Job/Unit: O42227
/KAP1
Date: 11-06-14 18:16:44
Pages: 13
K. Thiago de Oliveira et al.
FULL PAPER
5.3 Hz, 1 H, Th-H), 7.81 (dd, J = 5.3, 1.1 Hz, 1 H, Th-H), 7.83–
CD2Cl2): δ = 61.8 (C-3, C-13), 92.0 (C-2, C-12), 108.0 (C-5,C-10,
7.85 (dd, J = 1.2, 0.3 Hz, 1 H, Th-H), 7.85–7.88 (m, 3 H, Th-H), C-15, C-20), 125.6–132.3 (β-CH, Th-CH, Ph-CH), 135.8–155.5 (α-
7.98 (d, J = 10.0 Hz, 1 H, H-2), 8.32 (dd, J = 4.9, 1.4 Hz, 1 H, β-
C, Th-C, Ph-C) ppm. HRMS (ESI-TOF): m/z calcd for
H), 8.63 (dd, J = 4.9, 1.4 Hz, 1 H, β-H), 8.65–8.72 (d AB, J = C50H24Cl4N10O10S4 [M + H]+ 1192.9387; found 1192.9419.
4.6 Hz, 2 H, β-H), 8.82 (dd, J = 4.9, 1.4 Hz, 1 H, β-H), 8.92 (dd,
Compound 13c: UV/Vis (CH2Cl2): λmax (logε) = 393 (5.00), 542
J = 4.9, 1.4 Hz, 1 H, β-H) ppm. 13C NMR (101 MHz, CD2Cl2): δ
(4.55), 667 (3.92), 728 (4.85) nm. 1H NMR (400.15 MHz, CD2Cl2):
= 62.1 (C-3), 92.2 (C2), 106.5–116.6 (C-5,C-10,C-15,C-20), 125.2–
δ = –1.82 (s, 1 H, NH), –1.76 (s, 1 H, NH), 6.95–7.02 (m, 2 H, Ph-
134.3 (β-CH, Th-CH, Ph-CH), 135.9–142.9 (α-Cq, Th-Cq, Ph-Cq),
H), 7.23 (d, J = 9.9 Hz, 2 H, H-3, H-12), 7.26–7.34 (m, 5 H, Ph-
153.8–163.2 (α-Cq, C-1,C-4, C-31) ppm. HRMS (ESI-TOF): m/z
H, Th-H), 7.89 (d, J = 9.9 Hz, 2 H, H-2, H-13), 7.92–8.0 (s.l., 4 H,
calcd for C43H25Cl2N5OS4 [M + H]+ 826.0397; found 826.0414.
Th-H), 8.16 (s.l., 2 H, Th-H), 8.31 (d, J = 4.1 Hz, 2 H, β-H), 8.63
Compound 11b: The crude reaction product was purified by flash
column chromatography (dichloromethane/hexane, 6:4). The frac-
tion of interest was concentrated and reapplied in preparative sil-
ica-gel TLC and eluted with toluene/hexanes, 7:3. Subsequently,
the product was purified over Sephadex LH-20 using a mixture
of dichloromethane/methanol, 1:1 as eluent. Finally, chlorin 11b
(4.9 mg, 5.5 μmol, 8%) was crystallized from chloroform and meth-
anol and obtained. UV/Vis (CH2Cl2): λmax (logε) = 424 (5.31), 484
(3.77), 523 (3.85), 593 (4.07), 622 (4.52) nm. 1H NMR (CD2Cl2,
400.15 MHz): δ = 6.87 (d, J = 1.5 Hz, 1 H, Ph-H or Th-H), 6.88
(d, J = 1.6 Hz, 1 H, Ph-H or Th-H), 7.15–7.22 (m, 3 H, Ph-H, H-
3), 7.33–7.40 (m, 3 H, Th-H), 7.43 (d, J = 5.3 Hz, 1 H, Th-H), 7.68
(d, J = 4.9 Hz, 1 H, Th-H), 7.69–7.74 (m, 4 H, Th-H), 7.77 (d, J
= 10.4 Hz, 1 H, H-2), 8.06 (d, J = 4.5 Hz, 1 H, β-H), 8.35 (d, J =
4.7 Hz, 1 H, β-H), 8.56 (d, J = 4.5 Hz, 2 H, β-H), 8.63 (d, J =
4.7 Hz, 1 H, β-H), 8.72 (d, J = 4.7 Hz, 1 H, β-H) ppm. 13C NMR
(CD2Cl2, 101 MHz): δ = 61.2 (C-3), 90.8 (C-2), 106.6–118.0 (C-
5,C-10,C-15,C-20), 126.6–133.6 (β-CH, Th-CH, Ph-CH), 136.0–
156.4 (α-C, Th-C, Ph-C) ppm. HRMS (ESI-TOF): m/z calcd for
C43H23Cl2N5OS4Zn [M]+ 886.9454; found 886.9463.
