PP-ART-12-2009-000206 Supporting Information-revised · Title: Microsoft Word -...
Transcript of PP-ART-12-2009-000206 Supporting Information-revised · Title: Microsoft Word -...
S1
Supporting information
for
Photochemical deuterium exchange in phenyl-
substituted pyrroles and indoles in CD3CN-D2O
By
Nikola Basarić,*a Alfredo Franco-Cea,b Marija Alešković,a Kata Mlinarić-
Majerski,a and Peter Wan*b
a Department of Organic Chemistry and Biochemistry, Bijenička cesta 54, 10 000 Zagreb,
Croatia. Fax: + 385 1 4680 195; Tel: +385 1 4561 141; E-mail: [email protected]
b Department of Chemistry, University of Victoria, Box 3065 Stn CSC, Victoria BC,
V8W3V6, Canada, Fax: + 1 (250) 721-7147, Tel: + 1 (250) 721-8976;
E-mail: [email protected]
Electronic Supplementary Material (ESI) for Photochemical & Photobiological SciencesThis journal is © The Royal Society of Chemistry and Owner Societies 2010
S2
Table of contents:
1. Experimental procedure for the preparation of compounds S3
2. 1H NMR spectra after photolyses in deuterated solvents S5
3. Fluorescence study S23
4. Laser flash photolysis S40
S3
1. Experimental procedure for the preparation of compounds N-tert-Butoxycarbonyl-2-phenylpyrrole: To a stirred solution of iodobenzene (193 mg, 0.95
mmol), cesium carbonate (620 mg, 1.89 mmol) and tetrakis(triphenylphosphine)palladium (5
% mol) in toluene (20 mL) at reflux under nitrogen was added a solution of (1-tert-
butyloxycarbonylpyrrol-2-yl)boronic acid1 (200 mg, 0.95 mmol) in the mixture of toluene (10
mL) and methanol (3 mL) during 7 h. The mixture was stirred at reflux for 17 h, cooled and
methanol was evaporated under reduced pressure. To a toluene suspension was added water
(30 mL) and the layers were separated, the water layer was extracted with dichloromethane (3
× 25 mL). Combined organic extracts were washed with water (30 mL) and dried over
anhydrous MgSO4, and evaporated under reduced pressure. The resulting crude product was
purified by chromatography on silica eluting with the mixture of dichloromethane and hexane
(10 → 30%) to yield 185 mg (86 %) of N-tert-Butoxycarbonyl-2-phenylpyrrole as a clear oil.
The 1H NMR and 13C NMR spectra were identical to the literature data.2
2-Phenylpyrrole (8): A suspension of sodium methoxide (freshly prepared by reacting 84 mg
of sodium with 10 mL of methanol) was added to a stirred solution of N-tert-butoxycarbonyl-
2-phenylpyrrole (280 mg, 1.22 mmol) in methanol (40 mL) and stirred at reflux for 3h, and at
25 °C for 15 h. The solvent was evaporated and the residue was portioned between
dichloromethane and water. Water layer was extracted with dichloromethane (2 × 25 mL),
and the combined organic extracts were washed with brine (30 ml). Organic extracts were
dried over anhydrous MgSO4, solvent was evaporated to give 158 mg (90 %) of the product as
a white crystalline solid. The 1H NMR and 13C NMR spectra were identical to the literature
data.2
7-Phenylindole (12): A round bottom flask (50 mL) was charged with 7-bromoindole (255
mg, 1.3 mmol), phenylboronic acid (158 mg, 1.3 mmol),
tetrakis(triphenylphsophine)palladium (40 mg), K2CO3 (300 mg), toluene (10 mL) and
methanol (5 mL). The mixture was heated to reflux for 24 h under N2. During this time, the
orange solution turned to deep purple. After cooling to rt, 30 mL of HCl (1M) was added and
the mixture was extracted with CH2Cl2 (4 × 15 mL). The resulting deep-red organic extracts
were combined and dried over anhydrous MgSO4. The solvent was evaporated on a rotary
evaporator to yield the crude product in the form of dark oil that was purified by column
S4
chromatography on silica gel eluting with a mixture of CH2Cl2 - Hexanes (1:3). The resulting
clear oil crystallized spontaneously upon storage at 10 ºC.
