2876 J. Phys. Chem. B, Vol. 103, No. 15, 1999
Tsukahara et al.
Found: C, 67.30; H, 4.88; N, 8.44. 14: 1H NMR (270 MHz,
CD3CN, 34 °C, TMS) δ 8.77 (d, J ) 6.6 Hz, 4H, pyrrole B,Da),
8.67 (s, 4H, pyrrole C), 8.42-8.55 (m, 8H, o-phenyl I), 8.12-
8.18 (m, 8H, o-phenyl II), 7.88-8.07 (m, 12H, m-, p-phenyl
I), 7.96 (s, 4H, pyrrole A), 7.65-7.92 (m, 12H, m-, p-phenyl
II), 7.40 (d, J ) 6.6 Hz, 4H, pyrrole B,Db), 7.20 (d, J ) 6.0
Hz, 4H, 3,5-bpy), 6.60 (d, J ) 6.0 Hz, 4H, 2,6-bpy), 2.15 (t, J
) 8.1 Hz, 4H, -CH2-N+), -0.70 to -0.60 (m, 4H, -CH2-),
-4.65 to -4.45 (m, 4H, N-CH2-). Anal. Calcd for C104H78N10-
P2F12‚5H2O: C, 68.27; H, 4.85; N, 7.65. Found: C, 68.34; H,
4.61; N, 7.76. FAB-MS (3-NBA): m/z (rel intensity, %) 812
{[[(HP)2MV]2+ - [Htpp(CH2)3]+]+, 100}, 1468 {[(HP)2MV]+,
9; 17 in 1-thioglycerol}.
1H NMR (270 MHz, CDCl3, 34 °C, TMS) δ 8.95 (d, J ) 5.1
Hz, 2H, pyrrole B,Da), 8.86 (d, J ) 5.1 Hz, 2H, pyrrole B,Db),
8.85 (s, 2H, pyrrole C), 8.50-8.60 (br, 4H, o-phenyl I), 8.20-
8.31 (br, 4H, o-phenyl II), 8.19 (s, 2H, pyrrole A), 7.76-7.89
(m, 12H, m-, p-phenyl I, II), 2.64 (t, J ) 6.8 Hz, 2H, R-CH2I),
0.99-1.10 (m, 2H, â-CH2-), 0.15-0.24 (m, 2H, γ-CH2-),
-0.75 to -0.67 (m, 2H, δ-CH2-), -0.87 to -0.81 (m, 2H,
ꢀ-CH2-), -4.58 (t, J ) 7.3 Hz, 2H, N-CH2-). Anal. Calcd
for C50H40N4IZnCl‚H2O: C, 63.71; H, 4.49; N, 5.94. Found:
C, 63.41; H, 4.22; N, 5.86. 14Zn ([(ZnClP)2MV](PF6)2‚3H2O):
1H NMR (270 MHz, CD3CN, 34 °C, TMS) δ 8.80-8.95 (m,
8H, pyrrole B,D), 8.68 (br, 4H, o-phenyl I), 8.40 (d, J ) 8.8
Hz, 4H, pyrrole C), 8.28 (br, 4H, o-phenyl I), 8.10 (br, 8H,
o-phenyl II), 7.97 (br, 4H, pyrrole A), 7.80-8.00 (m, 24H, m-,
p-phenyl I,II), 7.62 (d, J ) 6.0 Hz, 4H, 3,5-bpy), 7.58 (d, J )
6.0 Hz, 2H, 2- or 6-bpy), 7.29 (d, J ) 6.0 Hz, 2H, 2- or 6-bpy),
2.38-2.50 (m, 4H, -CH2-N+), -0.18 to -0.13 (m, 4H,
-CH2-), -4.60 to -4.50 (m, 2H, N-CH2-), -4.70 to -4.60
(m, 2H, N-CH2-). Anal. Calcd for C104H76N10Zn2Cl2P2F12‚
3H2O: C, 62.10; H, 4.11; N, 6.96. Found: C, 62.14; H, 3.88;
N, 7.08. FAB-MS (3-NBA): m/z (rel intensity, %) 911
{[[(ZnClP)2MV]2+ - [ZnCl(tpp(CH2)3)]+ - H]+, 100}, 1667
{[(ZnClP)2MV]+, 30}.
