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Electronic Supplementary Information (ESI)

New Red-Emitting Schiff Base Chelates: Promising Molecular

Thermometers for Sensing and Imaging via Phosphorescence Decay Time

Sergey M. Borisov,*1 Reinhold Pommer,1 Jan Svec,2 Sven Peters,3 Veronika Novakova,2 Ingo

Klimant1

1 Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology,

Stremayrgasse 9, 8010, Graz, Austria. E-mai: sergey.borisov@tugraz.at

2 Department of Pharmaceutical Chemistry and Pharmaceutical Analysis, Faculty of Pharmacy in

Hradec Kralove, Charles University, Akademika Heyrovskeho 1203, Hradec Kralove, Czech Republic

3 Department of Ophthalmology, University Hospital Jena, Jena, Germany

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2018

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Table of Content

Attempted synthesis of (1)………………………………………………………………………...3

Figure S1. Emission spectrum of Pt-1 in anoxic toluene at 20 °C……………………...................3

Figure S2. Excitation and emission spectra Zn-1 in dimethylformamide at 20 °C……………….4

Figure S3. Excitation and emission spectra Gd-1 in ethanol…………………………...................4

Figure S4. Excitation and emission spectra Yb-1 in ethanol…………………………………..….5

Figure S5. Absorption spectra of Pt-1 in air-saturated toluene upon irradiation

with a high power 470 nm LED array……………………………………………………………..5

Figure S6. Absorption spectra of Ir(CS)2acac in air-saturated toluene upon irradiation

with a high power 470 nm LED array……………………………………………………………..6

Figure S7. Excitation and emission spectra Pt-1 in polystyrene……………………….................6

Figure S8. Comparison of the response of luminescence intensity and decay time

to temperature for Pd-1 immobilized into PViCl-PAN……………………………………………7

Figure S9. Temperature dependency of the decay time of Pd-1/PViCl-PAN

sensor obtained from time-resolved imaging experiments.………………………………………. 7

Figure S10. 1H NMR spectrum of (E)-4-(4-(dibutylamino)-2-hydroxybenzylideneamino)-

5-aminobenzene-1,2-dinitrile……………………………………………………………………...8

Figure S11. 1H NMR spectrum of Zn-1…………………………………………………………...8

Figure S12. 1H NMR spectrum of Pt-1……………………………………………………………9

Figure S13. 13C APT-NMR spectrum of Pt-1……………………………………………………..9

Figure S14. 1H NMR spectrum of Pd-1……………………………............................................10

Figure S15. 13C APT-NMR spectrum of Pd-1…………………………………………………..10

Figure S16. Mass-Spectrum of Zn-1…………………………………………………………….11

Figure S17. Isotope pattern of Zn-1……………………………………………………………..11

Figure S18. Mass-Spectrum of Pt-1……………………………………………………………..12

Figure S19. Isotope pattern of Pt-1………………………………………………………………12

Figure S20. Mass-Spectrum of Pd-1…………………………………………………………….13

Figure S21. Isotope pattern of Pd-1……………………………………………………………...13

Figure S22. IR spectra of the Schiff base complexes…………………………………………...14

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Attempted synthesis of (4E,5E)-4,5-bis(4-(dibutylamino)-2-hydroxybenzylideneamino)benzene-1,2-

dinitrile (1)

4-(dibutylamino)-2-hydroxybenzaldehyde (70.1 mg, 0.28 mmol, 3.4 eq.) and 4,5-diaminobenzene-1,2-

dinitrile (13 mg, 0.082 mmol, 1 eq.) were dissolved in 5 mL of anhydrous ethanol and the dispersion

was deoxygenated with argon in a Schlenk flask. The solution was heated to 50 °C and 12 μL of

methanesulfonic acid (18 mg, 0.19 mmol, 2.3 eq.) were added as a catalyst. A brown precipitate was

formed after 90 min, the reaction was stopped and the product was precipitated in methanol. The

precipitate was washed several times with cyclohexane to remove the excess of the aldehyde. The

monosubstituted product, (E)-4-(4-(dibutylamino)-2-hydroxybenzylideneamino)-5-aminobenzene-1,2-

dinitrile was isolated as a yellow solid.

Yield: 30 mg (93 %). UV-Vis (toluene), max/ (nm/M-1cm-1): 381/41100.

1H-NMR: (300 MHz, DMSO-d6): 8.30 (s, 1H), 7.89 (s, 1H), 7.9 – 7.75 (m, 3H), 6.46 (s, 1H), 6.25 (s,

1H), 3.44 – 3.19 (m, 4H), 2.39 (s, 2H), 1.53 (d, 4H), 1.36 (d, 4H), 0.94 (t, 6H).

