MC-6] Metallacrown Clusters: Structure, Magnetic and .... Figure S4. Ïm-1 vs T for 1 and 2, the red line represents the best fit of the data with ... Figure S6.
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2014
Electronic Supplementary Information (ESI) A Series of 3D Metal Organic Frameworks Based on [24MC-6] Metallacrown Clusters: Structure, Magnetic and Luminescent Properties Kai Wang,a,b Hua-Hong Zou,b Zi-Lu Chen,b Zhong Zhang,b Wei-Yin Sun,a Fu-Pei Liang,*b,c aCoordination
Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of
Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing, 210093, China bState
Key Laboratory Cultivation Base for the Chemistry and Molecular Engineering of
Medicinal Resources, School of Chemistry and Pharmacy, Guangxi Normal University, Guilin, 541004, China cCollege
of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China E-mail address: fliangoffice@yahoo. com (F. Liang)
1. KMnO4, KOH
HBr-HOAc HOOC
2. HCl
COOH
OMe
HOOC
COOH
OMe
OH
Scheme S1. The synthetic routes for H3ipO
1
2 2359.6 1295.5
757.4
609.0 715.0 757.4 450.0 1292.6
455.1
3164.7
1449.8
3149.3
2363.9
611.8 725.6
1449.3
3419.3
1480.6
1481.6 3431.3
1383.3
1601.6
1374.1
1602.6
4000 3500 3000 2500 2000 1500 1000
500
4000 3500 3000 2500 2000 1500 1000
/ cm-1
/ cm-1
S1
500
3
4 2360.1
2359.6
3178.2
629.2 449.8 761.8 1288.8 703.9
3431.9
640.8 454.7 720.3
3427.0 3092.9
1294.5
757.4
1553.0 1385.1 1446.9
1450.3 1481.1 1602.1 1373.6
1659.0
4000 3500 3000 2500 2000 1500 1000
4000 3500 3000 2500 2000 1500 1000
500
/ cm-1
/ cm-1
500
Figure S1. the IR spectras of 1-4. 1 2 3 4
100
TG (%)
80 60 40 20 0
200
400
600
800
T (oC)
1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0
1
10
1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0
20
30 40 50 2 Theta / Degree
60
simulate measure
2
10
simulate measure
3
Relative intensity
Relative intensity
1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0
simulate measure
Relative intensity
Relative intensity
Figure S2. TG curves for 1-4 under nitrogen atmosphere.
10
20
30 40 2 Theta / Degree
50
60
1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0
20
30 40 50 2 Theta / Degree
simulate measure
4
10
20
30 40 2 Theta / Degree
Figure S3. The PXRD patterns of complexes 1-4. S2
60
50
60
20 10
18
1
2
16
/ cm-3 mol1
/ cm-3 mol1
8 6 4 2
14 12 10 8 6 4
0 0
50
100
150
200
250
2
300
0
50
Temperture / K
100
150
200
250
300
Temperture / K
Figure S4. χm-1 vs T for 1 and 2, the red line represents the best fit of the data with Curie-Weiss law.
6
m / cm-3 mol1
ZFC FC
1
5 4 3 2 1 0
2
4
6
8
10
12
14
16
Temperture / K
Figure S5. The FC/ZFC curves for compound 1 at 20 Oe (left).
8
0.020
' / cm3 mol-1
6 4
0.015
0.010
2
'' / cm3 mol-1
10 Hz 100 Hz 300 Hz 601 Hz 997 Hz
0.005
0 2
3
4
5
6
7
8
0.000
Temperture / K
Figure S6. Temperature dependence of AC susceptibility at various frequencies of compound 1 (right).
