ER(III) AND LU(III) COMPLEXES OF 2(3),9(10),16(17),23(24)-TETRAKIS
3
2(3),9(10),16(17),23(24)-tetrakis-[4-(1-methyl-1-
H, 5.52; N, 4.54. IR (KBr): u, cm-1 3056, 3027 (Ar-H),
2966, 2930, 2867 (CH3), 1267 (Ar-O-Ar) (Suppl. 9).
MS (MALDI-TOF) m/z 2430 [M + 2H]- (Suppl. 4);
calculated [M] 2428.
Bis(2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato) Lu(III) (8a)
was obtained according to method A.Yield: 16% (0.15 g).
Elemental analysis found: C, 80.00; H, 5.65; N, 4.66%;
Anal. calculated for (C304H256LuN16O16) C, 79.94; H,
5.71; N, 4.59. IR (KBr): u, cm-1 : 3059, 3026 (Ar-H),
2963, 2925, 2859 (CH3), 1266 (Ar-O-Ar) (Suppl. 10).
MS (MALDI-TOF) m/z 4562 [M + 2H]+; calculated [M]
4564. Method B. Yield: 0.19 g (21%).
2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Er(III) chlo-
ride (6b) was obtained according to method A. Yield:
46% (0.22 g). Elemental analysis found: C, 76.12; H,
5.42; N, 4.67%; Anal. calculated for (C152H129ClErN8O8)
C, 76.03; H, 5.46; N, 4.60. 1H NMR (DMSO-d6: CDCl3):
d, ppm 8.26–8.20 m (H1; 8H), 7.97–7.95 m (H4; 16H),
7.61–6.59 m (H5,6; 24H), 7.21–6.93 m (H2,3; 32H),
1.63 s (CH3; 24 H). IR (KBr): u, cm-1 3055, 3026 (Ar-H),
2966, 2929, 2865 (CH3), 1267 (Ar-O-Ar).
phenylethyl)phenoxy]phthalocyaninato Lu(III) acetate
(3a) was obtained according to method B. Yield: 32%
(0.10 g). Elemental analysis found: C, 71.11; H, 4.76;
N, 7.06%; Anal. calculated for (C94H75LuN8O6) C, 70.99;
1
H, 4.82; N, 7.01. H NMR (DMSO-d6: CDCl3): d, ppm
8.29 s (H3; 4H), 7.86–7.78 m (H1; 4H), 7.44–7.13 m
(H2,5,6,7,8; 32H), 7.07–7.00 m (H4; 8H), 2.09 s (CH3;
3H), 1.66 s (CH3; 24H)IR (KBr): u, cm-1 3051, 3030
(Ar-H), 2966, 2926, 2855 (CH3), 1230 (Ar-O-Ar). MS
(MALDI-TOF) m/z 1588 [M + H]+; calculated [M] 1587.
Bis(2(3),9(10),16(17),23(24)-tetrakis-[4-(1-methyl-
1-phenylethyl)phenoxy]phthalocyaninato) Lu(III) (4a)
was obtained according to method A. Yield: 7% (0.04 g).
Elemental analysis found: C, 76.68; H, 5.04; N, 7.78%;
Anal. calculated for (C184H144LuN16O8) C, 76.42; H, 5.11;
N, 7.71. IR (KBr): u, cm-1 3052, 3030 (Ar-H), 2963,
2925, 2850 (CH3), 1234 (Ar-O-Ar). MS (MALDI-TOF)
m/z 2884 [M + 2H]+; calculated [M] 2882. Method B.
Yield: 9% (0.05 g).
2(3),9(10),16(17),23(24)-tetrakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Er(III) chlo-
ride (2b) was obtained according to method A. Yield:
48% (0.14 g). Elemental analysis found: C, 70.00; H,
4.66; N, 7.20%; Anal. calculated for (C92H72ClErN8O4)
C, 69.89; H, 4.71; N, 7.17. IR (KBr): u, cm-1 3052,
3029 (Ar-H), 2966, 2924, 2856 (CH3), 1232 (Ar-O-Ar).
