A Model for a Photosynthetic Composite
FULL PAPER
7.37 (d, J
(H,H)=5.4 Hz, 6H; Py), 7.34 (d, J
E
5-Bromo-15-[4-(1,3-dioxolanyl)phenylethynyl]-10,20-bis(4-ethoxycarbo-
nylphenyl)porphyrinatozinc(II) (8): Compound 7 (100 mg, 1.2ꢀ10ꢀ4 mol)
and 4-(trimethylsilylethynyl)phenyl-1,3-dioxolane (39 mg, 1.6ꢀ10ꢀ4 mol)
were placed in a Schlenk flask and the flask was evacuated and replaced
with Ar gas. Dry THF (10 mL) and a solution of 1m TBAF in THF
(0.47 mL, 4.7ꢀ10ꢀ4 mol) were sequentially added via a syringe. The mix-
7.22 (d, J(H,H)=8.4 Hz, 6H; Ph), 7.15 (d, JACTHUNGTRENNUNG
G
2.13 (s, 1H; OH), 1.62 ppm (s, 6H; CH3); 13C NMR (150 MHz, CDCl3,
258C): d=149.3, 146.2, 144.9, 131.0, 130.9, 130.8, 130.5, 130.2, 125.1,
120.8, 119.9, 94.34, 92.97, 86.71, 80.93, 64.96, 64.53, 31.06 ppm; MALDI-
TOF MS: m/z calcd for C51H36N3O [M+H]+: 706.9; found: 706.0.
ture was stirred for 30 min at room temperature and then [PdCl2ACHTUNGTRENNUNG(PPh3)2]
4-Ethynylphenyl-tris{4-[2-(4-pyridyl)ethynyl]phenyl}methane (6): Com-
pound
(11 mg, 1.6ꢀ10ꢀ5 mol), CuI (4.4 mg, 2.3ꢀ10ꢀ5 mol), and dry Et3N (3 mL)
were added. The solution was degassed by freeze–thaw cycles and re-
placed with Ar gas and stirred for 24 h at room temperature. The result-
ing mixture was concentrated to approximately 5 mL and the reaction
was quenched by the addition of water (ꢁ5 mL) and the product was ex-
tracted with CHCl3 and dried over anhydrous Na2SO4. After removal of
the solvent under reduced pressure, the resulting residue was purified
with a flash silica gel column eluting with CHCl3. The second band was
collected and evaporated to give a still-impure purple solid, which was
further purified by a second flash silica gel column (CHCl3) to give the
5
(20.8 mg, 3.0ꢀ10ꢀ5 mol), NaH (47 mg, 60% in oil, 1.2ꢀ
10ꢀ3 mol), and dry toluene (2 mL) were placed in a test tube with a screw
cap and purged with Ar gas. After the test tube was sealed, the reaction
mixture was heated in an oil bath. After the reaction mixture had been
stirred overnight at 1008C, the reaction was quenched by the addition of
water. The product was extracted with CHCl3 and the organic layer was
dried over anhydrous Na2SO4. The resulting crude product obtained by
evaporation of the solvent was purified with silica gel column chromatog-
raphy (CHCl3/MeOH 95:5). The first band absorbing UV light was col-
lected and the solvents were evaporated to afford the title compound as
a white solid (15.5 mg, 80%). TLC (silica gel, CHCl3/MeOH 9:1): Rf =
title compound as
CHCl3): Rf =0.4; 1H NMR (600 MHz, CDCl3, 258C, TMS): d=9.64 (d,
(H,H)=4.2 Hz, 2H; b-pyrrole), 9.55 (d, J(H,H)=4.2 Hz, 2H; b-pyr-
role), 8.814 (d, (H,H)=4.2 Hz, 2H; b-pyrrole), 8.807 (d, (H,H)=
4.2 Hz, 2H; b-pyrrole), 8.45 (d, (H,H)=7.8 Hz, 4H; Ph), 8.27 (d,
(H,H)=7.8 Hz, 4H; Ph), 7.48 (d, J(H,H)=7.2 Hz, 2H; Ph’), 5.30 (d,
(H,H)=7.2 Hz, 2H; Ph’), 4.56 (q, J(H,H)=7.2 Hz, 4H; CH2CH3), 2.04