S3
Table S1 Crystal Data and Structure Refinement Parameters for Compounds 1-4 Identification code
1
2
3
4
Empirical formula
C8H6O6Co
C8H6O6Mn
C8H6O6Cd
C48H38O37Zn6
Formula weight
257.06
253.07
310.54
1599.07
Temp/K
160.15
160.15
160.15
160.15
Crystal system
Cubic
Cubic
Cubic
Cubic
Space group
𝐼𝑎3̅
𝐼𝑎3̅
𝐼𝑎3̅
𝐼𝑎3̅
a/Å
22.308(2)
22.680(2)
22.990(18)
22.283(5)
α/deg
90
90
90
90
V/Å3
11101(2)
11666(2)
12150.7(16)
11064(4)
Z
48
48
48
8
Dc/g cm–3
1.831
1.715
2.024
1.903
m/mm–1
1.859
1.362
2.161
2.671
F(000)
6117
6000
7070
6323
Reflections collected
9624
8042
10260
6269
Independent reflections
1898
1714
2321
1622
Data/restrains/parameters
1898/0/139
1714/0/143
2221/0/139
1622/34/135
Rint
0.057
0.040
0.019
0.094
GOF
1.052
1.187
1.053
1.010
R1a (I> 2σ(I))
R1 = 0.0367,
R1= 0.0424,
R1= 0.0241,
R1= 0.0436,
wR2b(all data)
wR R 0.0549, 2 =0.0961 1=
wR R 0.0583, 2 =0.1255 1=
wR =0.0668 R 1=2 0.0254,
wR =0.0824 R 1=2 0.0814,
wR2 = 0.1087 wR2 =0.1437 = Fo–Fc/Fo, bwR2 = [w(Fo2–Fc2)2/w(Fo2)2]1/2
wR2 =0.0685
wR2 =0.0969
aR
1
Table S2. Selected bond lengths (Å) and angles (°) for 1. Atom Atom Length/Å
Atom Atom Length/Å
Co1 O3
Co1 O14 2.021(3)
2.166(3)
Co1 O51 2.098(3)
O3
C7
1.369(4)
Co1 O5
2.067(3)
C8
O4
1.244(5)
Co1 O42 2.039(3)
C1
O2
1.297(5)
Co1 O23 2.103(3)
C1
O1
1.241(5)
Atom Atom Atom
Angle/˚
Atom Atom Atom
Angle/˚
O5
79.31(10)
O14 Co1 O5
94.65(10)
174.74(10)
O14 Co1 O51
90.42(10)
85.34(10)
O14
Co1
O42
170.62(11)
90.03(10)
O14
Co1
O23
89.42(10)
97.18(10)
C7
O3
Co1
121.0(2)
Co1 O3
O51 Co1 O3 O42 O42
Co1 O3 Co1 O5
O42 Co1 O51
S4
O23 Co1 O3 O23 O23
92.73(10)
Co1 O5
C8
170.87(10)
C8
O5
Co1
125.2(2)
O5
Co15
122.5(2) 139.6(2)
O51
92.10(10)
C8
O4
Co16
O23 Co1 O42
84.83(11)
C1
O2
Co13
124.2(2)
O1
Co17
139.5(3)
O14
Co1
Co1 O3
Symmetry codes:
1+y,
87.54(10)
C1
21/2-z,
3-x,
1/2-z, 1/2+x; -x, 1/2+y; 1/2-y, +z; 6 7 1/2-y; -y, -1/2+z, 1/2-x; -y, +z, 1/2+x
4-1/2+z,
-x, +y; 5-1/2+z, +x,
Table S3. Selected bond lengths (Å) and angles (°) for 2. Atom Atom Length/Å
Atom Atom Length/Å
Mn1 O5
2.163(3)
O1
Mn17 2.104(3)
Mn1 O51 2.164(3)
O2
Mn14 2.176(3)
Mn1 O42 2.130(3)
C1
O1
1.247(5)
2.104(3)
C1
O2
1.292(5)
2.247(3)
C8
O5
1.283(5)
Mn1 O24 2.176(3)
C8
O4
1.240(5)
C7
O3
1.373(5)
Mn1
O13
Mn1 O3 O5
Mn15
2.164(3)
O4
Mn16
2.130(3)
Atom Atom Atom O5
Mn1
O51
Angle/˚
Atom Atom Atom
Angle/˚
97.11(13)
O14
Mn1
170.87(11)
Mn1 O3
