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Duk-Young Jung*, YooJin Kim and EunWon Lee

Replication of Magnetic Long Range Ordering in Self-assembled Coordination Polymers of Manganese Dicarboxylates. Duk-Young Jung*, YooJin Kim and EunWon Lee Department of Chemistry, SungKyunKwan University, South Korea. Abstract.

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Duk-Young Jung*, YooJin Kim and EunWon Lee

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  1. Replication of Magnetic Long Range Ordering in Self-assembled Coordination Polymers of Manganese Dicarboxylates Duk-Young Jung*, YooJin Kim and EunWon Lee Department of Chemistry, SungKyunKwan University, South Korea

  2. Abstract We synthesized a series of new three-dimensional organic/inorganic coordinate polymers, as single crystals or polycrystallines by the hydrothermal reaction of metal cations with saturated aliphatic dicarboxylic acids (glutaric to tetradecanedioic acid ) in the presence of base. The prepared manganese dicarboxylates were characterized by single-crystal (and powder) X-ray diffraction, thermal analysis and SQUID magnetic measurement. The crystal structure of these compounds is a pillared layer structure assembled from the molecular precursors in solution.

  3. Experimental HOOC(CH2)nCOOH Dicarboxylic acid HOOC(CH2)nCOOH n=3 glutaric n=4 adipic n=5 pimelic n=6 suberic n=7 azelic n=8 sebacic n=9 undecanedioic n=10 dodecanedioic n=11 tridecanedioic n=12 tetradecanedioic n = odd number MnCl2 4H2O + [Dicarboxylic acid] KOH + diglyme n = even number Hydrothermal synthesis ••••• Mn2(H2O)[CO2(CH2)nCO2]2 (n = 3 to 12) , MnDC-n compounds

  4. Interlayer Distance 20.42 Å (MnDC-12) (Å) d dicarboxylate Layer distance 8.99 Å (MnDC-3) dicarboxylate d = 1.269(1)n + 5.18(1) (8.99 [MnDC-3] –20.42 Å [MnDC-12] )

  5. XRPD Spectra 20.42Å MnDC-12 MnDC-11 MnDC-10 MnDC-9 MnDC-8 MnDC-7 19.14Å 17.87Å 16.58Å 15.32Å 14.06Å

  6. Crystal Structure Refinement for MnDC-n (n = 3 to 6) MnDC-3 MnDC-4 MnDC-5 MnDC-6 formula C10H14Mn2O9 C12H18Mn2O9 C14H22Mn2O9 C16H26Mn2O9 fw 388.10 416.15 444.20 472.25 crystal system orthorhombic monoclinic orthorhombic monoclinic space group Pbcm (No. 57) C2/c (No.15) Pbcm (No. 57) C2/c (No.15) T (K) 296(2) 297(2) 296(2) 295(2) a (Å) 7.6017(6) 21.671(2) 7.6089(8) 26.54(2) b (Å) 9.1156(4) 7.6023(7) 9.167(2) 7.617(7) c (Å) 17.9749(12) 9.1452(9) 23.070(3) 9.188(8)  (deg)90 90 90 90  (deg)90 108.849(7) 90 105.27(6) (deg)90 90 90 90 V (Å3) 1245.55(14)1425.9(2) 1609.1(4) 1792(3) Z 4 4 4 4 Dcalcd (mg cm-3) 2.070 1.938 1.834 - goodness-of-fit on F2 1.097 1.085 1.140 - final R1a0.0241 0.0380 0.0541 - final wR2b 0.0686 0.1012 0.1150 -

  7. Crystal Structure MnDC- 3 and MnDC-4 c a a b MnDC-3 MnDC - 4

  8. Crystal Structure MnDC- 5 and MnDC-6 c a a b MnDC-5 MnDC - 6

  9. Magnetic parameters of the MnDC-n ( n = 3 – 12) and Low T Compound C/cgsa/Kbeff(C)ceff(RT)dTN Wagnere Hillerf _____________________________________________________________ J(cm-1) g J(cm-1) g MnDC-3 4.35 -17.92 5.92 5.75 5.1 -2.10 2.01 -1.98 2.01 MnDC-4 4.36 -20.52 5.93 5.75 4.7 -2.16 2.00 -2.04 2.00 MnDC-5 4.34 -17.81 5.91 5.75 - -2.08 2.01 -1.96 2.01 MnDC-6 4.30 -22.61 5.89 5.70 - -2.15 1.96 -2.00 1.96 MnDC-7 4.29 -18.36 5.88 5.75 - -2.06 1.99 -1.91 1.98 MnDC-8 4.24 -16.21 5.85 5.69 - -2.03 1.95 -1.89 1.94 MnDC-9 4.41 -19.18 5.97 5.80 - -2.11 2.02 -1.96 2.00 MnDC-10 4.28 -17.67 5.87 5.70 - -1.97 1.97 -1.83 1.96 MnDC-11 4.33 -18.04 5.91 5.72 - -1.95 1.99 -1.81 1.98 MnDC-12 4.22 -18.44 5.84 5.60 - -2.03 1.97 -1.87 1.95 ____________________________________________________________________________________________ a Curie constant (50-300K), b Weiss constant (50-300K), c eff (C) = 2.84(C)1/2 , eff (spin only) = 5.92B, deff (RT) = 2.84(T)1/2 where T  300K, e ref 16 (5-300K), f ref 18 (5-300K). 4.7K MnDC-4 MnDC-3 5.1K

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