1. S. Martina, V. Enkelmann, G. Wegner, A.-D. Schlüter, Synthesis 1991 613-615.
2. A. Burghart, H. Kim, M. B. Welch, L. H. Thorensen, J. Reibenspies, K. Burgess, J.
Org. Chem. 1999, 64, 7813-7819.
S5
1H NMR spectra after photolyses in deuterated solvents
1H NMR (CD3CN + D2O) after thermal (“dark“) experiment for 7 in CD3CN – D2O SpinWorks 2.3: Nikola NB-159 + D2O
PPM 7.70 7.60 7.50 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 6.60 6.50 6.40 6.30
0.
998
1.
053
1.
075
0.
978
1.
008
0.
980
7.56
25
7.54
94
7.
4196
7.
4187
7.
4061
7.
4051
7.
2445
7.
2393
7.
1193
7.
1176
7.
1059
7.
0940
7.
0926
7.
0271
7.
0257
7.
0140
7.
0128
7.
0007
6.
4427
6.
4385
6.
4377
file: D:\PODACI-Nikola\NMR-Zagreb\N-159\2\fid expt: <zg30>transmitter freq.: 600.133901 MHztime domain size: 32768 pointswidth: 9541.98 Hz = 15.899760 ppm = 0.291198 Hz/ptnumber of scans: 16
freq. of 0 ppm: 600.130013 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000
S6
1H NMR (CD3CN + D2O) after photolysis (45min) of 7 at 254 nm in a quartz NMR tube SpinWorks 2.3: Nikola NB-159 + D2O na kraju
PPM 7.70 7.60 7.50 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 6.60 6.50 6.40 6.30
0.
998
1.
049
0.
782
0.
800
0.
913
0.
820
7.
5642
7.
5627
7.
5611
7.
5511
7.
5495
7.
5479
7.
4202
7.
4187
7.
4173
7.
4066
7.
4051
7.
4037
7.
2450
7.
2397
7.
1194
7.
1176
7.
1077
7.
1059
7.
1041
7.
0942
7.
0923
7.
0271
7.
0255
7.
0154
7.
0139
7.
0123
7.
0023
7.
0006
6.
4443
6.
4429
6.
4391
6.
4377
file: D:\PODACI-Nikola\NMR-Zagreb\N-159\4\fid expt: <zg30>transmitter freq.: 600.133901 MHztime domain size: 32768 pointswidth: 9541.98 Hz = 15.899760 ppm = 0.291198 Hz/ptnumber of scans: 24
freq. of 0 ppm: 600.130013 MHzprocessed size: 32768 complex pointsLB: 0.000 GB: 0.0000
S7
1H NMR (CDCl3) after photolysis (2h) of 8 in CH3CN – D2O (1M)
S8
1H NMR (CDCl3) after thermal (“dark“) experiment (2h) for 8 in CH3CN – D2O (1M)
S9
1H NMR (CD3CN) after photolysis (30 min) of 8 in CD3CN – D2O (1M)
S10
1H NMR (CDCl3) after thermal (“dark“) experiment for 8 in CD3CN – D2O (1M)
S11
1H NMR (CD3CN) after photolysis (4h) of 9 in CH3CN – D2O (1M)
S12
1H NMR (CD3CN) after thermal (“dark“) experiment (4h) for 9 in CH3CN – D2O (1M)
S13
1H NMR (CD3CN) after photolysis (30 min) of 9 in CD3CN – D2O (1M)
S14
1H NMR (CD3CN) after thermal (“dark“) experiment (30 min) for 9 in CD3CN – D2O (1M)
S15
1H NMR (CD3CN) after photolysis (30 min) of 9 in CD3CN
S16
1H NMR (CD3CN) after thermal (“dark“) experiment (30 min) for 9 in CD3CN
S17
1H NMR (CD3CN) after photolysis (15 min) of 10 in CD3CN – D2O (1M)
S18
1H NMR (CD3CN) after thermal (“dark“) experiment (15 min) for 10 in CD3CN – D2O (1M)
S19
1H NMR (CD3CN) after photolysis (4 h) of 12 in CH3CN – D2O (1M)
S20
1H NMR (CD3CN) after thermal (“dark“) experiment (4 h) for 12 in CH3CN – D2O (1M)
S21
1H NMR (CD3CN) after photolysis (30 min) of 12 in CD3CN – D2O (1M)
S22
1H NMR (CD3CN) after thermal (“dark“) experiment (30 min) for 12 in CD3CN – D2O (1M)
