Supporting information
Solvent Induced Rapid Modulation of Micro/Nano Structures of
Metal Carboxylates Coordination Polymers: Mechanism and
Morphology Dependent Magnetism
Kun Liu1*, Zhu-Rui Shen2*, Yue Li1, Song-De Han1, Tong-Liang Hu1, Da-Shuai Zhang1,
Xian-He Bu1 & Wen-Juan Ruan1
Table S1. The reaction time to achieve well-defined Co-pydc CPs in organic
solvent/water mixtures (v:v=15:10).
Sample
S-EtOH
S-THF
S-DMF
S-MeCN
S-DMSO
Reaction Time
10 min
10 min
20 min
10 min
1 min
Table S2. The reaction time to achieve well-defined Co-pydc CPs by changing the
volume ratios of organic solvent/water mixtures.
Sample
Volume Ratio
THF/H2O=10:15
THF/H2O=5:20
DMF/H2O=10:15
DMF/H2O=5:20
DMSO/H2O=10:15
DMSO/H2O=5:20
S-THF
S-DMF
S-DMSO
Reaction Time
10 min
20 min
30 min
60 min
20 min
30 min
Table S3. The chemical structures and molecular mass of organic solvents used here.
Name
EtOH
THF
DMF
MeCN
DMSO
MeOH
DMA
46.07
72.11
73.09
41.05
78.12
32.04
87.12
Structural
Formula
Mr
Fig. S1 The SEM and TEM images of S-H2O.
Fig. S2 The SEM and TEM images of S-DMSO.
Fig. S3 The PXRD pattern of S-DMSO.
Fig. S4 (a) The coordination mode of Co2+ ion, (b) the 2D layer structure. Colorcode:
Co, purple; O, red; N, bule; C, gray. The hydrogen atoms are omitted. Both the figures
were drawn using the CIF file of Co(pydc)(H2O)2.1
Fig. S5 (a) The coordination mode of Co2+ ion, (b) the 3D structure. Colorcode: Co,
sapphire; O, red; N, bule; C, gray. The hydrogen atoms are omitted. Both the figures
were drawn using the CIF file of {Co(Pydc)(H2O)4}.H2O.2
References:
1 Whitfield, T.; Zheng, L.-M.; Wang, X.-Q.; Jacobson, A. J. Solid State Sci. 2001, 3, 829.
2 Lu, T.-L.; Wu, J.-Y.; Chan, M.-C.; Huang, S.-M.; Lin, C.-S.; Chiu, T.-W.; Liu, Y.-H.; Wen, Y.-S.;
Ueng, C.-H.; Chin, T.-M.; Hung, C.-H.; Lu, K.-L. Inorg. Chem. 2006, 45, 2430.
Fig. S6 FT-IR spectra of the as-prepared Co-pydc CPs obtained using different
organic solvents as the capping agents.
Table S4. EA values and calculated chemical formulas of as-prepared Co-pydc CPs.
Calculate
Sample
Experiment
Chemical formula
C%
H%
N%
C%
H%
N%
32.05
32.18
32.38
3.11
2.95
2.92
5.42
5.71
5.47
Simulated
Pure H2O
EtOH/H2O
THF/H2O
Co(Pydc).2H2O
32.33
2.71
5.39
MeCN/H2O
DMF/H2O
{Co(Pydc)(H2O)4}.H2O
26.75
4.17
4.46
27.91
27.11
4.44
4.54
4.69
4.86
DMSO/H2O
Co(Pydc)0.7(OH)0.6.2H2O.1.2DMSO
27.88
4.45
3.12
27.73
4.51
3.76
Fig. S7 S 2p XPS spectrum for S-DMSO, purple line: the base line, red and blue line:
deconvoluted S 2p peaks, green line: the fitting curve of the spectrum.
110
100
DMF
MeOH
MeCN
DMSO
90
Weight/%
80
70
60
50
40
30
20
10
0
100
200
300
400
500
600
700
800
Temperature/oC
Fig. S8 TGA curves of the as-prepared Co-pydc CPs obtained with different organic
solvents.
Table S5. Detailed weight loss values of the as-prepared Co-pydc CPs.
