1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.4.7 5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[ 3,5 2 ]-Ethano- 5 6 -Methyl- 3 1 -Oxo-5, 10, 15, 20-
O
152
N
crystalline solid.
Tetraphenylporphyrinato-Zinc(II), Zn(II)-53
In a 100 mL round bottom flask, free base cycloketo-
porphyrin 53 (50 mg, 56 μmol) is dissolved in 20 mL of CH2Cl2
and a concentrated methanolic solution of 245 mg
(1.12 mmol, 20 eq.) is added. The mixture is stirred at rt for
1 h before water is added. The organic layer is separated and
washed with water twice. After drying over MgSO4, the
obtained green product is purified by FC (silica,
hexanes:CH2Cl2 = 2:3) to give 52.4 mg (54.8 μmol) of pure
Zn(II)-53 in 97.8 % yield based on 53 as green-purple
1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = 1.02 (s, 3 H, CH3), 1.48 (s, 9 H, t-Bu-H), 1.58 (s, 18 H,
t-Bu-H), 1.60 (s, 9 H, t-Bu-H), 3.89 (m, 1 H, CH2), 5.47 (m, 1 H, CH2), 7.28 (d, 4 J = 1.5 Hz, 1 H,
Ar’H), 7.55 (m, 1 H, ArH), 7.63 (m, 2 H, ArH), 7.68 (dd, 3 J = 8.1 Hz, 4 J = 2.0 Hz, 1 H, ArH), 7.73-
7.84 (m’s, in all 5 H, Ar’H+ArH), 7.88 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 1 H, ArH), 8.14 (dd,
3 J = 7.8 Hz, 4 J = 1.7 Hz, 1 H, ArH), 8.25 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 1 H, ArH), 8.31 (dd,
3 J = 7.8 Hz, 4 J = 1.5 Hz, 1 H, ArH), 8.77-8.82 (m, 5 H, β-H), 8.93 (d, 3 J = 4.6 Hz, 1 H, β-H), 9.06
(m, 1 H, β-H).
13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 31.4, 31.6 (2 signals), 34.6, 34.8 (2 signals),
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.
N
Zn
N
N
Zn(II)-53
C 63 H 62 N 4 OZn
M = 956.58 g·mol -1
MS (FAB+, NBA): m/z (%) = 954 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 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 [M -1 ·cm -1 ]) = 4469 (256000), 576 (10700), 633 (12200).
EA: C63H62N4OZn·CH3OH. Calc.: C 77.75, H 6.73, N 5.67; found: C 77.60, H 6.57, N 5.31.