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TRANSCRIPT
Porous Coordination Polymer (PCP) Metal-Organic Framework (MOF)
4500m2g-1
O. M. Yaghi, et al. Nature 423, 705 (2003) / S. Kitagawa, et al., Angew. Chem. Int. Ed. 43, 2334 (2004)
Ladder
Herringbone
Honeycomb Cube
Sheet Brick
4500m2g-1
pzdc (pyrazine-2,3-dicarboxylate) layer
L : pillar ligand [ Cu2(pzdc)2(L) ]
4 Å 6 Å 8 Å 6 Å 12 Å 6 Å
CPL-1 : L=pyrazine CPL-2 : L=4,4’-bypyrizine CPL-11 : L=bptz
-
SPring-8 BL02B2
X
IP Imaging Plate
N2 He
V V
V
L.T. He gas blower
X-ray
IP Imaging Plate
collimator sample
L.T. N2 gas blower
Gas import tube
sample
N2 gas blower 90 473 K He gas blower ( Helijet ) 10 150 K
Capillary
0.4mm��2mm
RIKEN BL44B2
Wavelength 0.8
SPring-8 BL02B2
(GVPC)
1 Pa 5.14 kPa
N /
mol
./u.c
. P / kPa
Cool down
190K
170K
150K
130K
110K
90K Methane gas pressure
8kPa
H C N O Cu pyrazine pillar-ligand
Cu2(pzdc)2 2D sheet 4 6 nanochannel
pillar
2D sheets 3D porous framework
ggandgand
Gas molecules
CPL-1 : Coordination Polymer 1 with Pillared Layer Structure
Monoclinic P21/c a=4.71534(6) b=19.8280(2) c=10.7184(1) � =95.1031(10)
O2
� = 0.8 Å
M. Takata et al. Nature 46, 377 (1995) M. Takata et al. Z.Kristallogr. 216, 71 (2001)
RWP = 2.1 % RI = 3.9 %
O2 molecule
1.0 e -3
With O2 molecules
Without guest molecules
R. Kitaura, S. Kitagawa, Y. Kubota, T. C. Kobayashi, K. Kindo, Y. Mita, A. Matsuo, M. Kobayashi, H. Chang, T. Ozawa, M. Suzuki, M. Sakata, M. Takata, Science 298, 2358 (2002)
Magnetic molecule with S = 1 p��antibonding
p��antibonding
p��bonding
p��bonding
+ +
Competed interaction
H-geometry
S-geometry T-geometry
L-geometry X-geometry
1. Electric quadrupole moment
2. Magnetic interaction
―
pppp
O2
O2-O2
O2 molecule: Simple magnetic entity S = 1
H-geometry
C. Uyeda, K. Sugiyama, M. Date, J. Phys. Soc. Jpn. 54, 1107 (1985)
S total = 0 singlet
S total = 2 quintet
(0, 0) z
x
(x, z)
K. Nozawa, N. Shima, K. Makoshi, J. Phys. Soc. Jpn. 71, 377 (2002)
H-geometry
Z = 0
S-geometry
Z ≠0
SSSSS total ===== 00000 singllllllllllllllllllllllleeeeeeeeeeeeeeeeeeeeeeeeeeeeeettttt SSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSS ttootalll = 2222 qqqquuuuiiinnnttttteeetttt
O2-O2 Spin-dependent intermolecular potential
θa θb
Φ
θa,θb,Φ
L (0,0,0) L (0,0,0) H (90,90,0) X (90,90,90) T (0,90,0)
B. Bussery et al., J. Phys. Chem. 101, 416-423 (1994)
Magnetic interaction exists between O2 molecules
H = 2 J Si Sj J : Spin coupling parameter
0
O2-O2
R. Kitaura et al., Science 298, 2358 (2002)
O2-O2 in a-solid is 3.20 Å
3.21 Å (J1 ~ - 30 K)
4.69 Å (J2 < -1 K) O2
3.56 Å
18
N2
1.0 e -3
1500 1550 1600 Raman Shift (cm-1)
Inte
nsity
(arb
.uni
ts)
16O2 17O2
without O2
1561cm-1
1513cm-1
Corresponds to the solid state at 2GPa
CPL-1
CPL-1 with O2
O2 adsorbed in CPL-1 (B–A)
Nonmagnetic ground state
W. Mori, T. C. Kobayashi et al., Mol. Cryst. Liq. Cryst. 305, 499 (1997)
Triclinic P-1 a=5.1335(2) b=9.8362(3) c=10.6881(3) � =72.557(3) � =82.450(5) =85.578(4)
MEM charge density of Cu-CHD with O2 at 90 K
Molecular O2
Guest-guest interaction Electric quadrupole moment (O2 < N2)
Magnetic interaction between O2
H-geometry S-geometry