(H,H)=7.2 Hz, 6H;
a purple solid (25.2 mg, 23%). TLC (silica gel,
0.5; 1H NMR (600 MHz, CDCl3, 258C, TMS): d=8.60 (d, J
5.4 Hz, 6H; Py), 7.48 (d, J(H,H)=8.4 Hz, 6H; Ph), 7.43 (d, J
8.4 Hz, 2H; Ph’), 7.37 (d, J(H,H)=5.4 Hz, 6H; Py), 7.22 (d, J
8.4 Hz, 6H; Ph), 7.18 (d, J(H,H)=8.4 Hz, 2H; Ph’), 3.09 ppm (s, 1H; C=
ACHTUNGTRENNUNG
J
N
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
J
N
JACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
AHCTUNGTRENNUNG
J
J
C
ACHTUNGTRENNUNG
CH); 13C NMR (150 MHz, CDCl3, 258C): d=149.8, 146.5, 146.0, 131.8,
131.5, 131.2, 130.9, 130.7, 125.5, 120.5, 120.4, 93.34, 87.20, 83.07, 77.79,
65.01 ppm; MALDI-TOF MS: m/z calcd for C48H30N3 [M+H]+: 648.8;
found: 648.1.
ACHTUNGTRENNUNG
(s, 1H; CH), 1.65 (brs, 2H; CH2), 1.57 (t,
JACHTUNGTRENNUNG
CH2CH3), 1.07 ppm (brs, 2H; CH2); 13C NMR (150 MHz, CDCl3, 258C):
d=166.8, 152.7, 150.1, 149.4, 149.2, 147.0, 134.5, 133.3, 133.1, 132.6, 132.5,
131.7, 130.8, 129.9, 127.8, 124.9, 124.7, 121.0, 106.0, 101.4, 101.1, 98.84,
93.06, 62.78, 61.35, 14.53 ppm; MALDI-TOF MS: m/z calcd for
C49H36BrN4O6Zn [M+H]+: 922.1; found: 921.5.
4-(Bromophenyl)-1,3-dioxolane: p-Bromobenzaldehyde (5 g, 2.7ꢀ
10ꢀ2 mol), ethylene glycol (3.2 mL, 5.9ꢀ10ꢀ2 mol), p-TsOH·H2O (1.02 g,
5.4ꢀ10ꢀ3 mol), and benzene (100 mL) were placed in a 300 mL flask
equipped with a Dean–Stark tube. After the reaction mixture had been
stirred for 6 h at reflux under an Ar atmosphere, the reaction was
quenched by the addition of ice-cold saturated aqueous NaHCO3. The or-
ganic layer was washed with saturated aqueous NaHCO3 and water, and
dried over anhydrous Na2SO4. The solvent was evaporated to afford the
title compound as a pale yellow oil (6 g, 97%). TLC (silica gel, CHCl3):
ZnP–Tripod: Compound 8 (12.4 mg, 1.4ꢀ10ꢀ5 mol), 6 (13.6 mg, 2.1ꢀ
2ACTHNUTRGNEUNG
10ꢀ5 mol), [Pd (dba)3] (4 mg, 3.9ꢀ10ꢀ6 mol), and AsPh3 (10 mg, 3.3ꢀ
10ꢀ5 mol) were placed in a Schlenk flask. The flask was evacuated and re-
placed with Ar gas, and then dry THF (1 mL) and dry Et3N (0.2 mL)
were added and the mixture was degassed by freeze–thaw cycles. After
the reaction mixture had been stirred for 48 h at room temperature, [Pd2-
Rf =0.6; 1H NMR (600 MHz, CDCl3, 258C, TMS): d=7.51 (d, J
8.4 Hz, 2H; Ph), 7.35 (d, J(H,H)=8.4 Hz, 2H; Ph), 5.77 (s, 1H; CH),
(H,H)=6.6 Hz, 2H; CH2), 4.03 ppm (t, J(H,H)=6.6 Hz, 2H;
ACHTUNGTRNE(NUNG H,H)=
AHCTUNGTRENNUNG
(dba)3] (1.5 mg, 1.5ꢀ10ꢀ6 mol) and AsPh3 (3.4 mg, 1.1ꢀ10ꢀ5 mol) were
AHCTUNGTRENNUNG
added. After stirring for 6.5 h at room temperature, the reaction was ter-
minated by evaporating the solvent. The residue was purified with a
silica gel column eluting with CHCl3/MeOH 9:1. The third band was col-
lected to afford the title compound as a green solid (8.7 mg, 43%). TLC
(silica gel, CHCl3/MeOH 9:1): Rf =0.5; 1H NMR (600 MHz, CDCl3,
4.11 (t, J
N
ACHTUNGTRENNUNG
CH2).
