6th_conductor...ttf ss ss 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (bdt-ttp or...
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S cm-1 = -1 cm-1
•
• ( ) ()
1) 2)
( )
(Tc)
MRI
100%( 90% )
• ( Tc 9 K)
• (Tc 23 K)
• (Tc 135 K)
• (Tc 40 K)
• (Tc 33 K)
• (Tc 14 K)
• BCS– -
–
–
– Tc 30K
–
BCS
-
++
-
+
- -
Tc
Little
-Tc 1000 K
•
•
•
•
酸化還元状態の制約
HOMO
LUMO
D0
LUMO
D+1
D+2 D0
D+0.5
D+1D0 D0D+1
HOMO-LUMO
D+0.5
D+1D0 D0
D+1
D+1
D+1 D
0D
+2
D+0.5
多段階酸化還元系+•
-e
+e +e
-e
-
- -
•
-e
+e
-e
+e
TCNQ TCNQ-• TCNQ2-
+ +
CNNC
NC CN
S
SS
S
CNNC
NC CN
CNNC
NC CN
S
SS
S S
SS
S
TTF TTF+• TTF2+
分子の積層様式
D D+
D A
有機導電体の歴史
NC CN
CNNC
S
S
S
S
perylene-Brx
(1954) TCNQ (1960)
-Brx (x = 3-4)
TTF (1970)
TTF•TCNQ
TTF•TCNQ
CN
CNNC
NC
TCNQ
S
SS
S
TTF
TTF•TCNQの導電性
-
kF(pF)( E)
T , E
E
kF(pF)
T ,
(TMI)
TMI
-kF -kF kFkF
kxkx
kyky
2kF
2kF ( )
k = ±kF
(b),(c)
(b)
TTF
Se
Se
Se
Se
Se Se
Se Se
TSF
S
S
S
S
S
S
S
S S S
S
S
S
S SS
BEDT-TTF
(TMTSF)+2X
-Se
Se
Se
Se
CH3
CH3H3C
H3C
TMTSF
X = ClO4
Tc = 1.4 K
TMTSF •••Se
(1980)
BEDT-TTF
S
S
S
S
S
SS
S
BEDT-TTF
Cava (1978)
(BEDT-TTF)2ClO4(TCE)0.5:
1.4 K ( ,1982)
”
BEDT-TTF
Tc 14.1 K
BEDT-TTF 70%
a1•b1 = 2 a1•b2 = 0a2•b1 = 0 a2•b2 = 2
b1 = (2 /a)e1, b2 = (2 /a)e2
e1, e2: , ya1 = ae1, a2 = ae2
TTF
T. Mori et al., Bull. Chem. Soc. Jpn., 557, 627 (1984)
Molecular orbital calculationfor a single moleculel(Extended Hückel method)
Intermolecular overlap integrals
Transfer integrals
Band structure and Fermi surface
HOMO ••• DonorLUMO ••• Acceptor
t = ES
Tight-binding method
EDT-TTF
BEDT-TTF HOMO
BEDT-TTF HOMO
Relative change of the overlap S as a function of the intermolecular sulfur-sulfur distance R, compared with the overlap S0 at R0 = 3.80 Å
-(BEDT-TTF)2I3
-(BEDT-TTF)2I3
(upper band)
BEDT-TTF
"-type-, -type
-type
M(dmit)2, M = Ni, Pd
DMET-TSFS,S-DMBEDT-TTF BETS
BEDO-TTF DMETBEDT-TTF
Acceptors
Donors
DTEDT
Se
Se
Se
SeMe