S23
3. Fluorescence study UV-vis spectra of 2-phenylpyrrole (8), 2-phenylindole (9) and 7-phenylindole (12) in CH3CN.
200 225 250 275 300 325 3500
10000
20000
30000
40000
50000
60000
Absorption spectra in CH3CN
Mol
ar a
bsor
ptio
n co
effic
ient
ε /
M-1cm
-1
Wavelength λ / nm
2-phenylpyrrole 2-phenylindole 7-phenylindole
Excitation and emission spectrum of 2-phenylpyrrole (8) in cyclohexane.
240 260 280 300 320 340 360 380 400 420
2-Phenylpyrrole in cyclohexane
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 350 nm λex = 290 nm
Excitation and emission spectrum of 2-phenylpyrrole (8) in CH3CN.
240 260 280 300 320 340 360 380 400 420 440
2-phenylpyrrole in CH3CN
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 350 nm λex = 375 nm
S24
Excitation and emission spectrum of 2-phenylpyrrole (8) in CH3OH.
240 260 280 300 320 340 360 380 400 420 440 460
2-Phenylpyrrole in CH3OH
Wavelength λ / nm
λem = 350 nm λex = 290 nm
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Emission spectra of 2-phenylpyrrole (8) in different solvents.
300 325 350 375 400 425 450
2-Phenylpyrrole in different solvents
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
cyclohexane CH3CN CH3OH
Fluorescence spectra of 2-phenylpyrrole (8) in CH3CN at different H2O content and Stern-Volmer plot of fluorescence quenching by H2O.
300 350 400 450 500
Fluorescece in CH3CN at different H2O content
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
c(H2O) = 0 M c(H2O) = 20.8 M
0 5 10 15 200,90
0,92
0,94
0,96
0,98
1,00
Φ0/Φ
c (H2O ) / M
S25
Fluorescence quenching of 2-phenylpyrrole (8) in CH3CN-H2O (1:4) by HClO4, and Stern-Volmer plot of the fluorescence quenching by HClO4.
300 350 400 450 500
c(H+)
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,0030
1,0
1,1
1,2
1,3
1,4
1,5
1,6
Φ0/Φ
c (H+) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 1,01204 0,00611B 180,78237 3,10335------------------------------------------------------------
R SD N P------------------------------------------------------------0,99721 0,01295 21 <0.0001------------------------------------------------
Relative fluorescence intensity of 2-phenylpyrrole (8) in CH3CN-H2O (4:1) at 358 nm as a function of HClO4 concentration. Red line represents the fitting of the model to the experimental values (black dots) obtained by the factor analysis in the SPECFIT program.
0,000 0,001 0,002 0,003
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (HClO4) / M
Relative fluorescence intensity of 2-phenylpyrrole (8) in CH3CN-H2O (4:1) in the protonated and non-protonated form, obtained by the factor analysis in the SPECFIT program.
300 350 400 450 500
Rel
ativ
e Fl
uore
scen
ce In
teni
sty
Wavelenght λ/nm
8 8H+
S26
Fluorescence quenching of 2-phenylpyrrole (8) in CH3CN-H2O (1:4) by NaOH, and Stern-Volmer plot of the fluorescence quenching by NaOH.
300 350 400 450 500
c(OH-)
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,0030
1,0
1,2
1,4
1,6
1,8
2,0
Φ
0 / Φ
c (NaOH) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 0,96782 0,00962B 295,77696 4,76303------------------------------------------------------------
R SD N P------------------------------------------------------------0,99755 0,02039 21 <0.0001-----------------------------------------------------------
Relative fluorescence intensity of 2-phenylpyrrole (8) in CH3CN-H2O (4:1) at 356 nm as a function of NaOH concentration. Red line represents the fitting of the model to the experimental values (black dots), obtained by the factor analysis in the SPECFIT program.
0,0000 0,0005 0,0010 0,0015 0,0020
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (NaOH) / M
S27
Excitation and emission spectrum of 2-phenylindole (9) in cyclohexane.
250 300 350 400 450
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λem = 370 nm λex = 300 nm
2-phenylindole in cyclohexane
Excitation and emission spectrum of 2-phenylindole (9) in chloroform.
