)

0

20

40

60

80

100

120

140

160

F1

Ch

em

ica

l S

hift

(pp

m)

7.70-7.65; 129.82; 131.68

7.47; 132.50

8.20; 137.46

2'-H

1'-H;

Ho-Ar Hm-Ar

HaxHeq

H2O*

Figure S4.

1H-

13C HSQC spectrum of 2a (DMSO-d6, 293 K).

S5


1

2

3

4

5

6

7

8

F1

Ch

em

ica

l S

hift

(pp

m)

2'-H

1'-H;

Ho-Ar Hm-Ar

HaxHeq

H2O*

Figure S5.

1H-

1H NOESY spectrum of 2a (DMSO-d6, 293 K).

16.15

8 7 6 5 4 3Chemical Shift (ppm)

24.113.944.0216.178.018.00

8.5

0

8.1

4

7.7

0

6.9

0

6.6

7

5.9

5

3.8

1

Ho-Ar (d) 3J=7.79 Hz

1'-H (d) 3J=16.06 Hz

Hm-Ar (d) 3J=8.15 Hz

2'-H (d) 3J=16.06 Hz

Hax (d) 2J=12.64 HzHeq (br s)

HOMe (s)

* * *H2O

Figure S6.

1H NMR spectrum of 2b (pyridine-d5, 293 K).

S6

8 7 6 5 4 3F2 Chemical Shift (ppm)

4

5

6

7

8

F1

Ch

em

ica

l S

hift

(pp

m)

2'-H

Ho-Ar

Hm-Ar

1'-H

HOMe

Hax

Heq

H2O

* * *

Figure S7.

1H-

1H COSY NMR spectrum of 2b (pyridine-d5, 293 K).

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

16

1.1

21

54

.86

14

3.0

51

38

.65

13

0.1

51

30

.03

12

8.9

51

14

.99

55

.62

38

.48

* * *

Figure S8.

13C NMR spectrum of 2b (pyridine-d5, 293 K).

S7


0

20

40

60

80

100

120

140

160

F1

Ch

em

ica

l S

hift

(pp

m)

2'-H

Ho-ArHm-Ar

1'-H

HOMe

Hax

Heq

3.81; 55.62

5.95; 38.48

6.67; 38.48

7.70; 130.03 6.90; 114.99

8.50; 138.65

8.14; 128.95

H2O* * *

Figure S9.

1H-

13C HSQC spectrum of 2b (pyridine-d5, 293 K).

S8

8 7 6 5 4 3F2 Chemical Shift (ppm)

4

5

6

7

8

F1

Ch

em

ica

l S

hift

(pp

m)

2'-H

Ho-ArHm-Ar

1'-H

HOMe

Hax

Heq

H2O* * *

Figure S10.

1H-

1H NOESY spectrum of 2b (pyridine-d5, 293 K).

S9

X-ray Diffraction Analysis

The crystal of 2a (C94H62N16OSMgBr8, M = 2127.16) used for study was triclinic, space group P-1, at T = 100

K: a = 15.325(3) Å, b = 27.895(6) Å, c = 33.306(7) Å, = 113.35(3)°, = 100.91(3)°, = 95.58(3)°, V =

12599(6) Å3, Z = 4, dcalc = 1.121 g/cm

3, F(000) = 4216, μ = 0.973 mm

–1. The X-ray diffraction study was

carried out on the ‘Belok’ beamline ( = 0.96990 Å) of the National Research Center “Kurchatov Institute”

(Moscow, Russian Federation) using a Rayonix SX-165 CCD detector. A total of 720 images (117852

reflections, 40519 independent reflections, Rint = 0.0851) were collected using an oscillation range of 1.0° (

scan mode, 2θmax = 76.44°) and corrected for absorption using the Scala program (Tmin = 0.848; Tmax =

0.898).2 The data were indexed, integrated and scaled using the utility iMOSFLM in CCP4 program.