Insertion of Zinc(II) into Porphyrins. A typical method is
described for chloro{[3-(1-methyl-4,4′-bipyridinio)propyl]-5,-
10,15,20-tetraphenylporphyrin}zinc(II) ([ZnCl(MVprtpp)](PF6)2‚
0.5CH3C6H5, 10Zn). Compound 10 (0.078 g, 0.067 mmol) and
zinc(II) chloride (0.091 g, 0.67 mmol) were dissolved in 5 mL
of THF including 2,6-lutidine (7.4 mg, 0.069 mmol), and the
mixture was heated at 40 °C for 40 min under argon with
stirring. After THF was evaporated, the residue was washed
with cold water and then with cold toluene. The resulting purple
powder was dissolved in MeCN and purified by Sephadex LH-
20 column chromatography with MeCN. Recrystallization from
CH2Cl2-toluene gave a purple powder (0.054 g, 64%). The
same method as previously described in the literature16 was used
Insertion of Na(I), Mg(II), Al(III), and Si(IV) into Por-
phyrins. Metalloporphyrins were prepared in situ by adding
NaPF6, MgCl2‚6H2O, AlCl3‚6H2O, and SiCl4 in slight excess
in MeCN. The 1:1 complex formation was confirmed by a molar
ratio method at Soret band maxima for Na+, Mg2+, Al3+, and
Si4+ ions.27 An attempt to isolate these metalloporphyrins as a
solid was unsuccessful; removal of excess metal ions gave a
mixture of metalloporphyrin with free-base porphyrin. A small
amount of water was added into MeCN due to the lower
solubility of the metal salts except for NaPF6 and SiCl4. The
water content of the sample solution was less than 0.055 M.
1
for the synthesis of compound 7Zn. 10Zn: H NMR (270 MHz,
CD3CN, 35 °C, TMS) δ 8.93 (d, J ) 4.8 Hz, 2H, pyrrole B,Da),
8.87 (s, 2H, pyrrole C), 8.77 (d, J ) 4.8 Hz, 2H, pyrrole B,Db),
8.77 (d, J ) 6.8 Hz, 2H, 2′,6′-bpy), 8.38 (s, 2H, pyrrole A),
8.22-8.32 (m, 4H, o-phenyl I), 8.05-8.10 (m, 4H, o-phenyl
II), 8.08 (d, J ) 6.8 Hz, 2H, 3′,5′-bpy), 7.79-8.02 (m, 6H, m-,
p-phenyl I, II), 7.83 (d, J ) 6.8 Hz, 2H, 3,5-bpy), 7.58 (d, J )
6.8 Hz, 2H, 2,6-bpy), 4.37 (s, 3H, N+-CH3), 2.36 (t, J ) 7.3
Hz, 2H, -CH2-N+), -0.26 to -0.15 (m, 2H, -CH2-), -4.63
to -4.57 (m, 2H, N-CH2-). Anal. Calcd for C58H45N6-
ZnClP2F12‚0.5CH3C6H5: C, 58.49; H, 3.91; N, 6.65. Found:
C, 57.95; H, 3.97; N, 6.39. FAB-MS (3-NBA): m/z (rel
intensity, %) 926 {[[ZnCl(MVprtpp)]2+ - H+]+, 100}, 1072
{[ZnCl(MVprtpp)]2+‚PF6-, 40}. 11Zn ([ZnCl(MVhxtpp)](PF6)2‚
0.5CH3C6H5): 1H NMR (270 MHz, CD3CN, 34 °C, TMS) δ
8.97 (d, J ) 4.8 Hz, 2H, pyrrole B,Da), 8.89 (d, J ) 4.8 Hz,
2H, pyrrole B,Db), 8.84 (s, 2H, pyrrole C), 8.80 (d, J ) 6.8 Hz,
2H, 2′,6′-bpy), 8.25, 8.62 (br, 4H, o-phenyl I), 8.44 (d, J ) 6.8
Hz, 2H, 2,6-bpy), 8.28 (s, 2H, pyrrole A), 8.24 (d, J ) 6.8 Hz,
2H, 3′,5′-bpy), 8.16 (d, J ) 6.8 Hz, 2H, 3,5-bpy), 8.09 (br, 4H,
o-phenyl II), 7.83-7.91 (m, 6H, m-, p-phenyl I,II), 4.37 (s, 3H,