250 300 350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λem = 360 nm λex = 300 nm
2-phenylindole in CHCl3
Excitation and emission spectrum of 2-phenylindole (9) in CH3CN.
250 300 350 400 450 500
2-phenylindole in CH3CN
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 380 nm λex = 300 nm
S28
Excitation and emission spectrum of 2-phenylindole (9) in CH3OH.
250 300 350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λem = 380 nm λex = 300 nm
2-phenylindole in CH3OH
Emission spectra of 2-phenylindole (9) in different solvents.
350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
2-phenylindole in different solvents
cyclohexane CHCl3 CH3CN CH3OH
Fluorescence spectra of 2-phenylindole (9) in CH3CN at different H2O content and Stern-Volmer plot of fluorescence quenching by H2O.
350 400 450 500
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
Fluorescece in CH3CN different H2O content2-phenylindole
c(H2O) = 0 M c(H2O) = 20.8 M
0 5 10 15 200,93
0,94
0,95
0,96
0,97
0,98
0,99
1,00 2-phenylindole in CH3CN
Φ
0/Φ
c (H2O ) / M
S29
Fluorescence quenching of 2-phenylindole (9) in CH3CN-H2O (1:4) by HClO4, and Stern-Volmer plot of the fluorescence quenching by HClO4.
350 400 450 500
c(H+)
2-phenylindole
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm0,0 0,1 0,2 0,3 0,4 0,5
1,00
1,05
1,10
1,15
1,202-phenylindole
Φ0 /
Φ
c(HClO4) / M
Stern-Volmer plot of the fluorescence quenching of 2-phenylindole (9) in CH3CN-H2O (1:4) by HClO4.
0,00 0,05 0,10 0,15 0,20 0,25 0,30
1,00
1,02
1,04
1,06
1,08
Φ0 /
Φ
c (HClO4) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 0,99285 0,00257B 0,26542 0,01472------------------------------------------------------------
R SD N P------------------------------------------------------------0,9894 0,004 9 <0.0001-----------------------------------------------------
Fluorescence quenching of 2-phenylindole (9) in CH3CN-H2O (1:4) by NaOH, and Stern-Volmer plot of the fluorescence quenching by NaOH.
350 400 450 500
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
c (OH-)
0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,0030
1,00
1,05
1,10
1,15
1,20
2-phenylindole
Φ0/Φ
c(NaOH) / M
S30
Stern-Volmer plot of the fluorescence quenching of 2-phenylindole (9) in CH3CN-H2O (1:4) by NaOH.
0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,0030
1,00
1,05
1,10
1,15
1,20
Φ
0/Φ
c(NaOH) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 0,99196 0,00216B 58,97811 1,07022------------------------------------------------------------
R SD N P------------------------------------------------------------0,99689 0,00458 21 <0.0001----------------------------------------------------------
Relative fluorescence intensity of 2-phenylindole (9) in CH3CN-H2O (4:1) at 377 nm as a function of NaOH concentration. Red line represents the fitting of the model to the experimental values (black dots), obtained by the factor analysis in the SPECFIT program.
0,000 0,001 0,002 0,003
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (NaOH) / M
S31
Excitation and emission spectrum of N-methyl-2-phenylindole (10) in cyclohexane.
250 300 350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λem = 360 nm λex = 300 nm
N-methyl-2-phenylindolecyclohexane
Excitation and emission spectrum of N-methyl-2-phenylindole (10) in CHCl3.
250 300 350 400 450 500
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 380 nm λex = 300 nm
N-methyl-2-phenylindoleCHCl3
Excitation and emission spectrum of N-methyl-2-phenylindole (10) in CH3CN.
250 300 350 400 450 500
N-methyl-2-phenylindoleCH3CN
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 380 nm λex = 300 nm
S32
Excitation and emission spectrum of N-methyl-2-phenylindole (10) in CH3OH.
250 300 350 400 450 500
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λem = 380 nm λex = 300 nm
N-methyl-2-phenylindoleCH3OH
Emission spectra of N-methyl-2-phenylindole (10) in different solvents.
350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
N-methyl-2-phenylindole
cyclohexane CHCl3 CH3CN CH3OH
Stern-Volmer plot of the fluorescence quenching of N-methyl-2-phenylindole (10) in CH3CN by H2O.