3 The

structure was determined by direct methods and refined by full-matrix least squares technique on F2 with

anisotropic displacement parameters for non-hydrogen atoms. Twelve of the sixteen para-bromophenyl

substituents were disordered over two sites each with equal occupancies. The independent part of the unit cell

of 2a contained several dimethylsulfoxide and water solvate molecules, which were strongly disordered. All

attempts to model and refine their positions were unsuccessful. Therefore, the contribution to the scattering by

the solvent molecules was removed by use of the utility SQUEEZE in PLATON06.4 The hydrogen atoms were

placed in calculated positions and refined within a riding model with fixed isotropic displacement parameters

[Uiso(H) = 1.5Ueq(C) for the methyl groups and 1.2Ueq(C) for the other groups]. The final divergence factors

were R1 = 0.1361 for 15689 independent reflections with I > 2(I) and wR2 = 0.2672 for all independent

reflections, S = 1.080. The calculations were performed using the SHELXTL program.5 Full crystallographic

data for the investigated compounds have been deposited with the Cambridge Crystallographic Data Center,

CCDC 1489687. Copies of this information may be obtained free of charge from the Director, CCDC, 12

Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033; e-mail: [email protected] or

www.ccdc.cam.ac.uk).

Figure S11. X-ray analysis data for 2a. Show packing of 2a in the crystal cell (hydrogen atoms are omitted

for clarity).

mailto:[email protected]

http://www.ccdc.cam.ac.uk/

S10

Figure S12. Views of the X-ray structure of 2a. Ellipsoid (left) and space filling (right) representations,

respectively (hydrogen atoms and (aryl)ethenyl substituents are omitted for clarity).

S11

Studies of the Extent of Dissociation

0.0 2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

0.0

0.2

0.4

0.6

0.8

1.0

CM

(tBuPh

Dz4PzMg)

Figure S13. The extent of dissociation () as function of concentration (mol L-1

) of 2c in DMSO (red line)

and in pyridine (black line).

0.0 2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

CM

(MeStyr

Dz4PzMg)

Figure S14. The extent of dissociation () as function of concentration of 2b (mol L

-1) in DMSO (red line)

and in pyridine (black line).

S12

Studies of the Influence of Fluoride Ion Concentration on the Dimer-Monomer Equilibria

Complex 2c in DMSO

400 600 800

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

677

640

Figure S15. UV-vis spectroscopic changes seen upon addition of tetrabutylammonium fluoride to a solution

of 2c in DMSO.

0.0 2.0x10-4

4.0x10-4

6.0x10-4

0.18

0.20

0.22

0.24

A640

Abso

rban

ce (

a.u.)

CM

(F-)

Figure S16. Change in absorbance at 640 nm seen upon titration of 2c with tetrabutylammonium fluoride in

DMSO. Concentrations are in mol L-1

.

3.2 3.4 3.6 3.8 4.0 4.2

-1.0

-0.5

0.0

0.5

1.0

1.5

tg () = 4

R2 = 97

Lg

(I6

40

)

pCM

(F-)

Figure S17. Plot of the indicator concentration ratio for 2c at 640 nm vs. the negative log of the

tetrabutylammonium fluoride concentration.

S13

Complex 2c in pyridine

400 600 800

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

641

679


of 2c in pyridine.

0.0 2.0x10-5

4.0x10-5

6.0x10-5

0.2

0.4

0.6

0.8

1.0

1.2

A679

A641

Ab

sorb

ance

(a.

u.)

CM

(F-)

Figure S19. Change in absorbance at 679 and 641 nm seen upon titration of 2c with tetrabutylammonium

fluoride in pyridine. Concentrations are in mol L-1

.

4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8

-3

-2

-1

0

1

2 pCM

(F-) - Lg(I641); tg()=2.6; R2=93

pCM

(F-) - Lg(I679); tg()=2.9; R2=96

Lg(I)

pCM(F

-)

Figure S20. Plots of the indicator concentration ratio for 2с at 679 and 641 nm vs. the negative log of the


S14

400 600 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

642

680A

400 600 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

642

680B

Figure S21. UV-vis spectroscopic changes during dissociation of dimeric form of 2c in pyridine seen upon

addition of tetrabutylammonium fluoride (A) and the following reverse dimerization process upon addition of

FeBr3 (B).

