Supporting information
Synthesis and Characterization of compound 4: 54,104,154,204-Tetra-t-butyl-[3,52]ethano-56methyl-31-oxo-5,10,15,20-tetraphenylporphyrinatozinc(II)
Necessary chemicals were purchased from Acros or Sigma-Aldrich and used without further
purification. CH2Cl2 was distilled from K2CO3, MeOH from MgSO4. Silica gel for flash column
chromatography (FC) was purchased from Macherey-Nagel.
The Zn(II) complex 4 was prepared by dissolving compound 1 (100 mg, 112 µmol) in CH2Cl2
(25 mL) and subsequent addition of a saturated methanolic solution (5 mL) of 20 equivalents of
Zn(OAc)·2H2O (490 mg). The reaction mixture was stirred for 3 h at room temperature before it
was transferred to a separatory funnel and trice washed with water. After drying over MgSO4,
the solvent was evaporated and the product was purified by FC (silica, CH 2Cl2:n-hexanes = 2:1)
yielding a dark green solid (yield: 104 mg, 109 µmol, 97 % based on 1).
NMR (400 MHz, CDCl3, rt): δ [ppm] = 1.04 (s, 3H, CH3), 1.48 (s, 9H, tBu-H), 1.58 (s, 18H,
tBu-H), 1.60 (s, 9H, tBu-H), 3.90 (d, 2J=11.3Hz,1H, CH2), 5.48 (d ,2J=11.7 Hz,1H, CH2), 7.28
(d, 4J=1.5 Hz, 1H, Ar’H), 7.55 (d, 4J=2.1 Hz, 1H, Ar’H), 7.63 (m, 2H, ArH), 7.68 (dd, 3J=8.0
Hz, 4J=2.0 Hz, 1H, ArH), 7.74-7.84 (m, 3H, ArH), 7.75 (dd, 3J=8.0 Hz, 4J=1.9 Hz, 1H, ArH),
7.79 (dd, 3J=7.7 Hz, 4J=1.8 Hz, 1H, ArH), 7.88 (dd, 3J=8.0 Hz, 4J=1.7 Hz, 1H, ArH), 8.14 (dd,
3
J=8.0 Hz, 4J=1.7 Hz, 1H, ArH), 8.25 (dd, 3J=8.0 Hz, 4J=1.5 Hz, 1H, ArH), 8.32 (dd, 3J=7.9 Hz,
4
J=1.4 Hz, 1H, ArH), 8.77-8.82 (m, 5H, β-pyrrH), 8.93 (d, 3J=4.7 Hz, 1H, β-pyrrH), 9.07 (d,
3
J=3.3 Hz, 1H, ArH).
13C NMR (100.5 MHz, CDCl , rt): δ [ppm] = 22.5, 31.4, 31.6 (2 signals), 34.7, 34.8 (2 signals),
3
53.7, 115.2, 120.4, 122.8, 123.7 (2 signals), 123.9, 124.2, 125.9, 126.5, 128.0, 131.8, 132.4,
132.8, 133.0, 133.1, 133.4, 134.1, 134.2, 134.3, 134.4, 135.3, 137.4, 138.4, 138.7, 139.2 (2
signals), 142.4, 145.9, 148.1, 149.8, 150.5, 150.6, 150.8, 150.9, 151.3, 151.6, 152.0, 152.1,
152.3, 192.6.
MS (FAB+, NBA): 954 [M]+·, 1911 [2M]+·.
IR (ATR): 3030, 2957, 2907, 2868, 1679, 1640, 1521, 1494, 1459, 1436, 1393, 1363, 1336,
1293, 1262, 1239, 1193, 1154, 1108, 1069, 1050, 996, 865, 838, 795, 721.
UV/Vis (CH2Cl2): λ [nm] (ε [l·mol-1·cm-1]) = 446 (256000), 576 (10700), 633 (12200).
EA for C63H62N4OZn · CH3OH (988.62); calc.: C 77.75, H 6.73, N 5.67;
found: C 77.60, H 6.57, N 5.31.
1H
S1
b
Max. of fluorescence spectrum, nm
Normalized fluorescence intensity
a
1.0
558 nm
608 nm
667 nm
0.8
0.6
0.4
0.2
0.0
710
708
706
704
702
700
698
696
694
692
650
700
750
800
850
690
900
400
Wavelength, nm
450
500
550
600
650
700
Excitation wavelength, nm
Figure S1. a – Steady-state fluorescence spectra of 2 at 558 (line), 608 (dashed) and 667 nm
(points) excitation wavelengths; b – Dependency of fluorescence spectrum maximum of 2
solved in DMF on excitation wavelength. All measurements were done at room temperature.
a
b
Max. of fluorescence spectrum, nm
Normalized fluorescence intensity
776
1.0
500 nm
574 nm
650 nm
0.8
0.6
0.4
0.2
774
772
770
768
766
764
762
760
0.0
758
700
800
900
1000
1100
400
Wavelength, nm
450
500
550
600
650
700
750
Excitation wavelength, nm
Figure S2. a – Steady-state fluorescence spectra of 3 at 500 (line), 574 (dashed) and 650 nm
(points) excitation wavelengths; b – Dependency of fluorescence spectrum maximum of 3
solved in DMF on excitation wavelength. All measurements were done at room temperature.
S2
Normalized fluorescence intensity
1.0
0.8
0.6
0.4
0.2
0.0
600
650
700
750
800
850
Wavelength, nm
Figure S3. Steady-state fluorescence spectrum of 4 at room temperature.
b
a
1.0
Fluorescence intensity, a.u.
Fluorescence intensity, a.u.
1.0
0.8
0.6
0.4
0.8
0.6
0.4
0.2
0.2
0.0
0.0
675
700
725
750
775
800
650
825
675
700
725
750
775
800
825
850
Wavelength, nm
Wavelength, nm
Figure S4. Comparison between decay-associated (points) and steady-state (line) fluorescence
spectra of 1 at 532 (a) and 612 nm (b) excitation
S3
b
0.08
Amplitude of fluorescence decay, a.u.
Amplitude of the fluorescence decay, a.u.
a
0.07
0.06
1.2 ns
3.3 ns
0.05
0.04
0.03
0.02
0.01
0.20
1.2 ns
3.3 ns
0.15
0.10
0.05
0.00
0.00
650
700
750
800
650
850
700
750
800
850
Registration wavelength, nm
Registration wavelength, nm
Normalized fluorescence amplitude
c
1.0
0.8
532 nm
612 nm
0.6
0.4
0.2
0.0
650
700
750
800
850
Registration wavelength, nm
Figure S5. Decay-associated fluorescence spectra of 2 at 532 (a) and 612 nm (b) excitation
wavelength. Comparison of normalized DAF spectra of 2 at 532 nm and 612 nm excitation
wavelength for the fast (c) and the slow (d) decay components.
S4