1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.5 A2B2-Type Poly-Annulated Cycloketo-Porphyrin Systems and
162
Precursors
6.2.5.1 5 4 , 10 4 , 15 4 , 20 4 - Tetra - t - Butyl - 5 2 , 5 6 - Bis - (Cyanomethyl) - 5 , 10 , 15 , 20 -
NC
Tetraphenylporphyrin, 72
Using GP I, bromomethyl porphyrin 46 (400 mg, 0.390 mmol)
is reacted under the following conditions: a.: CH2Cl2 (50 mL),
Zn(OAc)2·2 H2O (1.71 g, 7.8 mmol, 20 eq); b.: KCN (1.90 g,
29.3 mmol, 75 eq), PEG 400 (50 mL). Final purification is
achieved by FC over silica using CH2Cl2 and hexanes as eluent
(ratio 3 : 1). The pure product 72 is obtained as dark purple
powder in 338 mg (0.369 mmol) yield, equiv. to 95 % based
on 46.
1 H NMR (300 MHz, rt, CDCl3): δ [ppm] = -2.69 (s, 2 H, NH), 1.61 (s, 27 H, t-BuH), 1.67 (s, 9 H,
t-BuH), 3.28 (s, 4 H, CH2), 7.77 (m, 6 H, ArH), 7.98 (s, 2 H, Ar’H), 8.14 (m, 6 H, ArH), 8.52 (d,
3 J = 4.7 Hz, 2 H, β-H), 8.90 (s, 4 H, β-H), 8.93 (d, 3 J = 4.7 Hz, 2 H, β-H).
13 C NMR (75.5 MHz, rt, CDCl3): δ [ppm] = 31.3, 31.5, 32.3, 34.4, 34.7, 111.7, 120.5, 121.2,
123.1, 126.6, 130.6, 131.5, 131.6, 132.0, 134.2, 138.9, 139.1, 139.9, 140.0, 149.3, 149.4,
149.8, 149.9, 150.1, 151.7.
MS (FAB+, NBA): m/z (%) = 918 (100) [MH] +· .
IR (ATR): 𝜈� [cm -1 ] = 3320, 3030, 2957, 2903, 2868, 1603, 1559, 1505, 1475, 1397, 1363, 1334,
1266, 1220, 1197, 1185, 1108, 1069, 1023, 965, 930, 849, 807, 733.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (392000), 518 (17800), 553 (9170), 591 (5900),
648 (5420).
CN
N
NH HN
N
72
C 64 H 64 N 6
M = 917.23 g·mol -1
EA: C64H64N6·H2O·0.5 C6H14. Calc.: C 82.25, H 7.52, N 8.59; found: C 82.19, H 7.41, N 8.32.