skku inorganic material lab. chemical design and control of structures of metal-dicarboxylates [m =...

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SKKU Inorganic Material Lab. Chemical Design Chemical Design and and Control of Struc Control of Struc tures of tures of Metal-Dicarboxyl Metal-Dicarboxyl ates ates [M = Mn, Fe, Co, [M = Mn, Fe, Co, Ni, Zn Ni, Zn] 이이이 이이이 , , 이이이 이이이 , , 이이이 이이이 * * Department of Chemistry-BK21, Department of Chemistry-BK21, Sungkyunkwan Univ. Sungkyunkwan Univ.

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Page 1: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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.

Page 2: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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.

Page 3: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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

Page 4: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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

Page 5: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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)

Page 6: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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

Page 7: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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]

Page 8: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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]

Page 9: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

SKKU Inorganic Material Lab.

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

Page 10: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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.

Page 11: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

SKKU Inorganic Material Lab.

Page 12: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

SKKU Inorganic Material Lab.

Page 13: SKKU Inorganic Material Lab. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진,

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