azO-lInkeD COrner POrPhyrIn SyStemS
489
shielded from light. Iodine (99 mg, 0.75 eq., 3.90 × 10-4
mol) dissolved in DCM (12.5 mL) was added and the
solution was stirred for 30 min. Silver nitrite (120 mg,
1.5 eq., 7.80 × 10-4 mol) dissolved in acetonitrile (12.5
mL) was added. The starting material was consumed
after 1.5 h. The solvents were evaporated, leaving a dark-
purple solid which was redissolved in minimum amount
of DCM and filtered through a cotton wool plug. The sol-
vent was evaporated and the product recrystallized from
DCM/methanol. The product was a grey-purple powder.
Yield: 355 mg (93%), mp > 310 °C. 1H NMR (400 MHz;
CDCl3): δH, ppm 10.22 (s, 1H, 20-H), 9.47 (d, J = 5.3
Hz, 1H, 3-H), 9.41 (d, J = 5.3 Hz, 1H, 2-H), 9.35 (d,
J = 5.2 Hz, 1H, 7-H), 9.27 (d, J = 5.0 Hz, 1H, 18-H),
9.02 (d, J = 5.0 Hz, 1H, 17-H), 9.00 (d, J = 5.2 Hz, 1H,
8-H), 8.91 (d, J = 5.3 Hz, 1H, 13-H), 8.84 (d, J = 5.3 Hz,
1H, 12-H), 8.05 (d, J = 1.8 Hz, 2H, o-Haryl), 8.02 (d, J
= 1.8 Hz, 2H, o-Haryl), 7.83 (t, J = 1.8 Hz, 2H, p-Haryl),
1.54 (s, 18H, tBu-H), 1.53 (s, 18H, tBu-H), -2.71 (bs, 2H,
inner NH). 13C NMR (100 MHz; CDCl3): δC, ppm 149.1,
148.9, 140.6, 140.0, 134.1, 133.7, 132.8, 132.2, 132.0,
131.0, 129.8, 129.6, 128.5, 127.5, 127.3, 125.9, 124.9,
121.7, 121.6, 107.2, 35.0, 31.7. UV-vis (DCM): λmax, nm
(ε, 103 M-1.cm-1) 418 (149), 514 (9.16), 560 (7.80), 580
(6.45), 643 (4.31). MS (ESI): m/z 754.4098 (calcd. for
C48H53N5NaO2 [M + Na]+ 754.4097). IR (ATR): ν, cm-1
1500s (NO2 asym), 1314s (NO2 sym).
(150 mL/150 mL) that was bubbled with argon for
10 min. Argon atmosphere was maintained and then
10% palladium on carbon (255 mg) was added, followed
by stepwise addition of sodium borohydride (454 mg,
25 eq., 1.21 × 10-3 mol). After 1.5 h the starting material
was consumed. The solvent was evaporated and the resi-
due filtered through a cotton wool plug after dissolving
in DCM. The DCM solution was washed with water. The
product was purified by column chromatography using
DCM/hexane (1:1) as eluent. A single red fraction was
obtained. The solvent was evaporated and the product
was red/purple. Yield: 349 mg (95%). It was recrystal-
lized from DCM/pentane. The product was a purple pow-
der that is very soluble. Yield: 29 mg (8%), mp > 310 °C.
1H NMR (400 MHz; CDCl3): δH, ppm 9.36 s, 1H, 20-H),
9.09 (d, J = 4.9 Hz, 1H, 3-H), 9.01 (d, J = 4.9 Hz, 1H,
7-H), 8.88 (d, J = 4.9 Hz, 1H, 2-H), 8.85 (d, J = 4.9 Hz,
1H, 18-H), 8.61 (d, J = 4.9 Hz, 1H, 17-H), 8.59 (d, J =
4.9 Hz, 1H, 8-H), 8.57 (d, J = 5.1 Hz, 1H, 13-H), 8.51 (d,
J = 5.1 Hz, 1H, 12-H), 7.78 (t, J = 2.0 Hz, 4H, o-Haryl),
7.67 (m, J = 2.0 Hz, 2H, p-Haryl), 5.81 (bs, 2H, NH2), 1.45
t
(s, 36H, Bu-H). 13C NMR (100 MHz; CDCl3): δC, ppm
149.0, 148.9, 145.0, 144.9, 141.5, 141.4, 141.0, 140.9,
140.8, 139.9, 133.2, 133.0, 132.7, 131.7, 131.1, 130.0,
129.2, 128.3, 128.2, 128.0, 124.1, 123.8, 120.8, 120.7,
120.5, 116.0, 104.2, 35.0, 31.5. UV-vis (DCM): λmax, nm
(ε, 103 M-1.cm-1) 422 (160), 537 (9.79), 592 (9.96). MS
(ESI): m/z 780.3542 (calcd. for C48H53N5NaNi[M + Na]+
780.3552). IR (ATR): ν, cm-1 3392m, 1255m (NH2).
1,2-bis{[10,15-bis(3,5-di-tert-butylphenyl)porphy-
rinato]nickel(II)-5-yl}diazene (5). Porphyrin 4 (349 mg,
4.60 × 10-4 mol) was dissolved in 15 mL of toluene.
