Supporting Information
Field-induced slow magnetic relaxation in a hydrogen bonding
linked Co(II) 1D supramolecular polymer
Yuan-Yuan Zhua,c*, Ting-Ting Yina, Chang-Wei Liua, Chen Gaoc, Zong-Quan Wua*, Yi-Quan
Zhangb,c*, Bing-Wu Wangc, Song Gaoc
a
Key Laboratory of Advanced Functional Materials and Devices, Anhui Province, and School of
Chemical Engineering, Hefei University of Technology, Hefei 230009, P. R. China;
b
Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal
University, Nanjing 210023, P. R. China;
c
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials
Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University,
Beijing 100871, P. R. China.
*Corresponding authors. Email: yyzhu@hfut.edu.cn; zhangyiquan@njnu.edu.cn; zqwu@hfut.edu.cn.
Synthesis
All starting materials were purchased as reagent grade and were used without further purification.
Synthesis of the bpm ligands
Bmp (bis(pyrazol-1-yl)methane). ligand bmp was synthesized according to the modified literature
method.1 In ice bath, to a solution of 1H-pyrazole (2.288 g, 33.6 mmol) and TBAB (0.542 g, 1.68
mmol) in CH2Cl2 (40 mL) was slowly added 50% NaOH aqueous solution (20 mL). Then the
mixture was vigorously stirred under reflux for 12 hours. After cooled to room temperature, H2O (40
mL) was added to diluted the NaOH solution. The two layers were seperated and the aqueous phase
was extracted by CH2Cl2 (20 mL  3). The organic phase was combined and dried over anhydrous
Na2SO4. The solvent was evaporated under vacuum, and the crude product was subjected to flash
chromatography (eluant: ethyl acetate) to give bmp (2.34 g, 94%) as white solid.1H NMR (600 MHz,
CDCl3): δ 7.65 (d, J = 1.8 Hz, 2 H), 7.54 (d, J = 1.8 Hz, 2 H), 6.30 (s, 2 H), 6.28 (t, J = 1.8 Hz, 2 H).
Reference
1.
S. Juliá, P. Sala, J. del Mazo, M. Sancho, C. Ochoa, J. Elguero J. Heterocyclic Chem. 1982, 19,
1141.
Figure S1. 1H NMR spectrum of bpm ligand (600 MHz) in CDCl3 (10 mM).
Figure S2. IR spectrum of compound 1.
Figure S3. The powder XRD pattern of compound 1 and the simulated one based on the
single-crystal structure.
Table S1. Crystal data, data collection, solution, and refinement information of compound 1.
Formula
Formula weight
Crystal system
Space group
a, Å
b, Å
c, Å
, deg
, deg
, deg
V, Å3
Z
T, K
F(000)
DC, g cm-3
μ, mm-1
λ, Å
Crystal size, mm3
Tmin and Tmax
min, max, deg
no. total reflns.
no. uniq. reflns, Rint
no. obs. [I  2σ(I)]
no. params
no. restraints
R1 [I  2σ(I)]
wR2 (all data)
S
Δρ[a], e/Å3
max and mean Δ/σ[b]
1
C28H36Cl2Co2N22O10
1029.55
triclinic
P-1
8.7590(9)
8.9633(7)
13.5976(17)
84.673(9)
85.230(9)
76.619(8)
1031.98(19)
1
110
526
1.657
1.015
1.54178
0.42  0.36  0.32
0.53370, 1.00000
3.46, 26.02
6462
3971, 0.0406
3531
300
1
0.0694
0.1853
1.135
0.619, 1.371
0.000, 0.000
[a] Max. and min. residual density. [b] Max. and mean shift/σ.
Table 2. Selected bond lengths and angles for compound 1.[a]
Interatomic Distances (Å)
Co(1)-O(1W)
2.076(3)
Co(1)-N(4)
Co(1)-N(1)
2.138(4)
Co(2)-N(9)
Co(2)-N(5)
2.129(4)
Co(2)-N(8)
N(1)-N(2)
1.358(5)
N(3)-N(4)
N(5)-N(6)
1.360(5)
N(7)-N(8)
N(9)-N(10)
1.184(6)
N(10)-N(11)
Angles (deg)
O(1W)-Co(1)-N(4)#1 91.07(15)
N(9)#2-Co(2)-N(5)
O(1W)-Co(1)-N(4)
88.93(15)
N(9)-Co(2)-N(5)
O(1W)-Co(1)-N(1)
89.48(14)
N(9)#2-Co(2)-N(8)
O(1W)#1-Co(1)-N(1) 90.52(14)
N(9)-Co(2)-N(8)
N(4)#1-Co(1)-N(1)
92.06(15)
N(5)#2-Co(2)-N(8)
N(4)-Co(1)-N(1)
87.94(15)
N(5)-Co(2)-N(8)
[a] Symmetry operation: #1 -x+1,-y,-z+1; #2 -x,-y+2,-z+2.
2.120(4)
2.122(4)
2.139(4)
1.357(5)
1.362(5)
1.168(6)
89.45(15)
90.55(15)
91.16(15)
88.84(15)
92.21(15)
87.79(15)
Figure S4. The temperature dependence of the ac susceptibility at frequencies of 1-1000 Hz for 1.
Figure S5. M (in-phase) against frequency of 1 under 1500 dc field range from 100 to 10000 Hz at
different temperature (2 to 10 K, 1 K interval) in PPMS.
Figure S6. M (out-of-phase) against frequency of 1 under 1500 dc field range from 100 to 10000
Hz at different temperature (2 to 10 K, 1 K interval) in PPMS.
Figure S7. Arrhenius plots of relaxation times of 1 under 1500 Oe dc field, the data was collected
from the peaks of M (out-of-phase) against frequency at different temperature.
Table S3. The parameters of Cole-Cole fitting of 1 under 1500 applied dc field.
T (K)
2.0
3.0
4.0
5.0
6.0
X0
0.19102
0.13652
0.10731
0.08978
0.05939
Xt
1.31409
1.02824
0.84181
0.68015
0.56539


0.00254
0.00079
0.00033
0.00012
0.00004
0.13734
0.07038
0.06733
0.03732
0.04575
R
3.47  10-4
3.14  10-4
8.09  10-5
7.13  10-5
1.69  10-4
Figure S8. Calculated structures of [Co(bpm)2(N3)2] (a) and [Co(bpm)2(H2O)2]2+ (b); H atoms have
been omitted for clarity.
Figure S9. The calculated MT vs. T plots under 1 kOe applied dc field at 2-300 K for
[Co(bpm)2(H2O)2]2+ and [Co(bpm)2(N3)2] from compound 1, respectively.
Figure S10. The comparison of the experimental and calculated MT vs. T plots under 1 kOe applied
dc field at 2-300 K for compound 1 (The black dot represents the experimental data and the red solid
line represents the merge of calculated magnetic susceptibilities of [Co(bpm)2(H2O)2]2+ and
[Co(bpm)2(N3)2] from 1).
Figure S11. The calculated isothermal magnetization for [Co(bpm)2(H2O)2]2+ and [Co(bpm)2(N3)2]
from compound 1 from 0 to 20 T at 2 K, respectively.
Figure S12. The comparison of experimental and calculated isothermal magnetization for compound
1 at 2.0 K (The black dot represents the experimental data and the red solid line represents the merge
of calculated result of [Co(bpm)2(H2O)2]2+ and [Co(bpm)2(N3)2] from 1).