Please do not adjust margins
New Journal of Chemistry
Page 9 of 11
DOI: 10.1039/C6NJ03886G
Journal Name
ARTICLE
General procedure for preparation of
Magnesium(II) 2,3-bis(4-methoxyphenyl)-1,4-
(diaza)phthalocyanine (8)
6 and 7 were prepared according to Obtained product was purified by column chromatography
tetrapyrazinoporphyrazines (6 and 7)
Symmetrical macrocyclces
classical Linstead procedure.13 Magnesium turnings (1 equiv) using silica gel and eluents: CH2Cl2, n-hexane/THF (5:1),
were refluxed in n-butanol (7 mL for each mmol of substrate) CH2Cl2/MeOH (50:1) to give product as a deep green film (18%
1
with a catalytic amount of iodine for 3 hours. After cooling yield). Rf (CH2Cl2/MeOH 35:1) 0.43. H NMR (800 MHz, DMSO-
down of the slurry, 2,3-dicyanopyrazine derivative was added d6) δ, ppm: 9.38 (m, 4H), 8.24 (m, 4H), 7.90 (m, 6H), 7.17 (m,
and the mixture was refluxed for 20 hours. After cooling down, 6H), 3.96 (s, 3H), 3.95 (s, 3H). 13C NMR (201 MHz, DMSO-d6) δ,
reaction mixture was sonicated and Celite filtered, which was ppm: 159.6, 155.4, 155.0, 154.0, 152.3, 146.5, 145.7, 138.5,
rinsed with CH2Cl2. Filtrates were evaporated to dryness with 138.0, 131.4, 131.3, 131.3, 129.8, 129.5, 129.2, 122.5, 122.4,
addition of toluene, giving dark-green solid residue.
Magnesium(II) 2,3,9,10,16,17,23,24-octakis(4-
113.7, 113.6, 55.1, 55.0. UV/Vis (DMSO): λmax nm (log ε) 368
nm (4.66), 603 (4.22), 667 (4.95). HRMS (MALDI) Found [M]+
750.2125; molecular formula C44H26MgN10O2 requires [M]+
750.2091.
methoxyphenyl)-1,4,8,11,15,18,22,25-
(octaaza)phthalocyanine (6)
Magnesium(II) 2,3-bis[4-[3,5-
The obtained product was precipitated from CH2Cl2/n-hexane
mixture. Solid precipitate was filtered on blotting paper,
washed with n-hexane, CH3OH and acetone, then rinsed down
bis(benzyloxy)benzyloxy]phenyl]-1,4-(diaza)phthalocyanine
(9)
with CH2Cl2. Evaporation of the solvent gave 6 as a green Obtained product was purified by means of column
powder (13%): 1H NMR (800 MHz, DMSO-d6): δ, ppm: 7.41 (m, chromatography using silica gel and eluents: CH2Cl2, n-
16H), 6.95 (bs, 16H), 3.78 (s, 24H). 13C NMR (201 MHz, DMSO- hexane/AcOEt (7:2), CH2Cl2/CH3OH (200:1) to give a deep
1
d6) δ, ppm: 159.7, 131.3, 113.9, 55.3. UV/Vis (DMSO) λmax nm green film (48% yield). Rf (CH2Cl2/CH3OH 50:1) 0.61. H NMR
(log ε) 384 nm (4.91), 597 (4.28), 658 (5.08). HRMS (MALDI) (800 MHz, DMSO-d6) δ, ppm: 9.13-8.59 (m, 6H), 8.09-7.93 (m,
Found: [M]+ 1393.4336; molecular formula C80H56MgN16O8 6H), 7.89 (m, 4H), 7.47 (m, 8H), 7.41 (m, 8H), 7.35 (m, 4H), 7.22
requires [M]+ 1393.4345.
Magnesium(II) 2,3,9,10,16,17,23,24-octakis[4-[3,5-
(m, 4H), 6.81 (m, 4H), 6.69 (m, 2H), 5.18 (s, 4H), 5.13 (s, 8H).
13C NMR (201 MHz, DMSO-d6) δ, ppm: 159.6, 158.7, 154.7,
154.4, 153.8, 153.5, 152.4, 152.2, 152.0, 145.8, 145.7, 139.3,
138.5, 138.1, 138.0, 136.9, 132.5, 131.9, 129.4, 129.2, 128.4,
128.4, 128.3, 127.9, 127.7, 127.7, 122.5, 114.6, 106.6, 101.3,
69.4, 69.3. UV/Vis (DMSO): λmax, nm (log ε) 363 nm (4.37), 604
(4.36), 626 (4.38), 676 (5.07). HRMS (MALDI) Found [M+H]+
1327.4710; molecular formula C84H58MgN10O6+H+ requires
[M+H]+ 1327.4469. HPLC purity (see Supplementary data).
