N. Kobayashi et al.
FULL PAPER
[22,23,122,123-tetraoctyloxydibenzo[b,l]-7,8,17,18-tetra(p-tert-butylphen-
Porphyrin Handbook, Vol. 15 (Eds.: K. M. Kadish, R. M. Smith, R.
Guilard), Academic Press, New York, 2003, Chap 100.
[8] K. Ishii, N. Kobayashi in The Porphyrin Handbook Vol. 16 (Eds.:
K. M. Kadish, R. M. Smith, R. Guilard), Academic Press, New
York, 2003, Chap. 102.
yl)-5,10,15,20-tetraazaporphinato(2ꢀ)]palladium(ii)
(2OpPd),
and
[22,23,72,73,122,123-tetraoctyloxytribenzo[b,gl]-17,18-bis(p-tert-butylphen-
yl)-5,10,15,20-tetraazaporphinato(2ꢀ)]palladium(ii) (3Pd): Bis(p-tert-bu-
tylphenyl)fumaronitrile[43] (409 mg, 1.1910ꢀ3 mol) and 4,5-dioctyloxyph-
thalonitrile[42] (249 mg, 6.4710ꢀ4 mol) were dissolved in a 1-pentanol so-
lution (12 mL) containing lithium, and the solution refluxed for 1 h under
nitrogen. After removing the solvent, the residue was purified by silica
gel (toluene, CHCl3, and hexane/CHCl3 as eluents) and Bio-beads gel (S-
x1 or S-x2, CHCl3 as eluent) columns, and separated into three fractions:
metal-free oppositely dibenzo-, adjacently dibenzo-, and tribenzo-substi-
tuted TAPs. These metal-free compounds and PdCl2 were refluxed in a
mixed solution of chlorobenzene and DMF for 2 h. After evaporation of
the solvent, the residue was purified on silica gel and Bio-beads gel (S-x1
or S-x2, CHCl3 as eluent) columns, and by preparative TLC (silica,
hexane/CHCl3 as eluent). Recrystallization from CHCl3/methanol gave
2OpPd, 2AdPd, and 3Pd as dark blue powders in 2.7% (14 mg), 7.5%
(38 mg), and 5.5% (19 mg) yield, respectively. 2AdPd: ESI-TOF MS:
m/z=1560 [M+1]+; elemental analysis (%) calcd for C96H124N8O4Pd:
C 73.89, H 8.01, N 7.18; found: C 73.69, H 8.18, N 7.22; 1H NMR
(400 MHz, CDCl3): d=8.51 (br, 2H; ArH), 8.26–8.14 (brm, 10H; o-Ph,
ArH), 7.69 (d, 4H; m-Ph), 7.51 (d, 4H; m-Ph), 4.45–4.30 (brm, 8H;
OCH2), 2.10 (brm, 8H; OCH2CH2), 1.73 (brm, 8H; OCH2CH2CH2),
1.59–1.37 (brm, 68H; OCH2CH2CH2CH2CH2CH2CH2, tBu), 0.96 ppm
(m, 12H; CH3). 2OpPd: ESI-TOF MS: m/z: 1560 [M+1]+; elemental
analysis (%) calcd for C96H124N8O4Pd: C 73.89, H 8.01, N 7.18; found: C
73.97, H 8.25, N 7.23; 1H NMR (400 MHz, CDCl3): d=8.39 (s, 4H;
ArH), 8.30 (d, 8H; o-Ph), 7.68 (d, 8H; m-Ph), 4.45 (t, 8H; OCH2), 2.13
(quin, 8H; OCH2CH2), 1.72 (quin, 8H; OCH2CH2CH2), 1.59–1.39 (m,
68H; OCH2CH2CH2CH2CH2CH2CH2, tBu), 0.95 ppm (t, 12H; CH3).
3Pd; ESI-TOF MS: m/z: 1602 [M+1]+; elemental analysis (%) calcd for
C96H134N8O6Pd: C 71.95, H 8.43, N 6.99; found: C 71.63, H 8.25, N 7.09;
1H NMR (400 MHz, CDCl3): d=8.40 (br, 6H; ArH), 8.30 (d, 4H; o-Ph),
7.71 (d, 4H; m-Ph), 4.47 (brm, 12H; OCH2), 2.15 (brm, 12H;
OCH2CH2), 1.77 (brm, 12H; OCH2CH2CH2), 1.60–1.40 (m, 66H;
OCH2CH2CH2CH2CH2CH2CH2, tBu), 0.97 ppm (m, 18H; CH3).
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Acknowledgment
This work was partially carried out in the Advanced Instrumental Labo-
ratory for Graduate Research of the Department of Chemistry, Graduate
School of Science, Tohoku University, and was supported by a Grant-in-
Aid for Young Scientists (Category A No. 14703007), Scientific Research
in Priority Areas “Diagnosis and Treatment of Cancer” (No. 15025212
and 16023213), and the COE project, Giant Molecules and Complex Sys-
tems, 2004 from the Ministry of Education, Culture, Sports, Science and
Technology, Japan.
[16] In the case of 2AdZn, 2OpZn, and 3Zn, the first oxidation couple is
reversible, but the first oxidation couple of 4Zn seems to consist of
two overlapping waves. Overlapping waves are often observed for
aggregated Pcs. This was supported by CV measurements at various
scan rates; the re-reduction wave at more anodic potential became
more prominent at faster scan rates, while the less anodic counter-
part diminished. Therefore, the more anodic wave is assigned to the
monomer. The reduction couples are reversible except in the case of
2AdZn. H. Isago, C. C. Leznoff, M. F. Ryan, R. A. Metcalfe, R.
Davids, A. B. P. Lever, Bull. Chem. Soc. Jpn. 1998, 71, 1039.
[17] For all the zinc complexes, very weak absorption bands are observed
between the Soret and Q bands. For Pcs with alkoxyl groups, these
absorption bands are assigned to n–p* transitions. This broad band
is also seen for 0Zn, but not observed for tetra-tert-butylated
ZnTAP. Therefore, the broad band of 0Zn originates from transi-
tions related to phenyl groups. This is supported by the CI calcula-
tions, which show that transitions at around 400 nm become more
intense with increasing number of phenyl groups (Figure 12). a) N.
Kobayashi, A. B. P. Lever, J. Am. Chem. Soc. 1987, 109, 7433; b) L.
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Chem. Eur. J. 2004, 10, 4422 – 4435