4-(Trimethylsilylethynyl)phenyl-1,3-dioxolane: 4-(Bromophenyl)-1,3-di-
2A
oxolane (1 g, 4.4ꢀ10ꢀ3 mol), [PdCl (PPh3)2] (61 mg, 8.7ꢀ10ꢀ5 mol), and
CTHUNGTRENNUNG
CuI (17 mg, 8.9ꢀ10ꢀ5 mol) were placed in a test tube with a screw cap.
The test tube was evacuated and replaced with Ar gas. Dry THF (5 mL),
dry Et3N (1 mL), and trimethylsilylacethylene (0.9 mL, 6.5 ꢀ10ꢀ3 mol)
were added and the test tube was sealed under an Ar atmosphere. The
reaction mixture was heated to 808C and stirred for 25 h. The resulting
solution was cooled to room temperature and the solvent was evaporat-
ed. The residue was passed through a short silica gel column (hexane/
EtOAc 2:1) to remove insoluble black materials. The crude brown oil
was purified by distillation under reduced pressure. The second fraction
afforded the title compound as a pale yellow oil (437 mg, 40%). B.p.
1208C/0.045 KPa; TLC (silica gel, CHCl3): Rf =0.6; 1H NMR (600 MHz,
258C, TMS): d=9.73 (d,
(H,H)=4.2 Hz, 2H; b-pyrrole), 8.80 (d, J
role), 8.74 (d, J(H,H)=4.2 Hz, 2H; b-pyrrole), 8.42 (d, J
4H; Ph), 8.23 (d, J(H,H)=7.8 Hz, 4H; Ph), 8.04 (d, J
2H; Ph’), 7.83 (d, J(H,H)=8.4 Hz, 2H; Tripod-Ph’), 7.68 (d, J
7.8 Hz, 2H; Ph’), 7.30 (d, J(H,H)=8.4 Hz, 6H; Tripod-Ph), 7.23 (d,
(H,H)=8.4 Hz, 2H; Tripod-Ph’), 7.16 (d, J(H,H)=8.4 Hz, 6H; Tripod-
Ph), 6.75 (brs, 6H; Tripod-Py), 5.95 (s, 1H; CH), 4.59 (q, J(H,H)=
7.2 Hz, 4H; CH2CH3), 4.22 (t, (H,H)=7.2 Hz, 2H; CH2), 4.12 (t,
(H,H)=7.2 Hz, 2H; CH2), 3.2–3.8 (brs; Tripod-Py), 1.56 ppm (t,
(H,H)=7.2 Hz, 6H; CH2CH3); 1H NMR (600 MHz, CDCl3/2 drops of
(H,H)=4.2 Hz, 2H; b-pyrrole),
(H,H)=4.2 Hz, 2H; b-pyrrole), 8.81 (d, J(H,H)=4.2 Hz, 2H; b-
pyrrole), 8.80 (d, J(H,H)=4.2 Hz, 2H; b-pyrrole), 8.58 (d, J(H,H)=
5.4 Hz, 6H; Tripod-Py), 8.44 (d, J(H,H)=7.8 Hz, 4H; Ph), 8.25 (d,
(H,H)=7.8 Hz, 4H; Ph), 8.03 (d, J(H,H)=8.4 Hz, 2H; Ph’), 7.95 (d,
(H,H)=8.4 Hz, 2H; Tripod-Ph’), 7.68 (d, J(H,H)=7.8 Hz, 2H; Ph’),
(H,H)=8.4 Hz, 6H; Tripod-Ph), 7.41 (d, J(H,H)=8.4 Hz, 2H;
Tripod-Ph’), 7.38 (d, J(H,H)=5.4 Hz, 6H; Tripod-Py), 7.35 (d, J(H,H)=