X-ray crystallography
bis(benzyloxy)benzyloxy]phenyl]-1,4,8,11,15,18,22,25-
(octaaza)phthalocyanine (7)
Obtained green oil was purified on silica-gel using CH2Cl2 with
1% triethylamine. Collected samples were vaporized and
precipitated from CH2Cl2/CH3OH. Formed green solid was
subsequently washed with methanol, hexane and acetone to
give 32% yield of pure product as green powder. Rf (CH2Cl2+1%
triethylamine) 0.22. 1H NMR (800 MHz, DMSO-d6) δ, ppm: 7.79
(bs, 16H), 7.40 (d, J = 7.5 Hz, 32H), 7.34 (t, J = 7.5 Hz, 32H), 7.28
(t, J = 7.5 Hz, 16H), 7.04 (bs, 16H), 6.77 (s, 16H), 6.65 (s, 8H),
5.10 (s, 16H), 5.06 (s, 32H). 13C NMR (201 MHz, DMSO-d6) δ,
ppm: 159.43, 158.68, 152.98, 149.67, 138.91, 136.65, 131.46,
127.89, 127.82, 127.28, 127.06, 127.00, 114.25, 106.50,
101.42, 69.31, 69.20. UV/Vis (DMSO): λmax nm (log ε) 388 nm
(5.06), 597 (4.48), 658 (5.32). HRMS (MALDI) Found [M]+
3700.4450; molecular formula C240H184MgN16O24 requires [M]+
3700.4267. HPLC purity (see Supplementary data).
Reflection intensities for 5b and 5c were measured at 130 K
with an Oxford Diffraction Xcalibur E diffractometer using
MoKα radiation and with an Oxford Diffraction SuperNova
diffractometer using hi-flux micro-focus Nova CuKα radiation,
respectively. Data were processed with CrysAlis PRO
software.39 The structures were solved by direct methods
using SIR201440 and refined by full matrix least-squares based
on F2 (SHELXL-2014).41 C-bound hydrogen atoms were placed
at idealized positions. All hydrogen atoms were refined as
riding on their carriers with Uiso(H)=1.2Ueq (CH, CH2).
General procedure for synthesis of A3B type porphyrazines (8
and 9)
Crystal data for 5b: C32H22N4O2, M = 494.53 g/mol, monoclinic,
space group P21/n, a = 8.2968(3) Å, b = 11.2161(5) Å, c =
27.6291(10) Å, β = 97.453(3)°, V = 2549.38(17) Å3, Z = 4, T =
130(2) K, μ(MoKα) = 0.082 mm-1, Dcalc = 1.288 g/cm3, 14332
The magnesium butanolate solution was prepared according
to the previously described procedure [13]. Magnesium
turnings (5 equiv) were refluxed in n-butanol (7 mL for each
mmol of substrates) with a catalytical amount of iodine for 3
hours. After cooling down of the slurry, 2,3-dicyanopyrazine
derivative (1 equiv) and 1,2-dicyanobenzene (10 equiv) were
added and the mixture was refluxed for another 20 hours.
After cooling down, reaction mixture was sonicated and
filtered through Celite, which was rinsed with toluene and
CH2Cl2. Filtrates were evaporated to dryness giving dark-green,
solid residue.
reflections measured to θmax = 25.35°, 4651 unique (Rint
=
0.0376, Rsigma = 0.0506). The final R indices for 3332 reflections
with I > 2σ(I) and 343 refined parameters are R1= 0.046, wR2 =
0.086 (R1= 0.0741, wR2 = 0.0969 for all data)
Crystal data for 5c: C60H46N4O6∙2(CH2Cl2), M =1088.86 g/mol,
monoclinic, space group C2/c, a = 23.8249(7) Å, b = 15.5643(4)
Å, c = 16.2565(4) Å, β = 117.473(3)°, V = 5348.4(3) Å3, Z = 4, T =
130(2) K, μ(CuKα) = 2.474 mm-1, Dcalc = 1.352 g/cm3, 12425
reflections measured to θmax = 68.25°, 4913 unique (Rint
=
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins