Molecules 2016, 21, 16
20 of 24
1
˝
E-Dicarboxylic acid E-17 (83 mg, 82%). H-NMR (500 MHz, dmso-d6, 25 C)
δ
= 8.17 (2H, d, J = 1.5 Hz,
H-4), 7.84 (2H, dd, J = 1.5, 7.8 Hz, H-6), 7.48 (2H, d, J = 7.8 Hz, H-7), 3.18 (8H, m, CH2CH2). 13C-NMR
(75.5 MHz, dmso-d6, 25 ˝C)
δ = 167.9, 152.7, 143.1, 135.5, 129.7, 129.0, 125.6, 125.5, 31.8, 31.0. HRMS,
calc. for C20H16O4: m/z = 321.1121 [M + H]+, found 321.1118.
(3Z)-3-(6-Chlorocarbonylindan-1-ylidene)indane-5-carbonyl chloride (18). Dicarboxylic acid Z-17 (55 mg,
0.17 mmol) was added to a dried 25 mL round-bottomed flask together with dry CH2Cl2 (5 mL), oxalyl
chloride (0.9 mL) and DMF (3 drops). The mixture was stirred at RT under nitrogen atmosphere for
two hours. Volatile components were removed in vacuo and the residue was washed several times
with dry Et2O in which the product was soluble. The heterogeneous Et2O solution was filtrated (using
a grade 3 filter paper) to remove by-products and the filtrate was evaporated to leave the acid chloride
1
Z-18 as a pale yellow solid (yield: 45 mg, 74%). H-NMR (500 MHz, CDCl3, 25 ˝C)
δ = 8.80 (2H, d,
J = 1.8 Hz, H-4), 7.96 (2H, dd, J = 1.8, 8.0 Hz, H-6), 7.43 (2H, dm, J = 8.0 Hz, H-7), 3.10 (4H, m, CH2),
2.90 (4H, m, CH2).
(3Z)-N-(5,10,15,20-tetraphenylporphyrin-2-yl-ato)Zn(II)-3-[6-(5,10,15,20-tetraphenylporphyrin-2-yl-ato)Zn(II)-
carbamoyl)indan-1-ylidene]indane-5-carboxamide (2). TPP-NH2 6 (210 mg, 0.33 mmol) was added to
a dried round-bottomed flask and Z-stif-stilbene dicarboxylic acid chloride Z-18 (42 mg, 0.13 mmol)
dissolved in dry CH2Cl2 (20 mL) was added via syringe. Dry pyridine (0.2 mL) was added and the
mixture was allowed to stir for three days under nitrogen atmosphere and with protection from
light. The solvent was evaporated and the residue redissolved in CH2Cl2. The solution was washed
with HCl (1 M, 50 mL) and brine (5%, 50 mL). The organic phase was then dried over Na2SO4 and
the solvent evaporated. The crude compound was added to a flask together with Zn(OAc)2 2H2O
¨
˝
(1 g), methanol (20 mL), CH2Cl2 (20 mL) and the mixture was stirred at 50 C for one hour. The
solvents were removed by evaporation and the crude metallated compound was purified by column
chromatography (silica, CH2Cl2) followed by a subsequent silica column (CH2Cl2:methanol:acetic acid
96:4:1). The compound was further purified by washing several times with methanol to yield the target
compound Z-2 as a light/air sensitive purple solid (yield: 53 mg, 24%). Rf = 0.13 (dichloromethane).
1H-NMR (500 MHz, CDCl3, 25 ˝C)
δ
= 9.25 (2H, s, H-31), 8.81 (2H, br s, N-H), 8.78 (2H, d, J = 4.5 Hz,
-pyrrole), 8.76 (2H, d, J = 4.5 Hz, -pyrrole), 8.72 (2H, d, J = 4.6 Hz
-pyrrole), 8.38 (2H, d, J = 4.6 Hz, -pyrrole), 8.11 (2H, m, H-4),
β-pyrrole), 8.78 (2H, d, J = 4.5 Hz,
β
β
,
β-pyrrole), 8.43 (2H, d, J = 4.6 Hz,
β
β
8.11–8.07 (8H, m, Ph), 8.01 (4H, m, H-d), 7.77–7.66 (12H, m, Ph), 7.63 (2H, m, H-f), 7.46 (4H, m, H-e),
7.43 (4H, m, H-a), 7.38 (2H, d, J = 7.4 Hz, H-7), 7.09 (2H, m, H-6), 7.08 (2H, m, H-c), 6.90 (4H, m,
H-b), 3.22 (4H, m, CH2-2), 3.05 (4H, m, CH2-1). 13C-NMR (125 MHz, CDCl3, 25 ˝C)
δ = 164.8, 152.0,
150.7, 150.6, 150.2, 149.9, 149.6, 149.5, 149.0, 142.7, 142.6, 142.1, 141.4, 141.1, 140.0, 139.8, 135.3, 134.4,
134.3, 134.2, 133.8, 133.3, 133.0, 132.0, 131.8, 131.7, 131.5, 131.4, 130.9, 128.8, 128.1, 127.43, 127.40, 127.0,
126.7, 126.6, 126.50, 126.46, 126.1, 124.9, 121.9, 121.6, 121.0, 120.23, 120.19, 117.4, 35.3, 31.0. Z-2 UV-Vis
´1
105 M
´1
cm´1). MS (MALDI-MS,
(CH2Cl2)
λ
max: 425 nm (
ꢀ
= 6.0
ˆ
¨
cm´1), 552 nm (
ꢀ
= 5.1
ˆ
104 M
¨
dithranol, positive mode) m/z: 1669 [M + H]+). HRMS: m/z calcd. for C108H70N10O2Zn2, [M + H]+:
1669.4269; found: 1669.4193.
b
c
a
3
3'
4
3a
7
2
5
1
7a
6
d
f
e
Z-2