0 5 10 15 20
0,86
0,88
0,90
0,92
0,94
0,96
0,98
1,00 N-methyl-2-phenylindole
Φ0 /
Φ
c(H2O) / M
S33
Fluorescence quenching of N-methyl-2-phenylindole (10) in CH3CN-H2O (1:4) by HClO4, and Stern-Volmer plot of the fluorescence quenching by HClO4.
350 400 450 500
N-methyl-2-phenylindole
c(H+)
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
0,0 0,1 0,2 0,3 0,4 0,5
1,0
1,1
1,2
1,3
1,4
1,5
1,6
1,7
N-methyl-2-phenylindole
Φ0 /
Φc (HClO4) / M
Stern-Volmer plot of the fluorescence quenching of N-methyl-2-phenylindole (10) in CH3CN-H2O (1:4) by HClO4.
0,00 0,05 0,10 0,15 0,20 0,25
1,00
1,05
1,10
1,15
1,20
Φ
0 / Φ
c (HClO4) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 0,99225 0,00462B 0,82596 0,03368------------------------------------------------------------
R SD N P------------------------------------------------------------0,99587 0,00657 7 <0.0001------------------------------------------------------------
Relative fluorescence intensity of N-methyl-2-phenylindole (10) in CH3CN-H2O (4:1) at 384 nm as a function of HClO4 concentration. Red line represents the fitting of the model to the experimental values (black dots), obtained by the factor analysis in the SPECFIT program.
0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (HClO4) / M
S34
Fluorescence quenching of N-methyl-2-phenylindole (10) in CH3CN-H2O (1:4) by NaOH, and Stern-Volmer plot of the fluorescence quenching by NaOH.
350 400 450 500
c(OH-)
Wavelength λ / nm
Rel
ativ
e Fl
uore
scen
ce In
tens
ity N-methyl-2-phenylindole
0,000 0,001 0,002 0,003
1,00
1,02
1,04
1,06
1,08
Φ0 /
Φ
c(NaOH) / M
Stern-Volmer plot of the fluorescence quenching of N-methyl-2-phenylindole (10) in CH3CN-H2O (1:4) by NaOH.
0,000 0,001 0,002 0,003
1,00
1,02
1,04
1,06
1,08
1,10
Φ0 /
Φ
c(NaOH) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 1,00971 0,00126B 23,7247 0,6239------------------------------------------------------------
R SD N P------------------------------------------------------------0,99349 0,00267 21 <0.0001------------------------------------------------------------
S35
Excitation and emission spectrum of 7-phenylindole (12) in cyclohexane.
250 275 300 325 350 375 400 425
7-phenylindole in cyclohexane
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
λ em = 360 nm λ ex = 290 nm
Excitation and emission spectrum of 7-phenylindole (12) in CHCl3.
250 275 300 325 350 375 400 425 450
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λ em = 350 nm λ ex = 290 nm
7-phenylindole in CHCl3
Excitation and emission spectrum of 7-phenylindole (12) in CH3CN.
250 300 350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λ em = 375 nm λ ex = 290 nm
7-phenylindole in CH3CN
S36
Excitation and emission spectrum of 7-phenylindole (12) in CH3OH.
250 300 350 400 450 500
R
elat
ive
Fluo
resc
ence
Inte
nsity
Wavelength λ / nm
λ em = 350 nm λ ex = 290 nm
7-phenylindole in CH3OH
Emission spectra of 7-phenylindole (12) in different solvents.
300 325 350 375 400 425 450Wavelength λ / nm
R
elat
ive
Fluo
resc
ence
Inte
nsity 7-phenylindole
cyclohexane CHCl3 CH3CN CH3OH
Fluorescence spectra of 7-phenylindole (12) in CH3CN at different H2O content and Stern-Volmer plot of fluorescence quenching by H2O.
350 400 450 500
7-phenylindole / CH3CN
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
c (H2O) = 0 M c (H2O) = 21 M
0 5 10 15 200,90
0,92
0,94
0,96
0,98
1,00
7-phenylindole / CH3CN
Φ 0 /
Φ
c (H2O) / M
S37
Stern-Volmer plot of the fluorescence quenching of 7-phenylindole (12) in CH3CN-H2O (1:4) by HClO4.
