JOURNAL OF CHEMICAL RESEARCH 2017 295
Synthesis of metallophthalocyanines (4–12); general procedure
Electronic Supplementary Information
A mixture of desired phthalonitriles, compound 1 (0.073 g, 0.24 mmol)
or compound 2 (0.06 g, 0.24 mmol,), N,N-dimethylaminoethanol
(DMAE) (4 mL), DBU (1mL) and the corresponding metal salts
(0.06 mmol) were stirred at 150 °C for 24 h under N2. The progress
of the reaction was monitored by TLC. The mixture was left to
cool to r.t. then treated with ethylacetate to precipitate the product.
The crude product was collected by filtration and washed with
water, ethanol and ether, and then dried. The obtained green solid
product was purified by column chromatography (silica gel) with
chloroform:methanol (100:5) as the solvent system.
The ESI is available through:
stl.publisher.ingentaconnect.com/content/stl/jcr/supp-data
Received 11 February 2017; accepted 31 March 2017
Paper 1704596
Published online: 4 May 2017
References
Zn(II) phthalocyanine (4): White solid; m.p. 330 °C; yield 80%;
FTIR (KBr) (n cm−1): 3024 (C–Harom), 1387 (C–C), 1270 (C–N), 1607
(C=C), 1480 (C=N), 902 (Zn–N); 1H NMR (400 MHz, DMSO-d6): δ
3.75 (s, 4H, Hald), 6.87–7.72 (m, 16Harom), 3.1 (t, 3J = 6.00 Hz, 8H, H2¢),
4.32 (t, J = 6.20 Hz, 8H, H1¢); UV-Vis (DMF, λmax nm (log ε)): 636
(4.632), 697 (5.064), 343 (4.834). Anal calcd for C72H64N8O12Zn: C,
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2
3
3
4
5
6
66.58; H, 4.96; N, 8.62; found: C, 66.7; H, 5.2; N, 8.7%.
Ni(II) phthalocyanine (5): Elution solvent system:
chloroform:methanol (100:3); m.p. 330 °C; yield 76%; FTIR (KBr) (n
cm−1): 3020 (C–Harom), 1390 (C–C), 1272 (C–N), 1602 (C=C), 1482
7
1
(C=N), 903 (Ni–N); H NMR (400 MHz, DMSO-d6): δ 3.73 (s, 4H,
3
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3J = 6.20 Hz, 8H, H1¢); UV-Vis (DMSO, λmax nm (log ε)): 614 (4.436),
675 (4.968), 332 (4.645). Anal calcd for C72H64N8O12Ni: C, 66.93; H,
4.99; N, 8.67; found: C, 66.7; H, 5.1; N, 8.8%.
Co(II) phthalocyanine (6): m.p. 325 °C; yield 82%; FTIR (KBr) (n
cm−1): 3020 (C–Harom), 1385 (C–C), 1269 (C–N), 1606 (C=C), 1479
(C=N), 902 (Co–N); UV-Vis (DMSO, λmax nm (log ε)): 614 (4.320),
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(C=N), 900 (Cu–N); UV-Vis (DMSO, λmax nm (log ε)): 622 (4.462),
708 (5.054), 334 (4.728). Anal calcd for C72H64N8O12Cu: C, 66.68; H,
4.97; N, 8.64; found: C, 66.7; H, 5.1; N 8.7%.
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Zn(II) phthalocyanine (9): m.p. 315 °C; yield 75%; FTIR (KBr) (n
cm−1): 3015 (C–Harom), 1388 (C–C), 1228 (C–N), 1610 (C=C), 1476
1
(C=N), 905 (Zn–N); H NMR (400 MHz, DMSO-d6): δ 9.1 (s, 4H,
Hald), 6.81–7.82 (m, 28Harom); UV-Vis (DMSO, λmax nm (log ε)): 629
(4.541), 683 (4.986), 339 (4.673). Anal calcd for C60H32N8O8Zn: C,
68.09; H, 3.04; N, 10.58; found: C, 68.2; H, 3.1; N, 10.4%.
Ni(II) phthalocyanine (10): m.p. 320 °C; yield 95%; FTIR (KBr) (n
cm−1): 3016 (C–Harom), 1393 (C–C), 1234 (C–N), 1609 (C=C), 1480
1
(C=N), 910 (Ni–N); H NMR (400 MHz, DMSO-d6): δ 9.2 (s, 4H,
Hald), 6.85–7.85 (m, 28Harom); UV-Vis (DMSO, λmax nm (log ε)): 615
(4.159), 678 (4.943), 345 (4.617). Anal calcd for C60H32N8O8Ni: C,
68.52; H, 3.06; N, 10.65; found: C, 68.7; H, 3.1; N 10.7%.
Co(II) phthalocyanine (11): m.p. 330 °C; yield 74%; FTIR (KBr) (n
cm−1): 3015 (C–Harom), 1390 (C–C), 1236 (C–N), 1614 (C=C), 1475
(C=N), 900 (Co–N); UV-Vis (DMSO, λmax nm (log ε)): 615 (4.195),
686 (4.861), 334 (4.538). Anal calcd for C60H32N8O8Co: C, 68.51; H,
3.06; N, 10.65; found: C, 68.6; H, 3.1; N, 10.7%.
Cu(II) phthalocyanine (12): m.p. 315 °C; yield 80%; FTIR (KBr)
(n cm−1): 3017 (C–Harom), 1391 (C–C), 1231 (C–N), 1612 (C=C), 1478
(C=N), 910 (Cu–N); UV-Vis (DMSO, λmax nm (log ε)): 615 (4,195),
686 (4.861), 310 (4.238). Anal calcd for C60H32N8O8Cu: C, 68.21; H,
3.05; N, 10.60; found: C, 68.5; H, 3.2; N, 10.7%.
Acknowledgements
The authors would like to thank the Deanship of Scientific
Research at King Saud University for funding the work through
the research group project, no. PRG-1436-02.
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