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PDT ‡¢âØ#Ÿò2¨!1!
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1 - 3)
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YJH_J[F< PC 2s‹îì#~£2ï(
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J`KFGÈW[5YJH_J[F< PC #~£
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/ PDT Ìq‡¢âØ$W\Q4
´ùk$ Zn-PC W[ĉ9\V_úĊ
[_y~Ç/W[Q4[_y~Ç$|¶Š
'J`KFGÈW[5YJH_J[F< PC #
450 nm hô.]`@`q# 600850 nm "
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850 nm #ôóˆĆ…"™
|¶Š2¯.»
/)µíè!
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g$J`KFGÈW[5YJH_J[F
¿Ñ0
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tÄ2¯
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#-PC
< PC #~£#´ùk/Ą‘Õ# Zn-PC W
[ĉ9\V_úĊ #~£"
µí2å
y~Ç$ºci# PDT Ìq‡¢u#žÌ
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Ñ0ÿœ2ā)
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KM·÷l
2·×/)"H_J[X`ùk2¯PC y
(
~Ç2´ùk­éH_J[F< PC #~£2
) µí$58_C_?`PDTDNA
'
3,3’ H_J^_ùk$jb#,"å 16)
U<D`! &#žÌ°š/­é!H_J[
5YMBS^P8LI[\2w¼së 3,3’-5Y
F< PC #~£2ï(
MBS^P8_ú
3,3’-5YMBS^P
H_J[X`$¸±Ès‹
10KM·÷#•
8_ú#5YM†2 t-RI;AeÃút-Boc)",.o
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-0
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PC y~Ç#¹ß#Â$d
N-(t-Boc)5YMBS^P8_ú$7E]_B3Y
1
NC
HOOC
CN
O
O
O
+
Phtalic anhydride
NH2
O
O
O
N
N
Zn
N
O
N
O
N
N
O
Pyromellic dianhydride
N
HOOC
COOH
COOH
NH
HOOC
COOH
HOOC
N
O
3,3'-Iminodipropionic acid
3,3'- Iminodipropionitrile
COOH
COOH
COOH
N
H
N
H
COOH
Type 2 compound
COOH
Mole ratio between phthalic anhydride and pyromellic dianhydride
N
COB
BOC
Number of carboxylic acid
3:1
1:1
1:3
0:4
N
NH
O
N-(t-Boc)iminodipropionic acid
2
4
6
8
Scheme 3
NH2

G1
Scheme 1
DRNP=@µ—Œ˜—ŒE;Qµ!‘jf
Sg~+ VZG1)(Scheme 1)
ƒ)} 2 ¡¤! Zn-PC KP½2QJSµ¾"†
,!‚]-¦*²VZ-p' VZ
Ÿn/LAm +%) Œµe2P0MŒ
G1.5$j
•-›dŒb­-ª
PC ATB=>™KP/LA?SAP=4 PC !‰
PC + Zn-PC KP½2QJSµ¾"E;Qµ°x\y
ATB=>™KP/LA?SAP=4 PC "?S
¢-›+ Wyler  ”j-ªZn-PC K
ARS³[8 »! Zn-PC KP½2QJSµ¾
P½2QJSµ¾"s 2 ¡¤!fƒ)´j 8
-g~+}
»-j ¿!¡¤"@PNP=@µ—Œ˜
—ŒE;Qµ-jfƒ+&!Scheme 2
!¡¤"DRNP=@µX—Œ˜—ŒE;Qµ
FR@S‰œ‹1H-NMR)8H4@Q" 15 mg cm-3
-jfƒ+&!