0.0 2.0x10-5

4.0x10-5

6.0x10-5

8.0x10-5

1.0x10-4

0.2

0.4

0.6

0.8

1.0

1.2

CM

(F-) - A

680

CM

(F-) - A

642

CM

(Fe3+

) - A680

CM

(Fe3+

) - A642

Ab

sorb

ance

(a.

u.)

CM

(F-;Fe

3+)

Figure S22. Change in absorbance at 680 and 642 nm seen upon titration of 2c with tetrabutylammonium

fluoride in pyridine and upon titration of the resulting solution with FeBr3. Concentrations are in mol L-1

.

4.4 4.5 4.6 4.7 4.8 4.9 5.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5 pCM

(F-) - Lg(I

680); tg()=14; R

2

pCM

(F-) - Lg(I

642); tg()=14; R

2

pCM

(Fe3+

) - Lg(I680

); tg()=13; R2

pCM

(Fe3+

) - Lg(I642

); tg()=14; R2

Lg

(I

)

pCM

(F-; Fe

3+)

Figure S23. Plots of the indicator concentration ratio for 2c at 680 and 642 nm vs. the negative log of the

tetrabutylammonium fluoride or FeBr3 concentration.

S15

Complex 2b in DMSO

400 600 800 1000

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

660

702


of 2b in DMSO.

0.0 2.0x10-4

4.0x10-4

6.0x10-4

0.3

0.4

0.5

0.6

0.7

0.8

0.9 A702

A660

Abso

rban

ce (

nm

)

CM

(F-)

Figure S25. Change in absorbance at 702 and 660 nm seen upon titration of 2b with tetrabutylammonium

fluoride in DMSO. Concentrations are in mol L-1

.

3.80 3.85 3.90 3.95 4.00 4.05 4.10

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0 pC

M(F-) - Lg(I702); tg()=9; R

2=96

pCM(F-) - Lg(I660); tg()=8; R

2=96

Lg

(I)

pCM

(F-)

Figure S26. Plots of the indicator concentration ratio for 2b at 702 and 660 nm vs. the negative log of the


S16

300 400 500 600 700 800 9000.0

0.2

0.4

0.6

0.8

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

660

702

A

300 400 500 600 700 800 9000.0

0.2

0.4

0.6

0.8

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

660

702B

Figure S27. UV-vis spectroscopic changes during dissociation of dimeric form of 2b in DMSO seen upon


FeBr3 (B).

0.0 5.0x10-5

1.0x10-4

1.5x10-4

2.0x10-4

2.5x10-4

0.2

0.3

0.4

0.5

0.6

0.7

CM

(F-) - A

702

CM

(F-) - A

660

CM

(Fe3+

) - A702

CM

(Fe3+

) - A660

Ab

sorb

ance

(a.

u.)

CM

(F-;Fe

3+)


fluoride in DMSO and upon titration of the resulting solution with FeBr3. Concentrations are in mol L-1

.

3.8 4.0 4.2 4.4 4.6 4.8 5.0

-2

-1

0

1

2

pCM(F

-) - Lg(I

702); tg()=7; R

2

pCM(F

-) - Lg(I

660); tg()=6; R

2

pCM(Fe

3+) - Lg(I

702); tg()=4; R

2

pCM(Fe

3+) - Lg(I

660); tg()=4; R

2

Lg

(I

)

pCM(F

-; Fe

3+)



S17

Complex 2b in pyridine

400 600 800

0.0

0.2

0.4

0.6

0.8

1.0

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

666

706


of 2b in pyridine.

0 1x10-5

2x10-5

3x10-5

4x10-5

5x10-5

6x10-5

7x10-5

0.3

0.4

0.5

0.6

0.7

0.8

A706

A666

Ab

sorb

ance

(a.

u.)

Wavelength (nm)


fluoride in pyridine. Concentrations are in mol L-1

.

4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5 pCM

(F-) - Lg(I

706); tg() = 2.5; R

2 = 99.7

pCM

(F-) - Lg(I

666); tg() = 2; R

2 = 98

Lg

(I)

pCM

(F-)



S18

400 600 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Absorb

ance (

a.u

.)