500 600 700 800

0

2000

4000

6000

8000

10000

Inte

nsity, a.u

.

Wavelength, nm

Figure S1. Emission spectrum of Pt-1 in anoxic toluene at 20 °C. exc = 502 nm.

4

300 400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0

No

rma

lize

d in

ten

sity

Wavelength, nm

Excitation Emission

Figure S2. Excitation (em = 600 nm) and emission (exc = 400 nm) spectra Zn-1 in

dimethylformamide at 20 °C.

400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0

400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0

Wavelength, nm

N2

air

No

rma

lize

d L

um

ine

scen

ce

In

tensity

Excitation Emission

Figure S3. Excitation (em = 620 nm) and emission (exc = 480 nm) spectra Gd-1 in ethanol. The

complex was obtained via reaction of 1 with gadolinium(III) nitrate in ethanol in presence of KPF6 and

under basic conditions (addition of NaOH) and was not isolated.

5

350 400 450 500 550 850 900 950 1000

0.0

0.2

0.4

0.6

0.8

1.0

350 400 450 500 550 850 900 950 1000

0.0

0.2

0.4

0.6

0.8

1.0

Wavelength, nm

No

rma

lize

d L

um

ine

scen

ce

In

tensity

Excitation Emission

Figure S4. Excitation (em = 975 nm) and emission (exc = 505 nm) spectra Yb-1 in ethanol. The

complex was obtained via reaction of 1 with ytterbium(III) nitrate in ethanol in presence of KPF6 and

under basic conditions (addition of NaOH) and was not isolated.

300 400 500 600 700

0.0

0.2

0.4

0.6

Ab

so

rptio

n

Wavelength, nm

0 min

10 min

20 min

30 min

40 min

50 min

60 min

70 min

80 min

90 min

Figure S5. Absorption spectra of Pt-1 in air-saturated toluene upon irradiation with a high power 470

nm LED array (photon flux 5600 µmol s-1 m-2 µA).

6

300 400 500 600 700

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Absorp

tion

Wavelength, nm

0 min

4 min

8 min

16 min

20 min

24 min

Figure S6. Absorption spectra of Ir(CS)2acac in air-saturated toluene upon irradiation with a high

power 470 nm LED array (photon flux 5600 µmol s-1 m-2 µA).

400 500 600 700 800

0.0

0.2

0.4

0.6

0.8

1.0

No

rmaliz

ed L

um

ine

scen

ce

Inte

nsity

Wavelength, nm

excitation

emission

Figure S7. Excitation (em = 640 nm) and emission (exc = 480 nm) spectra Pt-1 in

polystyrene.

7

0 20 40 600.0

0.2

0.4

0.6

0.8

1.0

Intensity

Decay time

Norm

aliz

ed Inte

nsity/d

ecay tim

e

Temperature, °C

Figure S8. Comparison of the response of luminescence intensity and decay time to temperature for

Pd-1 immobilized into PViCl-PAN.

0 20 40 60

60

80

100

120

140

160

Decay tim

e, µ

s

Temperature, °C

Figure S9. Temperature dependency of the decay time of Pd-1/PViCl-PAN sensor obtained from

time-resolved imaging experiments.

8

Figure S10. 1H NMR spectrum (300 MHz, DMSO-d6) of (E)-4-(4-(dibutylamino)-2-

hydroxybenzylideneamino)-5-aminobenzene-1,2-dinitrile.

Figure S11. 1H NMR spectrum (300 MHz, DMSO-d6) of Zn-1.

9

Figure S12. 1H NMR spectrum (300 MHz, CDCl3) of Pt-1.

Figure S13. 13C APT-NMR spectrum (300 MHz, CDCl3) of Pt-1.

10

Figure S14. 1H NMR spectrum (300 MHz, CDCl3) of Pd-1.

Figure S15. 13C APT-NMR spectrum (300 MHz, CDCl3) of Pd-1.

11

Figure S16. Mass-Spectrum (MALDI-TOF) of Zn-1.