0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,0030
1,00
1,01
1,02
1,03
1,04
1,05
Φ
0/Φ
c(H+) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 1,00066 0,00107B 15,26137 0,54158------------------------------------------------------------
R SD N P------------------------------------------------------------0,98825 0,00226 21 <0.0001------------------------------------------------------------
Relative fluorescence intensity of 7-phenylindole (12) in CH3CN-H2O (4:1) at 381 nm as a function of HClO4 concentration. Red line represents the fitting of the model to the experimental values (black dots), obtained by the factor analysis in the SPECFIT program.
0,000 0,001 0,002 0,003
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (HClO4) / M
Relative fluorescence intensity of 7-phenylindole (12) in CH3CN-H2O (4:1) in the protonated and non-protonated form, obtained by the factor analysis in the SPECFIT program.
350 400 450 500 550
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
12 12H+
S38
Fluorescence quenching of 7-phenylindole (12) in CH3CN-H2O (1:4) by NaOH, and Stern-Volmer plot of the fluorescence quenching by NaOH.
350 400 450 500 550
c (OH-)
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
0,0000 0,0005 0,0010 0,0015 0,0020 0,0025 0,00300,9
1,0
1,1
1,2
1,3
1,4
1,5
1,6
1,7 7-phenylindole
Φ
0/Φ
c(NaOH) / M
Stern-Volmer plot of the fluorescence quenching of 7-phenylindole (12) in CH3CN-H2O (1:4) by NaOH.
0,0000 0,0002 0,0004 0,0006 0,0008 0,00100,95
1,00
1,05
1,10
1,15
1,20
1,25
1,30
1,35
7-phenylindole
Φ0/Φ
c(NaOH) / M
Y = A + B * X
Parameter Value Error------------------------------------------------------------A 0,99948 0,0114B 382,8361 20,50278------------------------------------------------------------
R SD N P------------------------------------------------------------0,99573 0,01444 5 3,35277E-4---------------------------------------------------------
Relative fluorescence intensity of 7-phenylindole (12) in CH3CN-H2O (4:1) at 378 nm as a function of NaOH concentration. Red line represents the fitting of the model to the experimental values (black dots), obtained by the factor analysis in the SPECFIT program.
0,000 0,001 0,002 0,003
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
c (NaOH) / M
S39
Relative fluorescence intensity of 7-phenylindole (12) in CH3CN-H2O (4:1) in the neutral and deprotonated form, obtained by the factor analysis in the SPECFIT program.
350 400 450 500 550
Rel
ativ
e Fl
uore
scen
ce In
tens
ity
Wavelength λ / nm
12NH 12N-
S40
4. Laser flash photolysis
Transient absorption spectra of 2-phenylpyrrole (8) in N2-purged CH3CN solution.
300 400 500 600 700 800-0,10
-0,05
0,00
0,05
0,10
0,15
0,20 2-phenylpyrrole in CH3CNN2 purged
Δ A
Wavelength λ / nm
0.55 μs 2.4 μs 5.0 μs 8.0 μs
Transient absorption spectra of 2-phenylpyrrole (8) in O2-purged CH3CN solution.
300 400 500 600 700 800
0,00
0,05
0,10
0,15
0,20
0.55 μs 2.4 μs 5.0 μs 8.0 μs
2-phenylpyrrole in CH3CNO2 purged
Wavelength λ / nm
Δ A
Transient absorption spectrum of 2-phenylpyrrole (8) in O2-purged CH3CN solution 550 ns after the laser pulse.
400 500 600 700 8000,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
Δ
A
Wavelength λ / nm
2-phenylpyrrole in CH3CNO2 purged 550 ns after the pulse
300 400 500 600 700 800
0,00
0,05
0,10
0,15
0,20
400 500 600 700 8000,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
Δ
A
Wavelength λ / nm
2-phenylpyrrole in CH3CN
O2 purged
550 ns after the pulse
2-phenylpyrrole in CH3CNO2 purged
Δ A
Wavelength λ / nm
S41
Transient absorption spectra of 2-phenylpyrrole (8) in N2-purged CH3CN-H2O (1:1) solution, pH = 7.
300 400 500 600 700 800-0,05
0,00
0,05
0,10
0,15
0,20
0,25 Ph-py / CH3CN-H
2O 1:1 pH = 7
N2 purged
Δ A
Wavelength λ / nm
0.5 μs 2.2 μs 7.2 μs 16 μs
Transient absorption spectra of 2-phenylpyrrole (8) in O2-purged CH3CN-H2O (1:1) solution, pH = 7.
