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, 정덕영 * Department of Chemistry-BK21, Sungkyunkwan Univ. Sungkyunkwan Univ.

2. 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.

3. SKKU Inorganic Material Lab. Experimental Procedure Distilled water + aqueous KOH Metal ion source + Dicarboxylic acid Heat in oven for 24 h under Hydrothermal conditions Quench in cold water Teflon Vessel ~pH 4.5 oven 180ºC HO OH O O n Crystal / Powder Products (Filter, wash with alcohol) CoFeMnNiZn

4. SKKU Inorganic Material Lab. Formula weight193.02g/mol Temperature296(2) K Wavelength0.71073 Å Crystal systemOrthorhombic Space groupPca2 1 Cell dimensionsa = 9.6163(4) Å b = 7.3729(5) Å c = 8.3367(4) Å Volume, Z591.07(5) Å 3, 2 D calcd 2.169 mg/m 3 c b c a Asymmetric unit 2-D inorganic layer a b Crystal Structure of Mn-malonate Mn·2H 2 O[O 2 C(CH 2 )CO 2 ] 4.17 Å

5. SKKU Inorganic Material Lab. Crystal Structure of Mn-Dicarboxylate & Fe-Dicarboxylate M 2 ·H 2 O[O 2 C(CH 2 ) n CO 2 ] 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)

6. SKKU Inorganic Material Lab. Crystal Structure of Co-Dicarboxylate Co[O 2 C(CH 2 ) n CO 2 ] 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

7. SKKU Inorganic Material Lab.  eff = 5.71  B (at 300 K) C = 4.30(9) cm 3 K/mol  = -19(2) K Magnetization (1) Mn 2 ·H 2 O[O 2 C(CH 2 ) n CO 2 ] 2 (n = 5-10) MnFe·H 2 O[O 2 C(CH 2 ) 4 CO 2 ] 2  eff = 5.620  B (at 300 K) C = 4.001 cm 3 K/mol  = -5.825 K *  eff (expt) : 5.65-6.10  B for H.S. state of Mn 2+ [3d 5 ] Mn·2H 2 O[O 2 C(CH 2 )CO 2 ]

8. SKKU Inorganic Material Lab.  eff (expt): 4.30-5.20  B for H.S. 1.73  B for L.S. state of Co 2+ [3d 7 ]  eff = 4.49  B (at 300 K) C = 2.71 cm 3 K/mol  = -25.75 K Hysteresis Magnetization (2) Co[O 2 C(CH 2 ) 3 CO 2 ]

9. SKKU Inorganic Material Lab. Powder XRD Patterns Interlayer Distances between the Inorganic layers Nid = 1.21 n + 6.90 (Å) Mnd = 1.27 n + 5.18 (Å) Fed = 1.16 n + 5.62 (Å) Cod = 1.17 n + 3.52 (Å) Znd = 1.15 n + 3.59 (Å) Powder XRD Patterns of M-adipate Fe-adipate Ni-adipate Zn-adipate Mn,Fe-adipate Mn-adipate Co-adipate Intensity

10. SKKU Inorganic Material Lab. Conclusion We have synthesized M-dicarboxylate compounds with various 3 - dimensional 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. Acknowledgment We acknowledge the support by the Electron Spin Science Center at POSTECH, which was established by the KOSEF.

11. SKKU Inorganic Material Lab.

13. Powder XRD Patterns Interlayer Distances between the Inorganic layers Nid = 1.21 n + 6.90 Mnd = 1.27 n + 5.18 Fed = 1.16 n + 5.62 Cod = 1.17 n + 3.52 Znd = 1.15 n + 3.59 Powder XRD Patterns of M-adipate Fe-adipate Ni-adipate Zn-adipate Mn,Fe-adipate Mn-adipate Co-adipate