diazabicyclo[5.4.0]undec-7-ene (119 µL, 0.80 mmol) were stirred in 3 mL of boiling isoamil alcohol for 4 h (TLC-
control: SiO , F , toluene). The reaction mixture was cooled to room temperature and a MeOH:H O (4:1 V/V)
2
254
2
o
mixture was added. The precipitate was filtered and washed with a MeOH:H O (4:1 V/V) mixture and dried at 70 C
2
to give compound 1b (164.2 mg, 64%). UV-vis (THF): λmax (nm) (I/I ) 361 (0.61); 639 (0.37); 696 (1.00). IR
max
-
1
(
vaseline oil): ν (cm ) 1026-1095 (st C-Cl); 1556 (γ pyrrole); 1377 ( С- О) ; 1556 ( С= О) . MS (MALDI-TOF): m/z 1194
[
M-OAc-Cl]; 1212 [M-OAc-Cl+H O]; 1229 [M-OAc]; 1247 [M-OAc+H O]; 1346 [M-OAc-Cl+DHB]. MS (MALDI-
2
2
TOF/TOF): m/z Found: [M-OAc] 1229.4486; molecular formula C Cl ErN requires [M-OAc] 1229.4447.
3
2
16
8
Preparation of 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecachlorophthalocyaninato lutetium acetate 1c:
Tetrachlorophthalonitrile (213.0 mg, 0.80 mmol), Lu(OAc) ·4H O (85.6 mg, 0.20 mmol) and 1,8-
3
2
diazabicyclo[5.4.0]undec-7-ene (119 µL, 0.80 mmol) were stirred in 3 mL of boiling isoamil alcohol for 4 h (TLC-
control: SiO , F , toluene). The reaction mixture was cooled to room temperature and a MeOH:H O (4:1 V/V)
2
254
2
o
mixture was added. The precipitate was filtered and washed with a MeOH:H O (4:1 V/V) mixture and dried at 70 C
2
to give compound 1c (202.0 mg, 78%). UV-vis (THF): λmax (nm) (I/I ) 363 (0.68); 642 (0.33); 699 (1.00). IR
max
-
1
(
vaseline oil): ν (cm ) 1091 (st C-Cl); 1554 (γ pyrrole); 1377 ( С- О) ; 1554 ( С= О) . MS (MALDI-TOF): m/z 1444
[
M+DHB]; 1502 [M-OAc-Cl+2DHB]; 1536 [M-OAc+2DHB]; 1597 [M+2DHB]; 1655 [M-Cl+3DHB]; 1692 [M-
OAc+3DHB]. MS (MALDI-TOF/TOF): m/z Found: [M-OAc+2DHB] 1536.5028; molecular formula
C H Cl LuN O requires [M-OAc+2DHB] 1536.5046.
4
6
10
16
8
8
(
b) Approach with hexadecachlorophthalocyanine
Preparation of 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecachlorophthalocyaninato magnesium 2:
Tetrachlorophthalonitrile (426.0 mg, 1.60 mmol), Mg(OAc) ·4H O (172.0 mg, 0.40 mmol) and 1,8-
2
2
diazabicyclo[5.4.0]undec-7-ene (238 µL, 1.60 mmol) were stirred in 6 mL of boiling isoamil alcohol for 4 h (TLC-
control: SiO , F , toluene). The reaction mixture was cooled to room temperature and a MeOH:H O (4:1 V/V)
2
254
2
o
mixture was added. The precipitate was filtered and washed with a MeOH:H O (4:1 V/V) mixture and dried at 70 C
2
to give compound 2 (321.0 mg, 74%). UV-vis (THF): λmax (nm) (I/I ) 365 (0.51); 646 (0.45); 695 (1.00). IR (vaseline
max
-
1
oil): ν (cm ) 1051 - 1101 (st C-Cl); 1556 (γ pyrrole). MS (MALDI-TOF): m/z 1009 [M-2Cl]; 1027 [M-2Cl+H O];
2
1
045 [M-Cl]; 1063 [M-Cl+H O]; 1081 [M+H]. MS (MALDI-TOF/TOF): m/z Found: [M+H] 1080.5202; molecular
2
formula C HCl MgN requires [M+H] 1080.5191.
3
2
16
8
Preparation of 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecachlorophthalocyanine 3: The magnesium
complex 2 (216.0 mg, 0.20 mmol) was dissolved in concentrated sulphuric acid (10 mL). This solution was poured
into the ice. A green precipitate formed at the same time. This precipitate was filtered and washed with water until
the neutral pH and MeOH to give 3 (186.0 mg, 87%). UV-vis (THF): λmax (nm) (I/I ) 358 (0.76); 659 (1.00); 697
max
-
1
(
0.95). IR (vaseline oil): ν (cm ) 1039 - 1105 (st C-Cl); 1564 (γ pyrrole); 3300 (st NH). MS (MALDI-TOF): m/z 995