Wavelength (nm)

666

706

A

400 600 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

666

706

B

Figure S33. UV-vis spectroscopic changes during dissociation of dimeric form of 2b in pyridine seen upon


FeBr3 (B).

0.0 4.0x10-5

8.0x10-5

1.2x10-4

1.6x10-4

0.4

0.5

0.6

0.7

0.8

0.9

1.0

CM

(F-) - A

706

CM

(F-) - A

666

CM

(Fe3+

) - A706

CM

(Fe3+

) - A666

Ab

sorb

ance

(a.

u.)

CM

(F-;Fe

3+)


fluoride in pyridine and upon titration of the resulting solution with FeBr3. Concentrations are in mol L-1

.

4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8

-2

-1

0

1

2

pCM

(F-) - Lg(I

706); tg()=7; R

2

pCM

(F-) - Lg(I

666); tg()=6; R

2

pCM

(Fe3+

) - Lg(I706

); tg()=9; R2

pCM

(Fe3+

) - Lg(I666

); tg()=8; R2

Lg

(I

)

pCM

(F-; Fe

3+)



S19

Electrochemistry

Electrochemical analyses of 2a and 2b were carried out in pyridine containing 0.1 M [TBA][BF4] as the

supporting electrolyte. Under these conditions the complexes exist in their dimeric forms as illustrated in

Figure S36. One broad irreversible oxidation peak was observed at a potential of 0.804 and 0.777 V (vs. SCE)

for 2a and 2b, respectively. Reductive scans revealed more complex electrochemistry; up to five reversible

redox processes were observed (Table S1, Figure S37). Such behavior is consistent with the proposed dimeric

nature of the complexes, which can lead to a splitting of redox transitions similar to what is seen in the case of

double-decker sandwich complexes stabilized by a central lanthanide cation.6-8

The single broad oxidation

peak could result from two closely located irreversible redox transitions. Complexes 2a and 2b appear to be

noticeably more stable towards oxidation than monomeric phthalocyanine complexes9 and sandwich-type

double-decker systems.7, 8

The ΔR21 (R2 − R1) and ΔR43 (R4 – R3) values are larger for 2a than for 2b, which is

as expected given the greater Q-band splitting seen in the UV-vis spectrum (cf. Figures 2 and S36). The

reduction potentials R1, R2, and R3 for 2b were slightly shifted to more negative values relative to 2a,

meaning that the reduction of complex 2b is more difficult. Such a finding is as expected given the stronger

electron-donating effect of the substituents present in 2b.

300 400 500 600 700 800

0,5

1,0

1,5

2,0

2,5

3,0

704

700667

Absorb

ance

Wavelength (nm)

2a

2b

662

385

Figure S36. UV-vis spectra recorded for samples of 2a and 2b in pyridine in the presence of supporting

electrolyte. The concentrations of 2a and 2b were both ca. 0.1 mM; the cuvette path length was 1 mm.

-2,0 -1,5 -1,0 -0,5 0,0

-15

-10

-5

0

5

10

15

Curr

ent

/ A

Potential / V

2a

0,0 0,5 1,0 1,5 2,0 2,5

-15

-10

-5

0

5

10

Curr

ent

/ A

Potential / V

2a

S20

-2,0 -1,5 -1,0 -0,5 0,0

-10

-5

0

5

10

Curr

ent

/ A

Potential / V

2b

0,0 0,5 1,0 1,5 2,0 2,5

-10

-5

0

5

10

Curr

ent

/ A

Potential / V

2b

Figure S37. SWVA of complexes 2a and 2b in pyridine containing 0.1 M [TBA][BF4]. Amplitude, 50 mV;

frequency, 10 Hz; step potential, 5 mV; E1/2(ferrocene+/ ferrocene) = 0.49 V under these experimental

conditions.

Table S1. Reduction potentials for 2a and 2b in pyridine (values vs. SCEa)

Ox1b Red1 Red2 Red3 Red4 Red5

2a 1.294 -0.790 -1.016 -1.356 -1.646 -

2b 1.267 -0.883 -1.073 -1.433 -1.593 -1.793

a E1/2 (Fc

+/Fc) = 0.49 V.

b Irreversible process; the value of the peak potential is given.