(d, J = 2.0 Hz, 2 H, β-H) ppm. 13C NMR (CD2Cl2, 101 MHz): δ
= 61.82 (C-3, C-12), 91.1 (C-2,C-13), 107.8–108.6 (C-5, C-10, C-
15, C-20), 123.8–132.3 (β-CH, Th-CH, Ph-CH), 136.0–161.2 (α-C,
Th-C, Ph-C) ppm. HRMS (ESI-TOF): m/z calcd for
C50H24Cl4N10O10S4 [M + H]+ 1192.9387; found 1192.9416.
Compound 11d: The crude product was purified by flash column
chromatography (dichloromethane/toluene, 1:1). The fraction of
interest was concentrated under vacuum and reapplied in prepara-
tive silica-gel TLC using toluene/ethyl acetate, 9:1 as eluent. Sub-
sequently, the product was eluted over Sephadex LH-20 with a mix-
ture of dichloromethane/methanol, 1:1 and crystallized from
chloroform and methanol to give 11d (13.5 mg, 12.6 μmol, 22%).
UV/Vis (CH2Cl2): λmax (logε) = 429 (4.94), 527 (3.87), 596 (3.97),
1
630 (4.44) nm. H NMR (400.15 MHz, CD2Cl2): δ = 6.95 (dd, J =
16.0, 12.0 Hz, 1 H, Ph-H), 7.21–7.35 (m, 3 H, H-3, Th-H, Ph-H),
7.73–7.89 (m, 4 H, H-2, Th-H), 8.23 (td, J = 9.6, 4.8 Hz, 3 H, Th-
H), 8.29 (s, 1 H, β-H), 8.52 (dd, J = 7.4, 4.8 Hz, 1 H, β-H), 8.68–
8.75 (m, 2 H, β-H), 8.78 (t, J = 4.4 Hz, 1 H, β-H), 8.87 (t, J =
5.0 Hz, 1 H, β-H) ppm. 13C NMR (101 MHz, CD2Cl2): δ = 61.21
(C-3), 90.62 (C-2), 105.02–116.23 (C-5, C-10, C-15, C-20), 128.16–
133.93 (β-CH, Th-CH, Ph-CH), 136.05–159.29 (α-Cq, Th-Cq, Ph-
Cq) ppm. HRMS (ESI-TOF): m/z calcd for C43H19Cl2N9O9S4Zn
[M + H]+ 1067.89298; found 1067.89393.
Compounds 11c, 12c and 13c: The crude reaction product was puri-
fied by flash column chromatography (toluene/ethyl acetate,
9.5:0.5). Two fractions were collected, where the less polar was
identified as compound 11c and the more polar was as a mixture
of compounds 12c and 13c. The latter mixture was separated by
preparative silica-gel TLC using dichloromethane/hexane, 7:3 as
eluent. The compounds were reapplied in silica Sephadex LH-20
using dichloromethane/methanol, 1:1 and then crystallized with
chloroform and methanol. Compound 11c was obtained in 15%
yield (9.4 mg, 9.34 μmol), 12c in 14% yield (10.0 mg, 8.39 μmol)
and 13c in 13% yield (9.7 mg, 8.14 μmol).