MeMe S
Me S
S
S
S
SS
S
S
S
S
SMe
MeMe
Me
S
S
S
S
S
S
S
S
S
S
S
M
S
S
S
S
S
S S
S
S
S
S
O
OO
OSe
Se
S
SMe
SMe
S
Se
Se
Se
Se
S
S
S
S
S
SS
S
S
SS
S
S
S
S
SS
SMe Se
SeMe
Se
SeMe
SMe
S
TMET-STF
Se
Se
S
S
S
S
BEDSe-TTF
S
S
S
S
Se
SeSe
Se
ESET-TTF
S
S
S
S
S
SSe
Se
Se
Se
Se
SeS
S
S
S S
S
S
SS
S
BDA-TTP
MDT-TTF TMTSF
C60
TMTTF
MDT-TSF meso-DMBEDT-TTF
S
S
S
S
S
SS
SMe
Me
S
S
S
SS
S
O
O
DOHT
S
SS
S
S
SS
SS
SS
S
S
S
S
S
S
S
S
S S S
S
S
S
S SS
BEDT-TTF
( )TTF
BEDT-TTF
S
S
S
S
S
S
S
S S S
S
S
S
S SS
S-S
perylene
H
H
H H
H
H
H
H
HH
H
H
H
H H
H
H
H
HH
HH
H
S S
S S
TTT
BEDT-TTF
Overlap integrals of HOMO (x10-3)
b1 = 17.6, b2 = 22.4, p = 17.9,
q = 3.0, r = -4.7
Overlap integrals of LUMO (x10-3)
c1 = 15.7, c2 = 12.9, p
= -0.8, q = 0.12
S
S
S
S
Se
Se
CPDT-STF
CN
CNNC
NC
TCNQ
BEDT-TTF
-(BEDT-TTF)2X
Mott
BEDT-TTF U/W 1U:
W:
TTF
S
SR
SR
S
S
S
S
S
IVIIIIII
S
S
S
S
S
S
S
S S S
S
S
S
S SS
S
SS
S S
SS
S
BEDT-TTF
S S S
S S S
S
S
TTFS S
S S
2,5-bis(1,3-dithiol-2-ylidene)-
1,3,4,6-tetrathiapentalene
(BDT-TTP or simply TTP) TTP
S S S
S S S
S
S
S S S
S S S
S
S
S S
O
S S
O
S S S
S S S
S
S
R
RR
RS
S
S
R
R
S S
O
S S
S
S
S
S
O
S S S
S S S
O
R
RS S R
S S RR
R
P(OEt)3
R. R. Shumaker, E. M. Engler et al.,
J. Chem. Soc., Chem. Commun., 1979, 516
J. Am. Chem. Soc., 1980, 102, 6651.
R = CN, CF3, CO2Me
CV X CT
TTF
+
+ +
+
BDT-TTP
100%95%
47% 50%
82%
/ P(OMe)3
toluene
/ P(OEt)3 1) NaOMe/CH2Cl2-MeOH, r.t.
2) ZnCl2, Bu4NBr, r.t.
3) (Cl3CO)2CO/THF, -78 °C
HMPA
BDT-TTP 87%
110 °C
110 °C 90 - 120 °C
(Et4N)2
p-AcOC6H4CH2Cl
acetone reflux
CHCl3-AcOH
r.t.
S
SMeO2C
S
S
MeO2C
S
S
S
SCH2C6H4OAc-p
SCH2C6H4OAc-p
S
S
S
SS
S S
S
CO2Me
CO2Me
S
S
S
SS
S S
S
S
S
S
O
S
SS
S
S
S
Zn
S
S
S
S
S
S S
S
S
S
p-AcOC6H4CH2S
Sp-AcOC6H4CH2S
S
O
p-AcOC6H4CH2S
p-AcOC6H4CH2S
S
S
S
LiBr·H2O
Hg(OAc)2
Y. Misaki, et. al., Chem. Lett., 2321-2324 (1992).
BDT-TTP
TTF
Kilburn et al. Tetrahedron. Lett., 33, 3923 (1992).
