1P016
MTDH-TTP % C2TDH-TTP +ZnsR«
¹Y{m²º ´XM»iy»LI»v¶I
z
»qr¯u+( BDH-TTP Zn±NSt+g`
pU·+»©PsR+K( BDY (bis-fused 1,3-dithiol-2-ylidene)=>H+
¢([1]Of»,D1D9/j,D1DQ»Zn±NS%}µ
+a"+&($»BDH-TTP W69/BF+?7¹A9D9/ºj
%?7¹.9D9/ºj¤ MTDH-TTP C2TDH-TTP d\»)
&³¥ _«³Ps_+&¦(
S
S
S
S
S
S
S
S
S
S
BDH-TTP
BDY
S
S
S
S
SR
S
S
S
S
SR
MTDH-TTP: R = Me
C2TDH-TTP: R = Et
£ MTDH-TTP C2TDH-TTP d»78`d.7;D Me3Al-0:
@CF3b+.7;D 1a,b »|%d¹1a, 86%; 1b, 81%º
OH
MeO2C
OMe
4<FR 2 &78`d 3
MeSSiMe3, BF3·OEt2/CH2Cl2
or
EtSH, BF3·OEt2/CH2Cl2
SR
MeO2C
SR
1a: R = Me
1b: R = Et
s¹(i) NaOMe/ MeOH, (ii) Cl2SnBu2/THFº»»Me3Al
ohJ».7;D 1a b(»MTDH-TTP [¸R 4a 31%c~&)
e»3 1b Me 3Al-0:@CF3b%' 4b ~&)¹38%º4a,b + DDQ ®
`(%'»MTDH-TTP¹70%º C2TDH-TTP¹77%ºd+¬
S
S
S
S
S
S
O
S
S
2
S
S
S
S
3
S
SnBu2
S
S
S
S
S
4a: R = Me
4b: R = Et
SR
SR
MTDH-TTP C2TDH-TTP ®`³Q+ CV %'¨!¼MTDH-TTP, E1 = 0.63 V
(vs. SCE), E (E2 – E1) = 0.33 V; C2TDH-TTP, E1 = 0.60 V, E (E2 – E1) = 0.35 V½¡I®
`³Q¹E1ºV&»MTDH-TTP C2TDH-TTP ³nTK»BDH-TTP¼E1 = 0.56
V, E (E2 – E1) = 0.29 V½ªxZ^(*#»E2 V E1 Vw¹ Eº
&»MTDH-TTP C2TDH-TTP (/F5-<2HEFb»BDH-TTP !
l]
MTDH-TTP C2TDH-TTP +S§³¥ _°RG³¥ _kPs_+
Table 1 $
(MTDH-TTP)(T
CNQ)(C2TDH-TTP)(TCNQ)(C2T
Table 1. Conducting Behavior of CT Materials Based on
MTDH-TTP and C2TDH-TTP.
DH-TTP)(TCNQF4)%!B
Donor
Acceptor
D:Aa
rt/S cm–1b
A|[Ro(lWsq
MTDH-TTP
TCNQ
1:1
< 10–6
FX\rt 10–6 S cm–1 E?
I3 (plate)
4:1
0.20 (metallic)
MTDH-TTP I3–)4,;
I3 (block)
1:1
5.6 (Ea = 50 meV)
"mv~k5:1-v~k
BF4
1:0.71
4.3 (metallic)
PF6
3:1
1.7 (Ea = 98 meV)
TCNQ
1:1
< 10–6
TCNQF4
1:1
< 10–6
I3
—c
4.4 (metallic)
`"%mv~k X on
"~k 4:123<)4
C2TDH-TTP
,;}bp(eT#
MTDH-TTP /*6J
$
'Tq
a Determined
b Measured
by X-ray analysis.
by a four-probe technique on a single crystal. c Not determined.
dcs\HVa( Figure 1a zqdcWs"rY125 K DU
.8;6_IrY=h5:1-v~k1:123<)4,;T
#FXfKLXGyMTDH-TTP BF4 TZyfK(z
12 K
D'qdc>j(zFigure 1bqdc>j1.8 K t%(MTDH-TTP)3PF6 /*6T
-(MTDH-TTP)4I3 x#
LXGyfK(zC2TDH-TTP I3 T220 K D]ZyfK(z
Figure 1cT X on(&)4,;[ I3–CI2 I–
VQ$Na
$
zP%
`"%{Ku$ MTDH-TTP @709S C2TDH-TTP @+
09SO^i
$
M g w [1] In TTF Chemistry—Fundamentals and Applications of Tetrathiafulvalene, eds. J.
Yamada and T. Sugimoto, Kodansha & Springer, Tokyo, 2004, chapter 11; J. Mater.
Chem, 2 004, 14, 2951; Chem. Rev. , 2 0 04, 104, 5057.
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