N2 at 90K
O2 at 90K
O2 at 30K
13.2˚
12.5˚
B(O2) = 12.9(5) Å2
<u(O2)> = 0.40 Å
B(O2) = 9.4(5) Å2
<u(O2)> = 0.35 Å
B(N2) = 7.5(4) Å2
<u(N2)> = 0.31 Å
CPL-1 Cu-CHD
Dramatic changes of peak position caused by the adsorption of O2
Strong host-guest interaction Large
Insensible changes of peak position caused by the adsorption of O2 or N2
Week host-guest interaction small
Sinusoidal channel Straight channel (Si0.998Al0.002)O4
Si or Al
O
Charge density of MFI zeolite Ch d it f MFI li
Straight channel
Sinusoidal channel
MFI
32O2/unit cell
22O2/unit cell
Adsorption isotherms (77K)
N (m
olec
./u.c
)
P (kPa) T (K)
� M (e
mu/
mol
of O
2)
22O2/unit cell32O2/unit cellHext =0.1 T
22O2/unit cell
32O2/unit cell
Magnetic susceptibility
24O2/unitcell
O2 5.14 kPa
Monoclinic P121/n1
a=19.8272(2)Å
b=20.0911(2)Å β= 90.9615(9)
c=13.3501(1)Å
V=5279.21O2 0.018 kPa
Orthorhombic Pnma
a=19.9474(2)Å
b=19.9341(2)Å
c=13.3797(1)Å
V=5320.29
N (m
olec
./u.c
)
P (kPa)
32O2/unit cell
22O2/unit cell
32O2/unitcell
24O2/unitcell 32O2/unitcell
12O2/unitcell 12O2/unitcell
12O2/unitcell 20O2/unitcell
11.010.09.08.07.0
2� ( degree )11.010.09.08.07.0
2� ( degree )
90K
50K
30K
20K
30K
50K
Inte
nsity
(arb
. uni
ts)
No guest 90K
2θ(degree) 2θ(degree)
90K
20K
N2
No guest 90K
90K
Monoclinic
Orthorhombic
Monoclinic Monoclinic
O2 Orthorhombic
Orthorhombic
90
Orthorhombic a = 19.9474(2) Å
Pnma b = 19.9341(2) Å
c =13.3797(1) Å
V = 5320.29
20K 90K O2 5.14 kPa
ÅMonoclinic a = 19.8356(3) Å
P121/n1 b = 20.1044(3) Å β = 90.947(2)
c =13.3830(2) Å
V = 5263.10
O2 N2 CH4 Ar
R. Matsuda et al., J. Am. Chem. Soc. 126, 14063 (2004)
CPL-2 : pillar = 4,4’-bypyrizine
b ax
is
With C6H6 Anhydrous
Lattice shrinks in the direction of b axis with adsorption
CPL-p1 : [Cu2(dhbc)2bpy]n
Closed-Form Open-Form
20%
Gate open pressure
Pressure (atm)
N2 O2
R. Kitaura et al., Angew. Chem. Int. Ed. (2003)
0.2 MPa 200
0.434 g cm-3 40 MPa
R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature 436, 238 (2005)
1.0 e -3
CO2
5.3 Å
C2H2
5.5 Å
Pressure kPa
Am
ount
of a
dsor
ptio
n (m
olec
ules
/ un
it po
re)
b.p. 189.2 (K)
b.p. 194.7 (K)
Cool
ing
dow
n
Apohost phase I
Intermediate adsorbed phase M
Saturated adsorbed phase S
CPL-1
Vcell [Å3] 1019.25(5) → 1063.03(6) → 1036.18(3) expand contract
a
c
0 %
100 %
70 %
1
Y. Kubota, M. Takata, R. Matsuda, R. Kitaura, S. Kitagawa, T. C. Kobayashi, Angew. Chem. Int. Ed. 45, 4932 (2006)
CPL-1 MEM
Equi-contour level 1.0 eÅ-3
Containing O2 atom
Containing O1 atom
Containing O2 atom in saturated adsorbed phase S
0.00 - 1.00 eÅ-3 step 0.05 eÅ-3
2
Interaction between the acetylene and pore wall is rather weaker in phase M than that in the saturated phase S.
+
?
?
X XFEL(X-ray Free Electron Laser) Project
“
X SACLA 2011 6 1.2Å
60Hz CCD
XFEL
CCD
��
�
�
�
XFEL
SPring-8 BL19LXU
SPring-8
CCD IP CCD 10 ms 20 Hz
XFEL
G80Exp20ms110K329.ipw
Start
-1
Valve Open
1
2
3
4 5
6
7
-2 s
-1 s
0 s
1 s
2 s
3 s
4 s
5 s
6 s
7 s
8
8 s
-2 s
-2
0 s Adsorbed
No guest
-2 s 8 s
Exp. time / shot 0.02 s ( 20 ms ) Gain 80 Interval time 1.00 s
0.02 s
1.00 s
CPL-1 1 s
110 K
Δ
λ
N2 90 – 1000 K He 15 – 100 K He 15 – 300 K
X-ray
Laser