To this copper(II) acetate (11 mg, 5.52 × 10-5 mol, 12
mol.%) and pyridine (150 μL, 1.84 × 10-3, 4 eq) were
added. The mixture was stirred at 80 °C for 2 h. The solu-
tion was washed with water and the product extracted
into DCM. The solvent was evaporated and the product
recrystallized from DCM/methanol. The product was an
olive green powder. Yield: 230 mg (66%), mp > 310 °C.
1H NMR (400 MHz; CDCl3): δH, ppm 10.15 (d, J = 4.8
Hz, 2H, 3,3′-H), 10.08 (d, J = 5.3 Hz, 2H, 7,7′-H), 9.71
(s, 2H, 20,20′-H), 9.27 (d, J = 4.8 Hz, 2H, 2,2′-H), 9.01
(d, J = 4.8 Hz, 2H, 18,18′-H), 8.99 (d, J = 5.3 Hz, 2H,
8,8′-H), 8.83 (d, J = 4.8 Hz, 2H, 17,17′-H), 8.73 (d, J =
5.3 Hz, 2H, 12,12′-H), 8.71 (d, J = 5.3 Hz, 2H, 13,13′-H),
7.90 (d, J = 1.8 Hz, 4H, o-Haryl), 7.87 (d, J = 1.8 Hz,
4H, o-Haryl), 7.74 (m, J = 1.8 Hz, 4H, p-Haryl), 1.50 (s,
36H, tBu-H), 1.48 (s, 36H, tBu-H). 13C NMR (100 MHz;
CDCl3): δC, ppm 149.2, 149.0, 143.3, 143.2, 142.6, 142.5,
141.8, 141.5, 140.5, 140.4, 139.5, 139.4, 134.6, 134.2,
133.6, 133.5, 133.2, 132.9, 132.8, 132.2, 131.7, 128.6,
128.5, 128.4, 122.5, 122.4, 121.3, 106.0, 35.0, 31.7. UV-
vis (DCM): λmax, nm (ε, 103 M-1.cm-1) 402 (78.2), 487
(129), 738 (41.5). MS (LSI): m/z 1510.7024 (calcd. for
C96H102N10Ni2 [M]+ 1510.6996). Crystals of 5 for X-ray
data collection were grown by slow diffusion of metha-
nol into a solution of the azo-linked porphyrin in DCM.
[10,15-bis(3,5-di-tert-butylphenyl)-5-nitroporphy-
rinato]nickel(II) (3). Porphyrin 2 (354 mg, 4.84 × 10-4
mol) was dissolved in 15 mL of toluene and stirred. To
this, Ni(acac)2 (354 mg, 1.38 × 10-3 mol) was added.
The mixture was refluxed for 2 h, after which the start-
ing material was consumed. The product was purified by
column chromatography using DCM/hexane (1:1) as elu-
ent. A single red fraction was collected. The solvent was
evaporated to give a red residue (yield: 382 mg (100%))
which was recrystallized from DCM/pentane to give a
pale red powder. Yield: 218 mg (57%), mp > 310 °C. 1H
NMR (400 MHz; CDCl3): δH, ppm 9.84 (s, 1H, 20-H),
9.37 (d, J = 5.1 Hz, 1H, 3-H), 9.24 (d, J = 5.1 Hz, 1H,
7-H), 9.22 (d, J = 5.1 Hz, 1H, 2-H), 9.09 (d, J = 5.1 Hz,
1H, 18-H), 8.92 (d, J = 5.1 Hz, 1H, 8-H), 8.91 (d, J =
5.1 Hz, 1H, 17-H), 8.81 (d, J = 5.1 Hz, 1H, 13-H), 8.78
(d, J = 5.1 Hz, 1H, 12-H), 7.85 (t, J = 2 Hz, 2H, o-Haryl),
7.83 (t, J = 2 Hz, 2H, o-Haryl), 7.75 (m, J = 1.9 Hz, 2H,
t
t
p-Haryl), 1.48 (s, 18H, Bu-H), 1.47 (s, 18H, Bu-H). 13C
NMR (100 MHz; CDCl3): δC, ppm 149.1, 144.0, 143.8,
143.2, 143.0, 142.9, 142.7, 139.2, 139.1, 137.8, 137.5,
134.9, 134.4, 134.0, 133.5, 132.8, 132.3, 129.5, 128.7,
128.6, 126.3, 123.6, 123.0, 121.5, 106.5, 35.0, 31.7. UV-
vis (DCM): λmax, nm (ε, 103 M-1.cm-1) 411 (129), 528
(7.03), 565 (4.53). MS (ESI): m/z 810.3293, (calcd. for
C48H51N5NiNaO2 [M + Na]+ 810.3294). IR (ATR): ν, cm-1
1498s (NO2 asym), 1314s (NO2 sym).
[5-amino-10,15-bis(3,5-di-tert-butylphenyl)por-
phyrinato]nickel(II) (4). Compound 3 (382 mg, 4.84
× 10-4 mol) was dissolved in a DCM/methanol solution
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 489–493