R = H, CO2Me, SCnH2n+1 (n = 2-6)
R-R = -SCH2S-, -S(CH2)2S-, -S(CH2)3S-
R = H, CO2Me, SMe
R-R = -SCH2S-, -S(CH2)2S-, -S(CH2)3S-, -O(CH2)2O-
R = H, CO2Me, SeMe
R-R = -SCH2S-, -S(CH2)2S-, -O(CH2)2O-R = H, CO2Me, SMe, SeMe
R-R = -SCH2S-, -S(CH2)2S-, -O(CH2)2O-
R-R = -S(CH2)2S-, -S(CH2)3S-
R = H, CO2Me, SMe, SeMe
R-R = -SCH2S-, -S(CH2)2S-, -O(CH2)2O-
R = H, CO2Me, SMe, SeMe
R-R = -SCH2S-, -S(CH2)2S-, -O(CH2)2O-
R = H, CO2Me, SMe
R-R = -SCH2S-, -S(CH2)2S-, -S(CH2)3S-,
R = Me, SMe
R' = Me, Et, Prn
S
S
S
S
S
S
S
S
R
RMe
MeS
S
S
S
S
S
S
S
R
S
RO
OS
S
S
S
S
S
S
S
S
R
S
RMeS
MeS
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
R
R S
S
S
S
S
S
S
R
RS
S
S
S
S
S
S
S
S
S
R
RS
S
S
S
S
S
S
S
S
S
R
R
S
S
S
S
S
S
S
S
R
R
S
S
S
S
S
S
S
S
R
R
R'
R'
R = H, Me
R-R = -(CH2)3-, -(CH2)4-, -O(CH2)2O-
Se
Se
S
S
S
S
S
S
R
R
R = H, Me
R-R = -(CH2)3-, -(CH2)4-, -O(CH2)2O-
Se
Se
S
S
S
S
S
S
R
R
R = Me
R-R = -(CH2)3-, -(CH2)4-, -O(CH2)2O-
Se
Se
S
S
S
S
S
S
R
R
MeO2C
MeO2C
Se
Se
S
S
S
S
S
S
R
RMeS
MeS
R = H, CO2Me
Se
Se
S
S
S
S
Se
Se
R
R
R = H, SMe
R-R = -(CH2)3-, -(CH2)4-, -O(CH2)2O-
S
S
R = H, CO2Me
Se
Se
S
S
S
S
S
S
R
R
Se
Se
S
S
S
S
S
S
R
RMeSe
MeSe
R = Me
R-R = -O(CH2)2O-
R = SMe, SEt, SC6H13n
S
S
S
S
S
S
S
S
R
RS
SEtO2C
EtO2C
BDT-TTP
Table. Redox Potentials of TTP and Its Related Compounds in PhCN (V vS. SCE, Pt electrode, 25 °C)
Compound E1 E2 E3 E4 E2-E1
S
S
S
SS
S S
S
TTP
+0.44 +0.62 +1.05a) +1.13a) 0.18
S
S
S
S
TTF
+0.35 +0.77 0.42
S
S
S
SS
S Me
Me
MeDT-TTF
+0.45 +0.76 +1.14a) 0.31
S
S SMe
SMeS
S+0.44 +0.77 0.33
a) Irreversible step. Anodic peak potentials.
