822
D. ChumakOv et al.
Phosphorescencespectraandquantumyieldsweremea-
sured on Fluorolog-3 instrument equipped with HORIBA
Jobin Yvon FL 1073 detector. Right-angle detection was
used in all measurements. Assemblies of quartz cuvette
with graded quatz-borosilicate seal and a side flask for
freeze-pump-thaw degassing were used. DMF solutions
of the substances with OD no more than 0.1 at the excita-
tion wavelength were placed in the flask and the assembly
attached to a vacuum (10-2 Torr) line. After 5 to 7 freeze-
pump-thaw cycles the assembly was seal-detached in
vacuum, then frozen solution was melted and poured into
the cuvette. An identical cuvette was used for the stan-
dard – tetraphenylporphyrin, which was measured in ben-
zene solution in ambient atmosphere (quantum yield 0.11
[51]). Solutions were irradiated at 635 nm, range of emis-
sion detector was 640–850 nm. Slit widths in both excita-
tion and emission channels were 3 nm. Instrument built-in
correction factors are used to obtain true emission spectra.
Phosphorescence quantum yields were determined accord-
ing to [52], correction having been applied to amount of
absorbed light and to the difference of refraction indices
of the solvents. For details of phosphorescence measure-
ments at 77 K, see Supplementary material.
400 equiv.) dissolved in of CHCl3 (3.6 mg) 1 (50 mL,
54 µmol) was added. Then the reaction mixture was
brought to reflux and the reflux continued for 4 h. Reaction
mixture was quenched and processed as for the previous
compound. 38 mg of 3 (25 µmol, 46%) was obtained.
Molecular ion isotope distribution spectrum is identical
1
with simulated one. UV-vis spectrum see in Table 3. H
NMR (400 MHz, CDCl3, HMDS, ring designation – bold
letter – see in Chart 2): δH, ppm 8.14 (8H, d, o-Ph), 8.03
(4H, t, p-Ph), 7.93 (8H, t, m-Ph), 7.28 (8H, s, H-C). LDI-
TOF mass spectrum (see Supplementary material) shows
isotope distribution identical to the calculated one.
Mixture of palladium 2,9,16,23,-tetrabromo-6,13,
20,27-tetraphenyltetrabenzo[b:g:l:q]porphyrin [53],
palladium 2,3,9,16,23,-pentabromo-6,13,20,27-tetra-
phenyltetrabenzo[b:g:l:q]porphyrin, palladium 2,3,9,
10,16,23,-hexabromo-6,13,20,27-tetraphenyl-tetra-
benzo[b:g:l:q]porphyrin, palladium 2,3,9,10,16,17,23-
heptaromo-6,13,20,27-tetraphenyltetrabenzo[b:g:l:q]
porphyrin. This mixture was obtained on according
1
to Table 1, entry 7. Spectrum is shown in Chart 3c. H
NMR (400 MHz, CDCl3, HMDS, ring designation – bold
letter – see in Chart 2): δH, ppm 8.20–8.11 (8H, m, o-Ph),
8.06–7.80 (12H, p-,m-Ph), 7.36–7.29 (2H, m, H2-Bmaj
and H1-Bmin), 7.27 (s, H-Cmaj), 7.17 (quasi-d, H-Cmin
and H4-Bmaj), 7.08 (6H(together with 7.27 and 7.17),
Geometry optimizations were performed using Gauss-
ian 03 software at B3LYP/LanL2MB level of theory.
Optimized geomeries showed no imaginary frequencies
in vibrational analyses.
s H4-Bmin), 6.97 (d, JH H -Bmaj
(2H(together with 6.97), dd, JH H -Bmin
2.0, H2-Bmin).
1
2
= 8.8, H1-Bmaj), 6.87
Bromination of Pd Ph4TBP. Synthesis of palladium
2-bromo-6,13,20,27-tetraphenyltetrabenzo[b:g:l:q]-
porphyrin (2). Amount of Pd Ph4TBP relevant to concen-
tration specified in Table 2 was dissolved in the mentioned
solvent. Then reflux and stirring was begun, and Me4NBr3
added by equal portions in equal time periods (or added
dropwise if CH2Cl2 usedasathesolvent). Refluxandreagent
addition was continued until TLC showed mainly the for-
mation of the target porphynate.At the end reaction mixture
was washed by 10% aq. Na2SO3 and brine. Organic layer
wasdriedoverNa2SO4.Thenthesolventwasevaporatedand
the residue was analysed by LDI-TOF. For preparative pur-
poses (Table 2, entry 4) 1(50 mg, 54.4 µmol) were dissolved
in CHCl3 (3.3 mL) and NMe4Br3 (44 mg, 0.14 mmol) were
added in portions for specified time. After workup, residue
was chromatographed on silica, eluent CCl4/hexanes. Yield
33 mg, 63%. Molecular ion isotope distribution spectrum
is identical with simulated one. UV-vis spectrum see in
Table 3. 1H NMR (400 MHz, CDCl3, HMDS, ring designa-
tion – bold letter – see in Chart 3): δH, ppm8.25–8.20(8H, m,
1
2
= 8.9, JH H -Bmin
2
4
=
SUMMARY AND CONCLUSION
Bromination of Pd Ph4TBP 1 yields mono- and octa-
bromoderivative 2 and 3. These derivatives were isolated
and characterized. UV-vis, redox and phosphorescence
properties have been studied. Bromination was found to
exert little influence on UV-vis data. Reduction potentials
showed anode shift upon bromination, whereas at first
oxidation one remained unchanged; for second oxidation
one moved to cathode region. Unlike the results at 77 K,
octabromosubstitution did not give rise to increased
phophorescence quantum yield at room temperature.
Acknowledgements
Grant from Russian Foundation for Basic Research
(10-03-01071a) is gratefully acknowledged. Authors are
grateful to Mr. MizerevAA. for careful reading the manu-
script, Dr. Fedorov Yu. V. for assisting room temperature
phosphorescence measurements and to Prof. Vinogradov
S.A. (University of Pennsylvania) for helpful and stimu-
lating discussion.
o-Ph), 7.98–7.81 (12H, p-, m-Ph), 7.28 (1H, dd, JH1H -B
8.7, JH2H -B
= 1.7 Hz, H2-B), 7.21–7.19 (7H, m(quasi-AA’
part of AA’BB’), o-A, H2-B)), 7.10 (6H, m, m-A), 6.89
(1H, d, JH1H -B
= 8.7, H1-B). LDI-TOF mass spectrum
2
=
4
2
(see Supplementary material) shows isotope distribution
identical to the calculated one.
Bromination of Pd Ph4TBP. Synthesis of palladium
2,3,9,10,16,17,23,24-octabromo-6,13,20,27-tetraphenyl-
tetrabenzo[b:g:l:q]porphyrin (3). To the mixture of
NMe4Br (17 mg, 54 µmol) and Br2, (3.5 g, 22 mmol,
Supporting information
Figures S1–S5 are given in the supplementary mate-
rial. This material is available free-of-charge via the
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 822–824