N+-CH3), 3.98 (t, J ) 7.7 Hz, 2H, R-CH2-N+), 1.08-1.20
(m, 2H, â-CH2-), 0.05-0.17 (m, 2H, γ-CH2-), -0.83 to -0.71
(m, 2H, δ-CH2-), -0.92 to -0.86 (m, 2H, ꢀ-CH2-), -4.69 to
-4.63 (m, 2H, N-CH2-). Anal. Calcd for C61H51N6ZnClP2F12‚
0.5CH3C6H5: C, 59.37; H, 4.25; N, 6.44. Found: C, 59.86; H,
3.96; N, 6.35. FAB-MS (3-NBA): m/z (rel intensity, %) 966
Measurements. Fluorescence spectra were measured in
degassed MeCN and MeOH solutions at 25 °C with a Hitachi
850 spectrofluorometer. The fluorescence quantum yield was
determined by using that of 1 as a standard compound.16 The
excitation wavelength was the Soret maximum. Fluorescence
lifetimes were measured at 25 °C using a Horiba NAES-500
nanosecond-fluorometer. Glass filters were used for cutting off
the exciting light (B390 (HOYA)) and the emission (U330
(HOYA), L42 (TOSHIBA), and Y51 (HOYA)). The fluores-
cence was detected by a single-photon counting system and
analyzed as the sum of two exponential components after
deconvolution of the instrument response function. A picosecond-
photon-counting streak scope system (Hamamatsu Photonics
C4780) was also used for fluorescence lifetime measurements
of compounds 14, 10Zn, 11Zn, and 14Zn, where an N2/dye
laser was used for excitation at 430 nm (a 300 ps pulse width
and 10 µJ/pulse). T-T absorption spectra and the lifetimes of
the excited triplet state were measured using nanosecond-laser
flash photolysis;28 a XeCl excimer laser was used as a light
source where the excitation wavelength was 308 nm, and a Xe
lamp was used as a spectrum flash lamp. Time-resolved
difference absorption spectra over a delay time ranging from
0-6000 ps were measured using a picosecond-laser spectros-
copy system,29 where a mode-locked Nd3+:YAG laser (Con-
tinuum PY61C-10, fwhm ) 17 ps, 10 Hz) was used for
excitation at 532 nm. Conventional pulse flash photolysis was
also carried out for a slow reaction using a Photal RA-412 pulse
flash apparatus with a Xe flash lamp (a 30 µs pulse width). 1H
NMR spectra were measured with a JEOL JNM-GX270 FT
NMR spectrometer. UV-vis and IR spectra were recorded with
{[[ZnCl(MVhxtpp)]2+ - H+ - 2H]+, 100}, 968 {[[ZnCl-
(MVhxtpp)]2+ - H+], 90}, 1114 {[ZnCl(MVhxtpp)]2+‚PF6
,
-
32}. 3Zn ([ZnCl(HOPrtpp)]‚0.5H2O): 1H NMR (270 MHz,
CDCl3, 34 °C, TMS) δ 8.94 (d, J ) 5.1 Hz, 2H, pyrrole B,Da),
8.86 (d, J ) 5.1 Hz, 2H, pyrrole B,Db), 8.84 (s, 2H, pyrrole C),
8.53-8.63 (br, 4H, o-phenyl I), 8.21 (s, 2H, pyrrole A), 8.10-
8.20 (br, 4H, o-phenyl II), 7.70-7.90 (m, 12H, m-, p-phenyl I,
II), 1.83 (t, J ) 6.0 Hz, 2H, -CH2OH), -0.67 to -0.57 (m,
2H, -CH2-), -4.46 (t, J ) 7.3 Hz, 2H, N-CH2-). Anal. Calcd
for C47H35N4OZnCl‚0.5H2O: C, 72.22; H, 4.64; N, 7.17.
Found: C, 72.22; H, 4.72; N, 6.96. 7Zn ([ZnCl(IHxtpp)]‚H2O):