8.4 Hz, 6H; Tripod-Ph), 5.95 (s, 1H; CH), 4.59 (q, J(H,H)=7.2 Hz, 4H;
CH2CH3), 4.21 (t, J(H,H)=7.2 Hz, 2H; CH2), 4.12 (t, J(H,H)=7.2 Hz,
2H; CH2), 1.56 ppm (t,
(H,H)=7.2 Hz, 6H; CH2CH3); 13C NMR
JACHTUNGTRENNUNG
J
N
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
J
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
J
J
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
CDCl3, 258C, TMS): d=7.47 (d, J
(H,H)=8.4 Hz, 2H; Ph), 5.79 (s, 1H; CH), 4.11 (t, J
CH2), 4.03 (t, J(H,H)=7.2 Hz, 2H; CH2), 0.25 ppm (s, 9H; CH3).
ACHTUNGTRENNUNG
[D5]pyridine, 258C, TMS): d=9.72 (d, J
9.70 (d, J
ACHTUNGTRENNUNG
J
N
ACHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
5,15-Dibromo-10,20-bis(4-ethoxycarbonylphenyl)porphyrinatozinc(II)
(7): 5,15-Dibromo-10,20-bis(4-ethoxycarbonylphenyl)porphyrin (188 mg,
2.5ꢀ10ꢀ4 mol)[20] was dissolved in CHCl3 (30 mL) and a saturated zinc
acetate dihydrate solution in MeOH (2 mL) was added. The mixture was
stirred for 3 h at room temperature and then washed with water. The or-
ganic layer was dried over anhydrous Na2SO4 and the solvent was evapo-
rated. The resulting material was recrystallized twice from CHCl3/MeOH
to give the title compound as purple crystals (169 mg, 83%). TLC (silica
gel, CHCl3): Rf =0.2; 1H NMR (600 MHz, CDCl3, 258C, TMS): d=9.69
AHCTUNGTRENNUNG
J
J
C
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
7.55 (d, J
N
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
(150 MHz, CDCl3, 258C): d=166.9, 152.2, 151.9, 149.6, 149.4, 147.4,
147.3, 146.6, 145.4, 138.2, 134.5, 132.3, 132.2, 131.6, 131.39, 131.36, 131.2,
131.03, 130.95, 130.9, 130.8, 129.7, 127.7, 126.9, 125.1, 125.0, 122.5, 121.5,
120.1, 103.4, 101.4, 101.0, 96.41, 95.95, 93.86, 93.50, 86.52, 65.43, 65.00,
61.31, 29.70, 14.53 ppm; UV/Vis (pyridine): lmax (loge)=456.5 (5.57),
(d, J
N
ACHTUNGTRENNUNG
role), 8.44 (d, J
N
ACHTUNGTRENNUNG
Ph), 4.60 (q, J
N
ACHTUNGTRENNUNG
6H; CH3).
Chem. Eur. J. 2009, 15, 2317 – 2327
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2325