300 400 500 600 700 800
0,00
0,05
0,10
0,15
0,20
Ph-py / CH3CN-H2O 1:1 pH = 7O2 purged
400 450 500 550 6000,000
0,004
0,008
0,012
0,016
0,020
Δ A
Wavelength λ / nm
0.5 μs 3.1 μs 8.6 μs 16 μs
Δ A
Wavelength λ / nm
0.5 μs 3.1 μs 8.6 μs 16 μs
Transient absorption spectra of 2-phenylpyrrole (8) in N2-purged CH3CN-H2O (1:1) solution, pH = 12.
300 400 500 600 700-0,050
-0,025
0,000
0,025
0,050
0,075
0,100
0,125
0.6 μs 3.1 μs 7.9 μs 16 μs
Δ A
Wavelength λ / nm
Ph-py / CH3CN-H2O 1:1 pH = 12N2 purged
S42
Transient absorption spectra of 2-phenylpyrrole (8) in O2-purged CH3CN-H2O (1:1) solution, pH = 12.
300 400 500 600
0,00
0,05
0,10
0,15
0,20Ph-py / CH3CN-H2O 1:1 pH = 12O2 purged
0.6 μs 3.5 μs 9.3 μs 16 μs
350 400 450 500 550 6000,00
0,01
0,02
Wavelength λ / nm
Δ A
Wavelength λ / nm
Δ A
Transient absorption spectra of 2-phenylindole (9) in N2-purged CH3CN solution.
300 400 500 600 700 800
-0,05
0,00
0,05
0,10
0,15
0,20 2-phenylindole / acnN2 purged
Δ A
Wavelength λ / nm
0.51 μs 2.1 μs 4.9 μs 8.0 μs
Transient absorption spectra of 2-phenylindole (9) in O2-purged CH3CN solution.
300 400 500 600 700 800
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
Wavelength λ / nm
Δ A
0.20 μs 1.1 μs 3.7 μs 8.0 μs
2-phenylindole / acnO2 purged
S43
Transient absorption spectra of 2-phenylindole (9) in N2-purged CH3CN-H2O (1:1) solution.
300 400 500 600 700-0,05
0,00
0,05
0,10
0,15
2-phenylindole / CH3CN-H2O 1:1N2 purged
Δ A
Wavelength λ / nm
0.30 μs 1.3 μs 4.1 μs 7.7 μs
Transient absorption spectra of 2-phenylindole (9) in O2-purged CH3CN-H2O (1:1) solution.
300 400 500 600 700-0,04
-0,02
0,00
0,02
0,04
0,06
0,08
0,10
Δ
A
Wavelength λ / nm
2-phenylindole / CH3CN-H2O 1:1O2 purged
0.30 μs 1.4 μs 4.2 μs 7.8 μs
Transient absorption spectra of N-methyl-2-phenylindole (10) in N2-purged CH3CN-H2O (1:1) solution.
300 400 500 600 700 800-0,05
0,00
0,05
0,10
0,15
0,20N-methyl-2-phenylindole in CH3CN - H2O 1:1N2 purged
Δ A
Wavelength λ / nm
1.1 μs 7.5 μs 23 μs 40 μs
S44
Transient absorption spectra of N-methyl-2-phenylindole (10) in O2-purged CH3CN-H2O (1:1) solution.
300 400 500 600 700-0,04
-0,02
0,00
0,02
0,04
0,06
0,08
0,10
Δ A
Wavelength λ / nm
1.1 μs 7.5 μs 23 μs 40 μs
N-methyl-2-phenylindole in CH3CN - H2O 1:1O2 purged
Transient absorption spectra of 7-phenylindole (12) in N2-purged CH3CN solution.
300 350 400 450 500 550 600 650 700 750-0,05
0,00
0,05
0,10
0,157-phenylindole in CH3CNN2 purged
Δ A
Wavelength λ / nm
1.1 μs 5.1 μs 10 μs 16 μs
Transient absorption spectra of 7-phenylindole (12) in O2-purged CH3CN solution.
300 350 400 450 500 550 600 650 700 750-0,010
-0,005
0,000
0,005
0,010
7-phenylindole in CH3CNO2 purged
Δ A
Wavelength λ / nm
1.0 μs 5.1 μs 10 μs 16 μs