skku inorganic material lab. chemical design and control of structures of metal-dicarboxylates [m =...
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SKKU Inorganic Material Lab.
Chemical Design and Chemical Design and Control of Structures Control of Structures of of Metal-Dicarboxylates Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Z[M = Mn, Fe, Co, Ni, Znn] 이윤원이윤원 , , 김유진김유진 , , 정덕영정덕영 **
Department of Chemistry-BK21,Department of Chemistry-BK21, Sungkyunkwan Univ. Sungkyunkwan Univ.
SKKU Inorganic Material Lab.
Abstract
Understanding and controlling the structures of metal dicarboxylates is an important part of material chemistry as well as structural chemistry for the potential applications in catalysis, magnetism and etc. Crystal engineering through connecting transition metal centers has proven to be a reasonable approach to build three dimensional structures based on layered structural motifs, controlling the packing of layers by organic pillars of variable length and type.
Layered metal-dicarboxylate compounds [M = Mn, Fe, Co, Ni, Zn], synthesized under hydrothermal conditions, are represented with different lengths of dicarboxylates and characterized by SQUID, powder XRD and single-crystal XRD.
SKKU Inorganic Material Lab.
Experimental ProcedureDistilled water
+aqueous KOH
Metal ion source +
Dicarboxylic acid
Heat in oven for 24 h
under Hydrothermal conditions
Quench in cold water
TeflonVessel
~pH 4.5
oven
180ºC
HOOH
O
On
Crystal / Powder Products(Filter, wash with alcohol)
CoCoFeFeMnMn NiNi ZnZn
SKKU Inorganic Material Lab.
O1C3
C2
C1O3
O2
O5
O4O6
Formula weight 193.02g/molTemperature 296(2) K Wavelength 0.71073 Å Crystal system OrthorhombicSpace group Pca21 Cell dimensions a = 9.6163(4) Å
b = 7.3729(5) Å c = 8.3367(4) Å
Volume, Z 591.07(5) Å3, 2 Dcalcd 2.169 mg/m3
c
bc
a
Asymmetric unit
2-D inorganic layer
a
b
Crystal Structure of Mn-malonate Mn·2H2O[O2C(CH2)CO2]
4.17 Å
4.17 Å
SKKU Inorganic Material Lab.
Crystal Structure of Mn-Dicarboxylate & Fe-Dicarboxylate M2·H
2O[O2C(CH2)nCO2]2 (M = Mn or Fe)
2-D inorganic layer
M-glutarate(n = 3)
M-adipate(n = 4)
(n = odd)orthohombic
(n = even)monoclinic
c
a
a
b
8.99 Å 10.25 Å
Kim, Y.J. et al.Chem. Mater. (2001)
SKKU Inorganic Material Lab.
Crystal Structure ofCo-DicarboxylateCo[O2C(CH2)nCO2]
C. Livage et al. C. R. Acad. Sci. Paris, Chimie(2001)
b
c
2-D inorganic layer
a a
M-glutarate(n = 3)
M-pimelate(n = 5)
c c
EunWon Lee et al. Inorg. Chem. submitted
4.81 Å
4.63 Å
6.99 Å
7.01 Å
9.65 Å
9.09 Å
gauche-form
anti-form
SKKU Inorganic Material Lab.
0 50 100 150 200 250 300
0.00
0.05
0.10
0.15
0.20
0.25
0.30
M
Temperature(K)
2
4
M T0 50 100 150 200 250 300
0.00
0.02
0.04
0.06
0.08
0.10
MnDC-5 MnDC-6 MnDC-7 MnDC-8 MnDC-9 MnDC-10
M
Temperature(K)
0
1
2
3
4
M T
eff = 5.71 B (at 300 K) C = 4.30(9) cm3K/mol = -19(2) K
Magnetization (1)
Mn2·H2O[O2C(CH2)nCO2]2 (n = 5-10)
0 50 100 150 200 250 3000.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
M
Temperature (oC)
Mn-adipate Fe-adipate Mn,Fe-adipate
0
2
4
6
8
10
M T
MnFe·H2O[O2C(CH2)4CO2]2
eff = 5.620 B (at 300 K) C = 4.001 cm3K/mol = -5.825 K
*eff (expt) : 5.65-6.10 B
for H.S. state of Mn2+ [3d5]
Mn·2H2O[O2C(CH2)CO2]
SKKU Inorganic Material Lab.
0 50 100 150 200 250 3000.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
9 K
14 K
M
Temperature/ K
0
1
2
M T
eff (expt): 4.30-5.20 B for H.S. 1.73 B for L.S. state of Co2+[3d7]
-1500 -1000 -500 0 500 1000 1500-200
0
200
Ma
gn
eti
za
tio
n
Field(Oe)
2K 4.2K
eff = 4.49 B (at 300 K)C = 2.71 cm3K/mol = -25.75 K
Hysteresis
Magnetization (2)
Co[O2C(CH2)3CO2]
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2 3 4 5 6 7 8 9 10 11 12 136
8
10
12
14
16
18
20
22
Inte
rla
yer
Dis
tan
ce (
A)
Number of CH2 groups
Ni Mn Fe Co Zn
Powder XRD Patterns
Interlayer Distances between the Inorganic layers
Ni d = 1.21 n + 6.90 (Å)Mn d = 1.27 n + 5.18 (Å)Fe d = 1.16 n + 5.62 (Å)Co d = 1.17 n + 3.52 (Å)Zn d = 1.15 n + 3.59 (Å)
Powder XRD Patterns of M-adipate
5 10 15 20 25
2
Fe-adipate
Ni-adipate
Zn-adipate
Mn,Fe-adipate
Mn-adipate
Co-adipate
Inte
nsi
ty
SKKU Inorganic Material Lab.
ConclusionWe have synthesized M-dicarboxylate compounds with various 3 -dime
nsional crystal structures [M = Mn, Fe, Co, Ni, Zn].The unique feature facilitates structure prediction and provides guidance
for the design of inclusion compounds based on the dicarboxylate ligands. This large database of structural information, based on a systematic study of closely related compounds, has proven valuable for advancing general crystal engineering principles.
We anticipate that further investigation of these materials and the principles governing their characteristics will improve understanding of crystal engineering and produce a new generation of designer materials based on supramolecular assembly.
AcknowledgmentWe acknowledge the support by the Electron Spin Science Center
at POSTECH, which was established by the KOSEF.
SKKU Inorganic Material Lab.
SKKU Inorganic Material Lab.
SKKU Inorganic Material Lab.
Powder XRD Patterns
Interlayer Distances between the Inorganic layers
Ni d = 1.21 n + 6.90Mn d = 1.27 n + 5.18Fe d = 1.16 n + 5.62Co d = 1.17 n + 3.52Zn d = 1.15 n + 3.59
Powder XRD Patterns of M-adipate
5 10 15 20 25
2
Inte
nsity
Fe-adipate
Ni-adipate
Zn-adipate
Mn,Fe-adipate
Mn-adipate
Co-adipate
2 4 6 8 10 12
6
8
10
12
14
16
18
20
22
Inte
rla
ye
r d
ista
nc
e (
A)
Number of CH2 groups
Ni Mn Fe Zn Co