87.50(10)
O43
O5
Mn1 O3
75.16(10)
O14
O51
Mn1 O3
172.00(11)
O14
Mn1 O22
91.87(11)
93.41(11)
O22
Mn1 O3
94.50(10)
O51
Mn1
O22
O5
Mn1
O22
O43 O43 O43
167.83(11)
Mn1
O5
Mn15
Mn1 O51
97.45(11)
C8
O5
Mn1
127.5(2)
Mn1 O5
88.32(11)
C8
O5
Mn15
122.7(2)
O4
Mn16
140.9(3) 141.3(3)
Mn1 O3
84.58(10)
C8
109.70(12)
O43
Mn1
O22
84.24(11)
C1
O1
Mn17
O14
Mn1 O51
91.01(11)
C7
O3
Mn1
122.6(2)
O14
Mn1 O5
94.05(10)
C1
O2
Mn12
125.1(2)
Symmetry codes:
1-1/2+z,
21/2-x,
3-1/2+y,
1-x, +y; +y, 1-z; 3/2-z, 1-x; 6 7 1/2+x; 1-z, 1/2+x, 3/2-y; 1-z, 1-x, 1-y
41-y,
1-z, 1-x; 51-y, +z,
Table S4. Selected bond lengths (Å) and angles (°) for 3. Atom Atom Length/Å Cd2
O41
Atom Atom Length/Å
2.218(2)
O1
C1
1.245(4)
2.273(2)
O4
C8
1.248(4)
Cd2 O52 2.265(2)
O5
C8
1.277(4)
Cd2 O5
S5
Cd2 O3
2.371(2)
O3
C7
1.362(4)
Cd2
O23
2.278(2)
O2
C1
1.283(4)
Cd2
O14
2.205(2)
Atom Atom Atom Cd2
O41
O52
Cd2
O41
O3
Cd2
O41
O5
Angle/˚
Atom Atom Atom Angle/˚
88.65(8)
C1
O1
Cd27
140.1(2)
101.61(8)
O14
Cd2
O52
90.64(8)
83.49(8)
O14
Cd2
O5
96.15(8)
Cd2
O5
72.00(8)
O14
Cd2
O3
85.89(8)
O3
Cd2
O52
166.41(8)
O14
Cd2
O23
90.63(8)
O23
Cd2
O41
82.59(9)
C8
O4
Cd25
135.8(2)
O23
167.93(8)
C8
O5
Cd2
130.23(19) 124.56(19)
O3
Cd2
O5
O23
Cd2
O52
94.52(8)
C8
O5
Cd26
O23
Cd2
O3
98.64(8)
C7
O3
Cd2
122.28(18)
O14
Cd2
O41
166.38(9)
C1
O2
Cd23
124.03(19)
Symmetry codes: 13/2-y, 1-z, -1/2+x; 21-z, +x, -1/2+y; 33/2-x, +y, -z; 4+y, 1/2-z, -1/2+x; 51/2+z, 3/2-x, 1-y; 6+y, 1/2+z, 1-x; 71/2+z, +x, 1/2-y
Table S5. Selected bond lengths (Å) and angles (°) for 4. Atom Atom Length/Å
Atom Atom Length/Å
Zn1 O11 2.074(3)
O4
C7
1.294(6)
Zn1 O1
2.078(3)
O1
C1
1.288(6)
Zn1 O3
2.206(4)
O3
C8
1.368(6)
Zn1 O52 2.012(3)
O5
C7
1.241(6)
O2
C1
1.240(6)
Zn1
O23
2.046(3)
Zn1
O44
2.092(3)
Atom Atom Atom
Angle/˚
Atom Atom Atom Angle/˚
O3
Zn1 O1
77.67(14)
C7
O4
Zn14
123.5(3)
O3
Zn1 O11
172.95(14)
O44
Zn1
O11
93.75(13)
95.18(14)
O44
Zn1
O3
92.98(14)
91.79(14)
O44
Zn1
O52
89.26(14)
Zn1 O3
86.21(15)
O44
Zn1
O23
84.66(13)
O23 Zn1 O1
89.26(13)
C1
O1
Zn1
126.5(3)
O23 Zn1 O11
98.26(14)
C1
O1
Zn15
122.4(3)
O23
84.44(14)
C8
O3
Zn1
121.7(3) 139.0(4) 138.2(3)
O52 Zn1 O1 O52 O52
O23
Zn1
O11
Zn1 O3 Zn1
O52
O44 Zn1 O1 Symmetry codes:
11-z,
168.56(14)
C7
O5
Zn16
169.32(13)
C1
O2
Zn17
21-y,
31/2-y,
+x, 1/2+y; 1-z, 1-x; 1-z, 1/2+x; 6 7 x; 1-z, 1-x, 1-y; -1/2+z, 1/2-x, 1-y S6
4+x,
1-y, 3/2-z; 5+y, -1/2+z, 1-