Figure S17. Isotope pattern of Zn-1.

m/z150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600

%

0

100

%

0

100

Borisov_ZnDBADCNB1stfr_DCTB (0.016) Is (0.05,1.00) C38H46N6O2Zn TOF LD+ 3.09e12682.2974

684.2957

686.2944

687.2968

688.2982

Borisov_ZnDBADCNB1stfr_DCTB 21 (0.349) Sb (99,10.00 ); Sm (SG, 1x3.00); Cm ((8:11+19:24+29:34)) TOF LD+ 1.40e3682.3320

483.5406332.1740

234.9580

639.2527484.5558

684.3138

686.3166

687.3101

688.32231369.6257

698.3038 1365.6187 1371.6185

m/z677 678 679 680 681 682 683 684 685 686 687 688 689 690 691 692 693 694 695 696 697

%

0

100

%

0

100

Borisov_ZnDBADCNB1stfr_DCTB (0.016) Is (0.05,1.00) C38H46N6O2Zn TOF LD+ 3.09e12682.2974

684.2957

683.3005

686.2944

685.2973

687.2968

688.2982

Borisov_ZnDBADCNB1stfr_DCTB 21 (0.349) Sb (99,10.00 ); Sm (SG, 1x3.00); Cm ((8:11+19:24+29:34)) TOF LD+ 1.40e3682.3320

684.3138

683.3226

682.6022

686.3166

685.3239

684.8729

687.3101

686.6237

688.3223695.2837 696.3017

Theoretical

Experimental

Theoretical

Experimental

12

Figure S18. Mass-Spectrum (MALDI-TOF) of Pt-1.

Figure S19. Isotope pattern of Pt-1.

m/z300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600

%

0

100

%

0

100

Borisov_PtDBADCNB_DCTB (0.017) Is (1.00,1.00) C38H46N6O2Pt TOF LD+ 3.09e12813.3333

812.3309

814.3345

815.3370

816.3373

817.3397

Borisov_PtDBADCNB_DCTB 52 (0.867) Sb (99,10.00 ); Sm (SG, 1x4.00) TOF LD+ 1.13e3813.3456

812.3626

332.2998

483.5456374.3217

757.2805500.3656

815.3528

816.3572

829.3530

830.3463

1063.5073916.4078

m/z809 810 811 812 813 814 815 816 817 818 819 820 821

%

0

100

%

0

100

Borisov_PtDBADCNB_DCTB (0.017) Is (1.00,1.00) C38H46N6O2Pt TOF LD+ 3.09e12813.3333

812.3309

814.3345

815.3370

816.3373

817.3397

Borisov_PtDBADCNB_DCTB 52 (0.867) Sb (99,10.00 ); Sm (SG, 1x4.00) TOF LD+ 1.13e3813.3456

812.3626

814.3488

815.3528

816.3572

817.3426

818.3287

Theoretical

Experimental

Theoretical

Experimental

13

Figure S20. Mass-Spectrum (MALDI-TOF) of Pd-1.

Figure S21. Isotope pattern of Pd-1.

m/z300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700

%

0

100

%

0

100

Borisov_PdDBADCNB_DCTB (0.016) Is (1.00,1.00) C38H46N6O2Pd TOF LD+ 2.45e12724.2731

723.2737

722.2723

726.2728

728.2744

729.2769

Borisov_PdDBADCNB_DCTB 14 (0.232) Sb (99,10.00 ); Sm (SG, 1x4.00); Sb (99,10.00 ); Sm (SG, 1x4.00); Cm (14:26) TOF LD+ 1.57e3724.2634

723.2618

722.2610

332.2465

483.5098684.8884

726.2500

727.2537

729.2631

741.2462

974.4133759.2621

761.2582 972.4120977.4084

1473.4974979.4365

m/z718 719 720 721 722 723 724 725 726 727 728 729 730 731 732 733 734

%

0

100

%

0

100

Borisov_PdDBADCNB_DCTB (0.016) Is (1.00,1.00) C38H46N6O2Pd TOF LD+ 2.45e12724.2731

723.2737

722.2723

726.2728

725.2756 728.2744

727.2755

729.2769

Borisov_PdDBADCNB_DCTB 14 (0.232) Sb (99,10.00 ); Sm (SG, 1x4.00); Sb (99,10.00 ); Sm (SG, 1x4.00); Cm (14:26) TOF LD+ 1.57e3724.2634

723.2618

722.2610

726.2500

725.2656

727.2537728.2580

729.2631

730.2501

Theoretical

Experimental

Theoretical

Experimental

14

500 1000 1500 2000 2500 3000 3500 4000

C-N

C=N

Ab

so

rba

nce

Wavenumber, cm-1

CNC-H aliph.

C=C

C-O

C-H, Ar

C-N

Pt-1

Pd-1

Zn-1

Figure S22. IR spectra of the Schiff base complexes.