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Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn ]

Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn ]. 이윤원 , 김유진 , 정덕영* Department of Chemistry-BK21, Sungkyunkwan Univ. Abstract.

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Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn ]

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  1. Chemical Design and Control of Structures of Metal-Dicarboxylates [M = Mn, Fe, Co, Ni, Zn] 이윤원, 김유진, 정덕영* Department of Chemistry-BK21, Sungkyunkwan Univ.

  2. 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. oven 180ºC Quench in cold water Crystal / Powder Products (Filter, wash with alcohol) Mn Fe Co Ni Zn Experimental Procedure Teflon Vessel Metal ion source + Dicarboxylic acid Distilled water + aqueous KOH ~pH 4.5 O O H H O n O Heat in oven for 24 h underHydrothermal conditions

  4. Crystal Structure of Mn-malonate Mn·2H2O[O2C(CH2)CO2] • Formula weight 193.02g/mol • Temperature 296(2) K • Wavelength 0.71073 Å • Crystal system Orthorhombic • Space group Pca21 • Cell dimensions a = 9.6163(4) Å • b = 7.3729(5) Å • c = 8.3367(4) Å • Volume, Z591.07(5) Å3, 2 • Dcalcd 2.169 mg/m3 Asymmetric unit 2-D inorganic layer 4.17 Å c a b c 4.17 Å a b

  5. Crystal Structure of Mn-Dicarboxylate & Fe-DicarboxylateM2·H2O[O2C(CH2)nCO2]2 (M = Mn or Fe) (n = odd) orthohombic (n = even) monoclinic 2-D inorganic layer 10.25 Å 8.99 Å c a a b M-glutarate (n = 3) M-adipate (n = 4) Kim, Y.J. et al. Chem. Mater. (2001)

  6. Crystal Structure of Co-Dicarboxylate Co[O2C(CH2)nCO2] gauche-form anti-form 2-D inorganic layer 9.65 Å 6.99 Å 9.09 Å 7.01 Å a a b c c 4.81 Å M-glutarate (n = 3) M-pimelate (n = 5) c C. Livage et al. C. R. Acad. Sci. Paris, Chimie (2001) EunWon Lee et al. Inorg. Chem. submitted 4.63 Å

  7. Magnetization (1) MnFe·H2O[O2C(CH2)4CO2]2 Mn2·H2O[O2C(CH2)nCO2]2 (n = 5-10) eff= 5.71 B (at 300 K) C = 4.30(9) cm3K/mol Q = -19(2) K Mn·2H2O[O2C(CH2)CO2] eff= 5.620 B (at 300 K) C = 4.001 cm3K/mol Q = -5.825 K *eff (expt) : 5.65-6.10B for H.S. state of Mn2+ [3d5]

  8. Magnetization (2) Co[O2C(CH2)3CO2] Hysteresis eff = 4.49 B (at 300 K) C = 2.71 cm3K/mol Q = -25.75 K eff (expt): 4.30-5.20B for H.S. 1.73 B for L.S. state of Co2+[3d7]

  9. Powder XRD Patterns of M-adipate Fe-adipate Ni-adipate Zn-adipate Intensity Mn,Fe-adipate Mn-adipate Co-adipate Powder XRD Patterns Interlayer Distances between the Inorganic layers Ni d = 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)

  10. 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. Fe-adipate Ni-adipate Zn-adipate Mn,Fe-adipate Mn-adipate Co-adipate Powder XRD Patterns Interlayer Distances between the Inorganic layers Powder XRD Patterns of M-adipate Ni d = 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

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