S
S
S
S
S
S
S
SMeS
MeS SMe
SMe
TTM-TTP
I3
Mott
D+1
D+2D0
+
(TTM-TTP)I3
(TTM-TTP)(I3)5/3
Temperature / K
Resis
tivity /
cm
rt = 700 S cm-1
160 K
BDT-TTP
a1 a2
a/p 3 - 4
a1 = 25.1, a2 = 25.3, p1 = 7.9, p2 = 8.6, c = 0.8
BDT-TTP (ST-TTP, BDS-TTP)
S
S
S
S Y
Y
X
X
X = Y = S, BDT-TTPX = S, Y = Se, ST-TTPX = Y = Se, BDS-TTP
(ClO4, BF4, ReO4)
(PF6, AsF6, SbF6, TaF6)
(Au(CN)2)
(NO3)
(Re6S6Cl8, Mo6Cl14)
BEDT-TTF
3.1 Å 6.2 Å
7.3 Å
D : A = 2 : 1
(BDT-TTP)1/2+
D : A = 3 : 1
(BDT-TTP)1/3+D : A = 6 : 1
(BDT-TTP)1/3+
PF6- Au(CN)2
- Re6S6Cl82-
TTP
• side-by-
side
•
•
Self-aggregation to adopt -type structure
S
S
S
S
S
S
Se
Se
2
Au(CN)2
CH-TS-TTP
S
S
S
S
S
S
S
S
S
S
S
S
S
S
Se
Se
2
2
X = ClO4, (I3)0.62
X = AsF6, Au(CN)2
CH-TTP
X
CH-ST-TTP
X
-Type salts
S
S
S
S
S
S
Se
Se
TMET-TS-TTP
MeS
MeS S
S
2
TCNQ
Self-aggregation to adopt -type structure
S
S
S
S
S
S
S
SMeS
MeS S
S
TMET-TTP
S
S
S
S
S
S
S
SMeS
MeS Se
Se
TMES-TTP
S
S
S
S
S
S
Se
SeMeS
MeS S
S
TMET-TS-TTP
TCNQ2
4
(X)m
X = AuI2, PF6, ReO4, ClO4
I3
-Type salts
S
S
S
SS
S S
SO
O
EO-TTP
a1 a2
S
S
S
S S
SS
SO
O
CPEO-TTP2AsF6
(SbF6)0.4
Effect of methythio group
Strongly dimerized typeMolecular packing
S
S
S
S S
SSe
Se O
O
TMEO-ST-TTP
MeS
MeS 2AsF6
Steric hindrance SCH3 >> -(CH2)4-
BDT-TTP
S
S
S
S
S
S
S
S
CH-TTP
S
S
S
SS
S S
SO
O
EO-TTP
S
S
S
S S
SSe
Se O
OMeS
MeS
TMEO-ST-TTP
a1 a2
X
S
S
S
S
S
S
S
S
S
S
X
X
X
X
S
S
S
S
S
S S
S
S
S
S
S
S
S
X
X = O, S, Se
X = O, S
X = S, Se
S
S
S
S S
S S
S
XX = O, S
S
S
CH CH
S
S
S
S
CH CH
S
S S
S
CHX
CH
S
S
S
S
CHX
CH
S
S
X = S, CH=CH
TTP
S
S
S
S
S
S
S
S
BDT-TTP
HOMO
(DTEDT)3Au(CN)2 (Tc = 4 K)
DTEDT
DTEDT
BDT-TTP
30020010000.00
0.02
0.04
0.06
0.08
10864200.00
0.01
0.02
0.03
0.04
30020010000.0
0.5
1.0
No
rma
lized
Re
sis
tivity
T / K
rt = 50 - 900 S cm-1
T / K
Resis
tivity /
·c
m
DTEDT
DTEDT
I3
AsF6
GaCl4
SbF6
ReO4
S
S
S
S
S
S
S
S
DTEDT
Au(CN)2
DTEDT3
Se
Se
Se
Se
Me
MeMe
Me S
S
S
SS
S S
S
M3C60
Tc > 30K
(BEDT-TTF)2X
Tc ~ 10K
(TMTSF)2X
Tc ~ 1K
X
S
S
S
S
S
S
X = S, TPDT-TTPX = O, PDT-TTP
TTP
Side-by-side
~ ~
Tc
O
S
S
S
S
Se
Se
PDS-TTP
AsF6
2
S
S S
S S
S
O
SeMe
SeMe
(PF6)(PhCl)X
SM-PDT
X
S
S
S
S
Se
Se
SCH3
SCH3
X = O, TM-PDS, A = SbF6, ClO4, ReO4
X = S, TM-TPDS, A = AsF6
2
A
(PDS-TTP)2AsF6
triclinic,
space Group P1
a = 6.6089(7) Å
b = 6.9986(8) Å
c = 17.722(2) Å
= 81.371(6)°
= 79.765(8)°
= 79.632(3)°
V =787.6(1) Å3
Z = 1
R = 0.096
Crystal data:
Head-to-tail overlap mode in the stack
Two-dimensional conducting sheet
O-H hydrogen bond between conducting sheet
H-F hydrogen bond between donor and anion
.