MS (MALDI-TOF) m/z 1675 [M + 3K]+ (Suppl. 2);
calculated [M] 1556.
2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Er(III) acetate
(7b) was obtained according to method B. Yield: 35%
(0.17 g). Elemental analysis found: C, 76.40; H, 5.45; N,
4.63%; Anal. calculated for (C154H131ErN8O10) C, 76.36;
1
H, 5.50; N, 4.60. H NMR (DMSO-d6: CDCl3): d, ppm
2(3),9(10),16(17),23(24)-tetrakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Er(III) acetate
(3b) was obtained according to method B. Yield: 38%
(0.21 g). Elemental analysis found: C, 71.46; H, 4.78; N,
7.09%; Anal. calculated for (C94H75ErN8O6) C, 71.32; H,
4.80; N, 7.02. IR (KBr): u, cm-1 3050, 3029 (Ar-H), 2964,
2926, 2854 (CH3), 1232 (Ar-O-Ar).
Bis(2(3),9(10),16(17),23(24)-tetrakis-[4-(1-methyl-
1-phenylethyl)phenoxy]phthalocyaninato) Er(III) (4b)
was obtained according to method A.Yield: 10% (0.06 g).
Elemental analysis found: C, 76.88; H, 5.05; N, 7.80%;
Anal. calculated for (C184H144ErN16O8) C, 76.52; H, 5.08;
N, 7.76. IR (KBr): u, cm-1 3051, 3030 (Ar-H), 2962,
2926, 2851 (CH3), 1231 (Ar-O-Ar). MS (MALDI-TOF)
m/z 2875 [M + H]+ (Suppl. 1); calculated [M] 2874.
Method B. Yield: 21% (0.12 g).
8.39–8.19 m (H1, 8H), 7.97–7.95 m (H4, 16H), 7.61–
6.59 d (H5,6; 24H, J 10.60 Hz), 7.24–7.17 m (H3, 16H),
6.96–9.92 d (H2, 16H, J 9.00 Hz), 2.09 s (CH3; 3H) 1.63
s (CH3; 24 H) (Suppl. 6). IR (KBr): u, cm-1 3055, 3026
(Ar-H), 2966, 2931, 2858 (CH3), 1266 (Ar-O-Ar).
Bis(2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato) Er(III) (8b)
was obtained according to method A.Yield: 19% (0.17 g).
Elemental analysis found: C, 80.13; H, 5.66; N, 4.92%;
Anal. calculated for (C304H256ErN16O16) C, 80.09; H,
5.70; N, 4.90. IR (KBr): u, cm-1 : 3055, 3026 (Ar-H),
2967, 2930, 2866 (CH3), 1265 (Ar-O-Ar). MS (MALDI-
TOF) m/z 4559 [M + 3H]+ (Suppl. 5); calculated [M]
4556. Method B. Yield: 23% (0.21 g).
2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Lu(III) chlo-
ride (6a) was obtained according to method A. Yield:
35% (0.16 g). Elemental analysis found: C, 75.87; H,
5.40; N, 4.66%; Anal. calculated for (C152H129ClLuN8O8)
C, 75.72; H, 5.48; N, 4.59. IR (KBr): u, cm-1 3055, 3026
(Ar-H), 2967, 2930, 2869 (CH3), 1266 (Ar-O-Ar).
2,3,9,10,16,17,23,24-octakis-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninato Lu(III) acetate
(7a) was obtained according to method B. Yield: 29%
(0.14 g). Elemental analysis found: C, 76.16; H, 5.44; N,
4.61%; Anal. calculated for (C154H131LuN8O10) C, 76.21;
RESULTS AND DISCUSSION
Selection of rare-earth complexes synthesis
conditions
For the first time, the influence of synthesis conditions
and nature of reagents on yield and composition of
resulting products has been studied. Synthetic procedures
for lanthanide complexes have been carried out under
equal conditions utilizing a general set of compounds,
namely phthalonitrile derivatives containing one or two
4-(1-methyl-1-phenylethyl)phenol fragments, chlorides
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 3–9