Supporting Information · aGrupo depesquisa em Fotoquímica Orgânica Aplicada, Instituto Química,...
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1 Supporting Information Photophysical, photodynamical, redox properties and BSA-interactions of novel isomeric tetra-cationic peripheral palladium(II)-bipyridyl porphyrins Fabiano da Silveira Santos a , Carolina H. da Silveira, b Fábio Souza Nunes c , Daniele C. Ferreira d , Henrique F.V. Victória d , Klaus Krambrock d , Otávio Augusto Chaves e , Fabiano Severo Rodembusch a and Bernardo Almeida Iglesias b * a Grupo de pesquisa em Fotoquímica Orgânica Aplicada, Instituto de Química, Universidade Federal do Rio Grande do Sul, UFRGS. Av. Bento Gonçalves 9500, 91501- 970, Porto Alegre, RS, Brazil. b Laboratório de Bioinorgânica e Materiais Porfirínicos, Departamento de Química, Universidade Federal de Santa Maria, UFSM, Av. Roraima 1000, 97105-900, Santa Maria, RS, Brazil. c Departamento de Química, Universidade Federal Do Paraná, 81531-980 Curitiba, PR, Brazil. d Departamento de Física, Universidade Federal de Minas Gerais, Av. Antônio Carlos 6627, 31270-901, Belo Horizonte, MG, Brazil. Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2020
Transcript of Supporting Information · aGrupo depesquisa em Fotoquímica Orgânica Aplicada, Instituto Química,...
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Supporting Information
Photophysical, photodynamical, redox properties and BSA-interactions of novel
isomeric tetra-cationic peripheral palladium(II)-bipyridyl porphyrins
Fabiano da Silveira Santosa, Carolina H. da Silveira,b Fábio Souza Nunesc, Daniele C.
Ferreirad, Henrique F.V. Victóriad, Klaus Krambrockd, Otávio Augusto Chavese, Fabiano
Severo Rodembuscha and Bernardo Almeida Iglesiasb*
aGrupo de pesquisa em Fotoquímica Orgânica Aplicada, Instituto de Química,
Universidade Federal do Rio Grande do Sul, UFRGS. Av. Bento Gonçalves 9500, 91501-
970, Porto Alegre, RS, Brazil.
bLaboratório de Bioinorgânica e Materiais Porfirínicos, Departamento de Química,
Universidade Federal de Santa Maria, UFSM, Av. Roraima 1000, 97105-900, Santa Maria,
RS, Brazil.
cDepartamento de Química, Universidade Federal Do Paraná, 81531-980 Curitiba, PR,
Brazil.
dDepartamento de Física, Universidade Federal de Minas Gerais, Av. Antônio Carlos
6627, 31270-901, Belo Horizonte, MG, Brazil.
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2020
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Tables:
Table S1: Elemental analysis and NMR data of porphyrins 3-PdTPyP and 4-PdTPyP.
Elemental analysis, exp. (calc.)
[C80H58Cl4N16Pd4](PF6)4 · 10H2O
3-PdTPyP %C: (37.37) 37.40; %H: (3.06) 3.08; %N: (8.72) 8.75
[C80H58Cl4N16Pd4](PF6)4 · 12H2O
4-PdTPyP %C: (36.86) 36.88; %H: (3.17) 3.16; %N: (8.60) 8.63
Compound 1H NMR, DMSO-d6
-2.98 (2H, bs, NH); 7.79 (8H, dd, J = 6.0 Hz, 4,4´); 7.95 (8H, m, Hc); 8.33
(8H, dd, J = 6.0 Hz, 3,3´); 8.53 (4H, d, J = 12.0 Hz, Hd); 8.59 (8H, dd, J = 6.0
3-PdTPyP Hz, 2,2´); 8.65 (4H, m, Hb); 8.98 (4H, m, He); 9.55 (8H, s, β-H) and 9.93 (8H,
d, J = 6.0 Hz, 1,1´)
-3.04 (2H, bs, NH); 7.79 (8H, dd, J = 6.0 Hz, 4,4´); 8.33 (8H, d, J = 5.8 Hz,
4-PdTPyP Hb); 8.54 (8H, dd, J = 6.0 Hz, 3,3´); 8.79 (8H, d, J = 5.6 Hz, 2,2´); 9.12 (8H,
s, β-H); 9.29 (8H, d, J = 5.7 Hz, Hc) and 9.50 (8H, d, J = 6.0 Hz, 1,1´)
Compound 13C NMR, DMSO-d6
3-PdTPyP 164.4, 162.6, 150.2, 142.5, 141.6, 128.8, 128.1, 128.0, 127.8, 125.0, 124.8,
124.2
4-PdTPyP 156.9, 151.7, 150.2, 142.8, 142.5, 141.6, 127.4, 124.9, 124.3
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Figures:
Figure S1: 1H NMR spectrum of compound 3-PdTPyP, in 600 MHz, DMSO-d6. *residual peaks.