+Scheme 3
¶Œ¢e7N<Q8QI36A•
COOH
HOOC
Bruker
AM-400 m‰œ‹a¼«§-›“w
N
O
O
O
+
Zn
N
N
O
±r¥khIR)8H4@Q"zŽ FTIR-8100A mE
N
N
HOOC
N
TP1q±rb``|¯-›¨e2P0M¸c
N
N
O
Phthalic anhydride
O
Trimellic anhydride
HOOC
 (*“w
COOH
Type 1 compound
£ r i ¬ k h UV-Vis) 8 H 4 @ Q " z Ž
Mole ratio between phthalic and trimellic anhydride
3:1
1:1
1:3
0:4
Number of carboxylic acid
UV-2400PC m£ri¬b``|¯-›“w
1
2
3
4
“w›t"DP7S@Q1SŒ(#7N<Q8
Scheme 2
QI36A(DMSO)-^›1.0 x 104 mol dm-3 !–|
Zn-PC KP½2QJSµ¾!j" ¿!¡¤ 2 !¡¤&@PNP=@µ—Œ˜
+"DRNP
©`8H4@Q!“w"„žF-4500mb`©``
=@µX—Œ˜—ŒE;Qµ!‘jOQŠ-
|¯(#„‡b` JASCO FP-6600 mb`©``|
,, 4:03:11:1 (# 3:1 ‘jfƒ-›
¯-^›“w•t"DP7SŒ(# DMSO
-›1.0 x 104 mol dm-3 !–|
,)!‘jfƒ"oeY·(II)1,2,4-@P4R
ºu8DSa¼(ESR) 8H4@Q"„‡ºu
RGS:S•tW 7.5C64R[5.4.0]-7-0S?
JFS-FA200 mºu8DSa¼«§-›{’“w
9S®tvlU€w!’|…¹ g~
g~š˜"Œ.9@S 6 mol dm-3 oµ
_¢bˆ" Perkin-Elmer 2400CHN m_¢bˆ«§
2
0Ž‡q
9C4>J
‡qµ Š¢! 1.9712 S
¤
*" 2.0245 S¤ g Wnfv! +.
Table 2 ESR spectral data of H2-PC, Zn-PC, and
H2-PCZn-PCZn-PC <>H2JDL§
*"14
Zn-PC tetracaboxylic and
:2JDL§!›ŸeUx.+ ]‹!
octacarboxylic acids
Compound
..000000 *" 00%
g value
H2-PC
624.5, 654.0, 687.5
Zn-PC
607.0, 655.5
UV-Vis 9C4>J
PC ! 690 nm + 770
Zn-PC tetracarboxylic acid
690.5, 772.5
nm S¤ HOMO-LUMO ¬ -¦”h Q
Zn-PC octacarboxylic acid
747.0, 769.0
Table 1 UV-Vis 9C4>J=M:
*" log r}0’
wb]Œ.
Zn-PC H2-PC 0ģ-
Oy©t €‰!b]‚m Œ.-…«m
v! +.Zn-PCZn-PC <>H
– 1 ™š
*"–´™š
2JDL§14:2JDL§ *2JD37J
§²!ˆ›Ÿ˜x
hjZ-b]‚m Tœ!«…«X#7A>
– 1 ™š
+2JD37Jh } jZ
?2JDL§82JDL§>I2JDL§
*"
)b]‚m…«05L>KMJ-^ž{
<>H2JDL§!.. 594453 *"
’d.-Nlog!Oy©t €‰vŒ.
29%'–´™š
Oy©tRª0€-W!s
L§² ]‹!82JDL§<>H2JDL§
OyRª0€- PC ak0ƒ£-log!%
B362JDL§
*"14:2JDL§!.
&—+Oy©t •¯u_.-
. 221622 *" 35%
+.-
†`\~0Ž PC !†`\~ [o¨¡ƒ
H2-PC
Zn-PC
Zn-PC tetracarboxylic acid
Zn-PC octacarboxylic acid
PC |Š`|.-^ž{°
~
[o¨¡ƒz®r“g PC `|
Zn-PCtetracarboxylic and octacarboxylic acids
max/nm
Zn-PC EI±2JD
‘+.- 12, 15)$ †`\
absorption coefficientof H2-PC, Zn-PC, and
Compound
Zn-PC EI±2JDL§² ]‹!G
z®r“g
Table 1 UV-Vis spectral data and molar
Zn-PC EI±2JDL
.-/!Y¥$–³™š
*"–´™
log 624.5
2.46
š †`\~!®r“ PC ­-icV!