.
.
.
O
S
S
S
S
Se
Se
PDS-TTP
AsF6
2
2.69A°
(PDS-TTP)2AsF6 O
S
S
S
S
Se
Se
PDS-TTP
AsF6
2
S
S
S
S
X
X
X
X
O
S
S
S
S
Se
Se
S
S
S
S X
X
S
S
S
S
S
S Se
SeTCNQ
AsF6
AX = S, A = Au(CN)2X = Se, A =TaF6
Am X = S, SeA: various anions
2
3
(PDS-TTP)2AsF6
The intermoleculer overlap integral (x10-3)
b1 = 10.0, b2 = 8.7, p1 = 3.1, p2 = 4.9, a = 1.2
(PDS-TTP)2AsF6
(TM-TPDS)2AsF6
SS
S
S
S
Se
Se
SCH3
SCH3
TM-TPDS2
AsF6
"edge-to-side"
O
S
S
S
S
Se
Se
SCH3
SCH3
TM-PDS
X2
(X = ClO4, ReO4, PF6, SbF6)
" "
" "
(TM-TPDS)2AsF6
(TM-PDS)2X (TM-PDS)2AsF6
(SM-PDT)2AsF6(PhCl)
Se---Se : 3.694(2), 3.738(2) A ( ) cf. vdw radius; Se : 1.90 A
rt = 4.8 S cm-1, Ea = 0.050 eV
side-by-side
"edge-to-edge" (= bc )
1:1
°
°
(SM-PDT)2AsF6(PhCl)
"
S
S S
S S
S
O
SeMe
SeMe
SM-PDT
The intermolecular overlap integrals
c1 = 6.3, c2 = 8.1, p1 = -2.3, p2 =
0.00, b = -0.8 (x10-3).
"edge-to-edge" ( 30-40% )
O
S
S
S
S
Se
Se
SMe
SMe
2
OS
S
S
S
S
S
SeMe
SeMe
SM-PDT
PF6(PhCl)m
TM-PDS
SbF6O
S
S
S
S
Se
Se
2
PDS-TTP
AsF6
side-to-edge
edge-to-edgeside-by-side
Se-Se
side-by-side
side-by-side
S
Se
Se
Se
Se
S
S
O
S
S
S
S
S
S
TeMe
TeMe
SMe
SMe
O
S
S
S
S
O
"Windmill" type structure with higher 3D character
Psedo "-type structure with higher 2D character
O
S
S
S
S
S
S
SeMe
SeMe
O
S
S
S
S
Se
Se
SMe
SMe
O
S
S
S
S
Se
Se
-Type structure with larger interlayer interaction
Next Targets
S
S
S
S
S
S S
S
S
S
S
SS
S S
S
BDT-TTP
S
S
S
SS
S S
SS
S
S
S
S
SS
S S
S
S
S
S
SS
S S
S N
NO
O+_
·S
SS
S S
SS
S
BDA-TTP
O
R
R
R
RR
R
S
S
S
SS
S S
SR
R
N N O·
(BDA-TTP)2X (X = PF6, AsF6, SbF6)
Yamada et alAngew. Chem. Int. Ed. Engl.,38, 810 (1999)
Yamada et. al
Chem. Coomun., 1996, 2517
Yamada et al.J. Am. Chem. Soc., 123, 4174 (2001).
Sugawara et al.
Kobayashi et al.Synth. Met., in press
Takahashi et al.
Se
Se
S
SS
S S
S
R
RMe
Me
Yamada et al.
J Org. Chem., 61, 3987 (1996)S
S
S
S
SNi
S
S
S
S
S
S
S
Tanaka et al.,Science, 291, 285 (2001)
S
S
S
S S
S
S
S
Summary
BDT-TTP
BDT-TTP
TTF
S
S
S
S
S
S
S
SO
S
S
S
S
X
X
R
R
DTEDT X = S, PDT-TTP
X = Se, PDS-TTP
R = H, SMe, SeMe
PDT-TTP, PDS-TTP
TTP
(
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