Figure S2: 1H NMR spectrum of compound 4-PdTPyP, in 600 MHz, DMSO-d6. *residual peaks.
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Figure S3: 13C NMR spectrum of compound 3-PdTPyP, in 150 MHz, DMSO-d6.
Figure S4: 13C NMR spectrum of compound 4-PdTPyP, in 150 MHz, DMSO-d6.
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Figure S5: COSY 2D NMR spectrum of compound 3-PdTPyP, in DMSO-d6.
Figure S6: COSY 2D NMR spectrum of compound 4-PdTPyP, in DMSO-d6.
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Figure S7: Steady-state fluorescence emission spectra in solution of different wavelengths [ca. 10-6 M] of porphyrins (a) 3-PdTPyP and (b) 4-PdTPyP obtained at the absorption maxima.
Figure S8: Excitation spectra in solution of different organic solvents [ca. 10-6 M] of porphyrin 3-PdTPyP using as observation wavelengths (a) 650 nm and (b) 710 nm.
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Figure S9: Excitation spectra in solution of different organic solvents [ca. 10-6 M] of porphyrin 4-PdTPyP using as observation wavelengths (a) 650 nm and (b) 710 nm.
Figure S10: Time-resolved fluorescence decays of porphyrins 3-PdTPyP and 4-PdTPyP in DMSO and 1,4- dioxane [~10-6 M] using an excitation wavelength of 405 nm (LED). IRF=instrument response factor.
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60 70 80 90 100 110 120
Time (ns)
4
2
0
-2
-4
60 70 80 90 100 110 120
Time (ns) B3 DIO
1000
IRF
Decay
FIT
100
10
60 70 80 90 100 110 120
Time (ns)
4
2
0
-2
-4
60 70 80 90 100 110 120
Time (ns) B3 DMSO
Figure S11: Time resolved fluorescence emission spectra of 3-PdTPyP in 1,4-dioxane (up) and DMSO
(down) and the respective residuals.
1000
IRF
Decay
FIT
100
10 R
esid
ua
ls
Co
unts
Resid
uals
C
ounts
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60 70 80 90 100 110 120
Time (ns)
4
2
0
-2
-4
60 70 80 90 100 110 120
Time (ns) B4 DIO
1000
IRF
Decay
FIT
100
10
60 70 80 90 100 110 120
Time (ns)
4
2
0
-2
-4
60 70 80 90 100 110 120
Time (ns) B4 DMSO
Figure S12: Time resolved fluorescence emission spectra of 4-PdTPyP in 1,4-dioxane (up) and DMSO
(down) and the respective residuals.
1000
IRF
Decay
FIT
100
10
Resid
uals
C
ou
nts
Re
sid
ua
ls
Co
un
ts
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Figure S13: (a) UV-Vis absorption (DRUV) and (b) diffuse reflectance spectra of porphyrins 3-PdTPyP and 4-PdTPyP.
Figure S14: Thin-layer UV-visible spectra features for reduction processes of 4-PdTPyP, I = 0.10 mol L-1
TBAPF6 in DMF. Insets show the voltammetry scans.
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Figure S15: Thin-layer UV-visible spectra features for reduction processes of 4-PdTPyP, I = 0.10 mol L-1
TBAPF6 in DMF. Insets show the voltammetry scans.