S21

In Vitro and in Vivo Toxicity Tests

Compounds 2a,b were converted into water-soluble forms by co-solvation with polyvinylpyrrolidone (PVP)

for biological testing.

Cell viability was recorded as dehydrogenase activity as inferred from 3-(4,5-dimethylthiazol-2-yl)-2,5-

diphenyltetrazolium bromide (MTT) assays.10

Briefly, the SH-SY5Y cells or primary culture of rat cerebellar

granule cells were incubated with the test compounds or equivalent volume of vehicle (less than 1% of the

whole volume of medium under the layer of cells) for 24 h. Then, 20 μL of MTT (2 mg mol L–1

in PBS) were

added to each well and the cells were incubated at 37°C for 2 h. The supernatants were aspirated carefully,

200 μL of DMSO were added to each well to dissolve the precipitate, and the absorbance was measured at

570 nm using a microplate reader Victor (Perkin Elmer).

Acute intraperitoneal toxicity of complexes 2a and 2b was determined using male hybrid mice BDF1

(weighing 20−22 g) by injection of single doses of 25, 50, 100, and 150 mg kg–1

body weight, respectively.

Mice were kept under specific pathogen-free conditions; water and food were provided ad libitum. All

animals were observed for clinical signs of toxicity within the first 30 min following dose administration, and

then – with an interval of 1–4 h and further – once daily for 14 days. No deaths were registered during the 14

day study periods associated with either complex. The data obtained were plotted as a dose–effect curve, from

which the acute toxicity values (MTD, LD50 and LD100) of complexes 2a and 2b were determined.

Table S2. Acute toxicity studies of compounds 2a and 2b as determined using mal hybrid mice BDF1.

Compound Injected dose, mg

kg–1

Number of animals

per group

Number of deaths at

day 14 after injection

PVP

100 6 0

250 6 0

500 6 0

750 6 0

1500 6 0

3750 6 0

7500 6 0

2a

10 6 0

50 6 0

100 6 0

150 6 0

2b

10 6 0

50 6 0

100 6 0

150 6 0

References

1. P. A. Tarakanov, M. P. Donzello, O. I. Koifman and P. A. Stuzhin, Macroheterocycles 2011, 4(3),

177-183

2. P. Evans, Acta Crystallogr., Sect. D: Biol. Crystallogr., 2005, D62, 72-82.

3. T. G. Battye, O. Kontogiannis L Fau - Johnson, H. R. Johnson O Fau - Powell, A. G. W. Powell Hr

Fau - Leslie and A. G. Leslie, Acta Crystallogr., Sect. D: Biol. Crystallogr., 2011, D67, 271-281.

4. A. L. Spek, Journal, 2006.

5. G. M. Sheldrick, Acta Crystallographica Section A, 2008, 64, 112-122.

6. E. N. Tarakanova, S. A. Trashin, A. O. Simakov, T. Furuyama, A. V. Dzuban, L. N. Inasaridze, P. A.

Tarakanov, P. A. Troshin, V. E. Pushkarev, N. Kobayashi and L. G. Tomilova, Dalton Trans., 2016,

45, 12041-12052.

7. V. E. Pushkarev, A. Y. Tolbin, N. E. Borisova, S. A. Trashin and L. G. Tomilova, Eur. J. Inorg.

Chem., 2010, DOI: 10.1002/ejic.201000511, 5254-5262.

S22

8. P. Zhu, F. Lu, N. Pan, Dennis P. Arnold, S. Zhang and J. Jiang, Eur. J. Inorg. Chem., 2004, 2004,

510-517.

9. E. Ough, T. Nyokong, K. A. M. Creber and M. J. Stillman, Inorg. Chem., 1988, 27, 2724-2732.

10. M. Nikš and M. Otto, J. Immunol. Methods, 1990, 130, 149-151.

supporting information · 2018. 4. 9. · s9 x-ray diffraction analysis the crystal of 2a (c 94 h...

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