Singlet Oxygen (1O2) Generation Quantum Yield (ΦΔ): Singlet oxy-
gen (1O2) generation, quantum yield (ΦΔ) and 1O2 lifetimes were
determined by using the phosphorescence detection method. Two
different laser equipment were used as excitation sources: a Contin-
uum Surelite III Nd:YAG laser (532 nm; pulse duration: 5 ns; fre-
quency of pulsation: 10 Hz, Q-switch: 350 μs – Santa Clara, USA),
which was also used to pump a Continuum Jaguar dye laser with
(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyran-4-yl-
idene)propanedinitrile in ethanol (635 nm; pulse duration: 5 ns; fre-
Compound 11c: UV/Vis (CH2Cl2): λmax (logε) = 430 (5.09), 521
(4.20), 554 (4.19), 609 (3.93), 662 (4.46) nm. 1H NMR quency of pulsation: 10 Hz, Q-switch: 240 μs – Santa Clara, USA).
(400.15 MHz, CD2Cl2): δ = –1.80 (s, 1 H, NH), –1.86 (s, 1 H, NH),
6.91 (dd, J = 7.3, 1.8 Hz, 1 H, Ph-H), 7.24–7.34 (m,3 H, Ph-H, Th-
H), 7.38 (d, J = 9.9 Hz, 1 H, H-3), 7.85 (d, J = 4.1 Hz, 1 H, Th-
The 1270 nm radiation emitted from singlet oxygen was detected
at right angles with an Edinburgh Analytical Instruments time-re-
solved NIR fluorometer (Livingston, UK) equipped with a liquid-
H), 7.86 (d, J = 4.1 Hz, 1 H, Th-H), 7.94 (br. d., J = 24.5 Hz, 2 H, nitrogen cooled Hamamatsu R55009 photomultiplier (Bridgewater,
Th-H), 8.04 (d, J = 9.9 Hz, 1 H, H-2), 8.28–8.35 (m, 3 H, Th-H), NJ) and a fast acquisition MSA-300 board (Becker & Hickl –
8.52 (dd, J = 5.0, 1.3 Hz, 1 H, β-H), 8.74–8.80 (m, 3 H, β-H), 8.93 Berlin, Germany). For quantum yield measurements, a 5,10,15,20-
(dd, J = 5.0, 1.3 Hz, 1 H, β-H), 9.05 (dd, J = 5.0, 1.3 Hz, 1 H, β- tetraphenylporphyrin (TPP, 2) solution in chloroform was used as
H) ppm. 13C NMR (101 MHz, CD2Cl2): δ = 62.2 (C-3), 92.1 (C- a standard (ΦΔ = 0.50)[28] and both standard and PSs had ab-
2), 105.4–115.0 (C-5, C-10, C-15, C-20), 125.8–134.2 (β-CH, Th-
CH, Ph-CH), 136.1–163.6 (α-C, Th-C, Ph-C) ppm. HRMS (ESI-
TOF): m/z calcd for C43H21Cl2N9O9S4 [M + H]+ 1005.9795; found
1005.9793.
sorbances around 0.25 at the excitation wavelength. Lifetime mea-
surements were performed by accumulation of 1000 decays. The
value of ΦΔ was obtained by comparing the absorbances and
higher intensity emissions of samples and standard as published
before.[24] Phosphorescence decay curves at 1270 nm were fitted to
second-order exponential decays for the determination of O2 life-
time using the Origin 8.0 software (OriginLab – Northampton,
MA).
Compound 12c: UV/Vis (CH2Cl2): λmáx (logε) = 392 (4.98), 540
(4.52), 668 (3.79), 728 (4.79) nm. 1H NMR (CD2Cl2, 400.15 MHz):
δ = –1.82 (s, 2 H, NH), 6.84 (dd, J = 8.8, 2.0 Hz, 2 H, Ph-H), 7.18–
7.32 (m,5 H, Ph-H, Th-H), 7.22 (d, J = 9.9 Hz, 2 H, H-3, H-13),
1
7.66–8.13 (m, 5 H, Th-H), 7.95 (d, J = 9.9 Hz, 2 H, H-2, H-12), Fluorescence Quantum Yield (Φfl): Fluorescence spectra were re-
8.29 (d, J = 4.0 Hz, 2 H, Th-H), 8.33 (d, J = 2.0 Hz, 2 H, β-H),
corded in the 550–800 nm range using 515 nm as excitation wave-
length, 10 nm excitation slit and 20 nm emission slit with a Cary
8.48 (dd, J = 4.9, 1.8 Hz, 2 H, β-H) ppm. 13C NMR (101 MHz,
10
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0