Replication of Magnetic Long Range Replication of Magnetic Long Range Ordering in Self-assembled CoordinaOrdering in Self-assembled Coordination Polymers of Manganese Dicarbotion Polymers of Manganese Dicarbo

xylatesxylates

Duk-Young Jung*, YooJin Kim and EunWon Lee

Department of Chemistry, SungKyunKwan University, South Korea

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.

Abstract Abstract

ExperimentalExperimental

n = odd number

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

MnCl2 4H2O + [Dicarboxylic acid]

KOH + diglyme

Hydrothermal synthesis

Mn2(H2O)[CO2(CH2)nCO2]2 (n = 3 to 12)

,

MnDC-n compounds

•••••

n = even number

HOOC(CH2)nCOOH

0 1 2 3 4 5 6 7 8 9 10 11 12 130

2

4

6

8

10

12

14

16

18

20

22

24

Inte

rlay

er D

ista

nce

Number of CH2 groups

( Å )

Interlayer DistanceInterlayer Distance

Layer distance

d = 1.269(1)n + 5.18(1)

(8.99 [MnDC-3] –20.42 Å [MnDC-12] )

20.42 Å (MnDC-12)

8.99 Å (MnDC-3)

d dicarboxylate

dicarboxylate

XRPD SpectraXRPD Spectra

20.42Å

19.14Å

17.87Å

16.58Å

15.32Å

14.06Å

MnDC-12

MnDC-11

MnDC-10

MnDC-9

MnDC-8

MnDC-7

Crystal Structure Refinement for MnDC-n (n = 3 to 6) Crystal Structure Refinement for MnDC-n (n = 3 to 6)

MnDC-3 MnDC-4 MnDC-5 MnDC-6formula C10H14Mn2O9 C12H18Mn2O9 C14H22Mn2O9 C16H26Mn2O9

fw 388.10 416.15 444.20 472.25crystal system orthorhombic monoclinic orthorhombic monoclinicspace 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 90V (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 R1a 0.0241 0.0380 0.0541 -

final wR2b 0.0686 0.1012 0.1150 -

Crystal Structure MnDC- 3 and MnDC-4 Crystal Structure MnDC- 3 and MnDC-4

MnDC-3 MnDC - 4a

c

b

a

MnDC-5 MnDC - 6

Crystal Structure MnDC- 5 and MnDC-6 Crystal Structure MnDC- 5 and MnDC-6

a

c

b

a

Compound C/cgsa /Kb eff(C)c eff(RT)d TN 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) = 5.92B,

d eff (RT) = 2.84(T)1/2 where T 300K, e ref 16 (5-300K), f ref 18 (5-300K).

MnDC-4

MnDC-3

5.1K

4.7K

Magnetic parameters of the MnDC-n ( n = 3 – 12) and Low TMagnetic parameters of the MnDC-n ( n = 3 – 12) and Low T