654.0
2.10
–³™š †`\~`|.- Zn-PC EI±2J
687.5
2.03
DL§²!>IFI;>§‰„Š‰„A:J§ †
607.0
4.54
`GJƒz2JDL§ }³+µ'
655.5
4.58
-N– 2 ™š †`\~`|.- Zn-PC
690.5
3.60
!@KFI;>§P‰„Š‰„A:J§ †`G
772.5
4.22
Jƒz
2JDL§ }!´+8 ',
747
4.21
'@KF;I>§P‰„Šlpžh-(
769.0
4.26
P¨U+Q¨U' EI(Zn-PC)|-^ž
{- 16)
Table 2 ESR 9C4>J=M:0’ESR
- Zn-PC EI±2JDL§² 2
3
Table 3
Comp. type
1
2
Spectral data of synthesized zinc phthalocyanine poly(carboxylic acid).
max / nm
Raw materials (mole ratio)
log Fmax / nm
Trimellitic anhydride
Phtalic anhydride
1
3 677
6.86
695
2
2 676
6.81
710
3
1 685
6.87
720
4
0 673
6.78
720
Pyromelliyic dianhydride
Phtalic anhydride
1
3 685
6.83
700
2
2 688
6.93
710
3
1 697
6.88
715
4
0 695
6.84
715
849”šUO]`Q(dRT&
1& 2)"D~Fgh**FUj_
OKiT‹…yH=n)Q OK
Zq*{ 1 &{ 2 }€
[P*)OKiTmuNV+Š#
%utj Zn-PC 57ž-849”ŸMb*
Q OK[PC o^tOK[(
)%‚'*)
e‡I‘(HOMO)-e?z‘(LUMO)˜ *
šU“yQ
max 650 nm Žq*)iT
A
A
A
B
A
B
B
B
OK(68OEAdXd log 4.5 >;
A
A
B
A
A
B
B
B
B+x"Q OK[–C™Aq*)†E
A
A
A
B
A
B
B
B
iT Fmax ‹…yH%mucQ+f
A
P
A
P
B
P
B
P
) PC jbJUdSFU‘‰|&
A
P
A
P
B
P
P
A
P
B
P
B
) Q OK[=n<Lƒ)
A
P
B
P
B
P
A
P
A
P
B
P
Q OK[iTOKl— max { }€Zn-PC 5
A
P
B
P
7ž-849”ŸZ ,#'*{
P
P
P
P
A
B
P
Fig.1 Schematic dyagram of phthalocyanine isomers synthesized
from trimellic anhydride and phthlic anhydride.
2 }€ !-849”d_‹…yH)
ˆW*ž Table 3 Ÿ
A
A
A
A
A
A
A
P
A
P
P
A
†E+s)v'*)
A
P
A
P
{ }€ Zn-PC 57ž-849”Ÿ-849”
A
P
{ }€ Zn-PC 57ž-849”Ÿ Q OK[
iTOKl— max -849”d_yH
†EiT Fmax yH:„ PC
‹…EGŒ*)e?:•œpa(GŒ
pa%\›`$wStorks/21
d’Yr`@d{ 2 }€k
P
P
A
P
Fig.2 Schematic dyagram of phthalocyanine isomers
synthesized from pyromellic anhydride and phthlic anhydride.
S$OK03.18Zq*
†E03.18Zq*‚'*)(Figs.
4
NH2
O
NH
3,3’-&B9-=I:(85FG$VjU„3,3’-
N
&B9-=I:(JŠ3,3’-&B9-=
HN
N
N
O
H 2N
NH
NH2
O
O
O
O
NH
HN
NH
COB
NH2
NH2
H 2N
O
O
HN
NH2
N
N
H
N
N
HN
+
I:(JŠ&B9[$ t-<5*,NlŠt-Boc)
O
H 2N
H 2N
O
N
N
Zn
N
N
O
NH2
O
!S† N-(t-Boc)&B9-=I:(JŠ`
HN
COOH
HOOC
H 2N
N
# N-(t-Boc)&B9-=I:(JŠ'0HJ-
N
N
O
N
N
O
O
Zn
N
N
%BJWb" G1 #eR$
N
€!ˆMP$\G1.5 Yd
COOH
NH
NH2
NH2
O
O
O
HN
NH
N
N
HOOC
N
N
N
NH
N
N
HN
COOH
COOH
NH2
N
H
NH2
NH
NH2
HN
NH2
NH2
COOH
COOH
Scheme 5
3,3’-&B9-=I:(85FG$VjU„3,3’-&
B9-=I:(JŠXq 88%t‚yh`
x 1 {} G1-Zn-PC 4J6FAKXq 25%
~‚yh`x{} Zn-PC 4J6
3,3’-&B9-=I:(JŠ&B9[$ t-<5*,
FAK G1 G1.5 ## 18% 9%~‚yh
NlŠt-Boc)S† N-(t-Boc)&B9-=
`"
#
I:(JŠXq 13%t‚‹o|g`
3 Zn-PC 4J6
FAK;/I,%8Jnau Q ZX^ 690
'0HJ-%BJ N-(t-Boc)&B9-=I:(J
nm O‡r#!715 nm O‡ƒTr#
Š G1 Xq 70%Œ‚kQ`
3 Zn-PC 4J6FAK_o6K7
G1.5 Xq 93%zc"m‚kQ`
12o"$U],CBHK,DJ
3,3’-&B9-=I:(JŠN-(t-Boc)&B9-=I
w…
:(JŠG1 G1.5 1H-NMR IR .>
+5Gvui‰L f
1)
B. Paquette, H. Ali, R. Langlis, J. E. van Lier:
Photochem. Photobiol., 47, 214 (1998).
2)
x{} Zn-PC @F)G?JŠŽ Zn-PC
D. Wohrle, N. Iskander, G. Graschew, H.Sinn, E. A.
Fridrich, W. Maier-Borst, P. Schlag: Photochem.
35E)G?JŠŽG1 Y
Photobiol., 51, 351 (1990).
Zn-PC 4J6FAK$Yd(Scheme 4)
3) K. Fukushima, K. Tabata, I. Okura: J. Porphyrins
Phthalocyanines, 2, 219 (1998).
NH2
O
NH2
H2N
NH
4) G. Jori: J. Photochem. Photobiol., B:Biol., 36, 87
NH
HN
O
O
COB
p
N
H2N
O
O
5) K. Tabata, K. Fukushima, K. Oda, I. Okura: J.
N
N
N
+
Zn
N
N
N
N
Porphyrins Phthalocyanines, 4, 278 (2000).
O
N
O
N
H2N
(1996).
N
N
NH2
NH2
H
N
H
N
NH
O
N
N
H
N
H
6) T. J. Dougherty: J. Photochem. Photobiol., 58, 895
NH2
COOH
HOOC
O
N
HN
NH
(1993).
N
N
Zn
N
O
N
N
H2N
N
NH2
7) M. J. Cook, I. Chambrier, S. J. Cracknell, D.A. Mayes,
N
HOOC
COOH
Scheme 4
D. A. Russel: Photochem. Photobiol., 62, 542 (1995).
x{} Zn-PC @F)G?JŠŽ Zn-PC
8) M. P. De Dilippis, D. Dei, L. Fantetti, G. Roncucci:
(+/)G?JŠŽ$sG1(Scheme 5) "
Tetrahedron Lett., 41, 9149 (2002).
G1.5 Y
9) K. Sakamoto, E. Ohno-Okumura, T. Kato: J. Jpn. Soc.,
5
Colour Mater., 76, 342 (2003).
10) 1!, # : .$, 75, 214 (2002).
11) I. Seotsanyana-Mokhosi, N. Kuznetsova, T. Nyokong:
J. Photochem. Photobiol. A: Chem., 140, 215 (2001).
12) (5# 5%"05)-.,
5
5&3 2004 4.
13) K. Sakamoto, E. Ohno-Okumura, Taku Kato, Recent Rsearch
Development of Inorganic Chemistry, 5, 1 (2006).
14) K. Sakamoto 5 E. Ohno-Okumura 5 Current Topics in
Electrochemistry 5 9 5 117 (2003).
15) +*/5'25
)-5
5& (1997).
16) D.R.Boston 5 J.C.Bailar.Jr 5 Inorganic Chemistry 5 11, 1578
(1972).
6