Calculated
Sample
o
Water
EtOH/H2O
THF/H2O
MeOH/H2O
MeCN/H2O
DMF/H2O
DMSO/H2O
Experimental
o
25-250 C
25-700 C
13.8%
69.1%
28.65%
74.45%
41.3%
74.5%
o
25-250 C
10.7%
11.0%
11.6%
27.2%
23.7%
25.5%
38.1%
25-700 oC
64.3%
68.0%
65.8%
76.7%
67.4%
72.0%
80%
It is shown that all the TGA curves taken in air had two major stages of rapid weight
loss in the range from room temperature to 700 oC, corresponding to the release of
water or organic solvent molecules and the decomposition of the organic ligands,
respectively. For each CPs product, the detailed weight loss data were listed in Table
S5, and their theoretical and experimental values were well consistent with each other.
Table S6. The chemical structures and “R” groups of the alcohols used here.
methanol
ethanol
n-propanol
n-butanol
R1-OH
R2-OH
R3-OH
R4-OH
R1=CH3-
R2=CH3CH2-
R3= CH3CH2CH2-
R4= CH3CH2CH2CH2-
phenylcarbinol
R5-OH
R5=
Fig. S9 SEM images of the as-prepared Co-pydc CPs using (a) ethanol, (b)
n-propanol, (c) n-butanol and (d) phenylcarbinol as the capping agents, respectively.
Phenylcarbinol
Intensity/a.u.
n-Butanol
n-Propanol
EtOH
0
10
20
30
40
50
2 Theta/deg.
Fig. S10 PXRD patterns of the as-prepared Co-pydc CPs using (a) ethanol, (b)
n-propanol, (c) n-butanol, (d) phenylcarbinol as the capping agents, respectively.
Fig. S11 SEM images and PXRD patterns of the as-prepared Co-pydc CPs using (a, b,
e) MeOH, (c, d, f) DMA as the capping agents, respectively.
Fig. S12 SEM images of Co-pydc CPs obtained using kinds of organic solvents THF:
(a1) 1 min, (a2) 2 min, (a3) 6 min, (a4) 10 min; MeCN: (b1) 1 min, (b2) 2 min, (b3) 6
min, (b4) 10 min; DMSO: (c1) 1 min, (c2) 2 min, (c3) 6 min, (c4) 10 min.
Fig. S13 PXRD patterns of the time-depended samples obtained using: (a) THF, (b)
MeCN, (c) DMF and (d) DMSO, respectively.
Fig. S14 FT-IR spectra of the time-depended samples obtained using: (a) THF, (b)
MeCN, (c) DMF and (d) DMSO, respectively.
Fig. S15 SEM images of Co-pydc CPs obtained after reaction for: (a) 6 min, (b) 10
min, (c) 16 min and (d) 20 min using DMF as the capping agent.
Modulation kinetics of organic solvents as the capping agents
To investigate the modulation kinetics of organic solvents, several time-dependent
experiments were performed using THF, MeCN and DMSO as the capping agents,
respectively.
When using THF as the capping agent, the SEM images (Fig. S12) showed that
short lumps with small holes were formed in the initial stage (1 min, 2 min, Fig.
S12a1 and S12a2). After reaction for 6-10 min, the short lumps gradually transformed
into the microtubes, and the inner diameter of microtube became larger (Fig. S12a3
and S12a4). It is known that hollow structures was usually formed following the
kirkendall effect or Ostwald ripening mechanism, which induced by transformation of
the composition or crystalline structure.3,4 However, the PXRD patterns and FT-IR
spectra of CPs resembled to each other regardless of their reaction time (Fig. S13a
and Fig. S14a) providing their identical crystalline phase and chemical structures.
Moreover, their PXRD peaks even had the similar FWHM values and intensities (Fig.
S13a), indicating a very close crystallinity. Therefore, a typical kirkendall or Ostwald
ripening mechanism could be excluded, and the formation of microtubes was ascribed
to the anisotropic growth induced by THF.
When using MeCN, the embryonic form of nanopolyhedrons assemblies emerged
in an early stage (1 min, Fig. S12b1), and they transformed into final products via a
fast crystal growth process (Fig. S12, b2-b4, 2-10 min). Additionally, the SEM
showed that the CPs obtained using DMF had a similar growth process, which further
proved the identical modulation effect of MeCN and DMF (Fig. S15). The PXRD
patterns and FT-IR spectra displayed no obvious difference at any reaction stage both
for MeCN and DMF (Fig. S13b, S13c and Fig. S14b, S14c), which was similar to the
CPs obtained using THF. While for DMSO, the growth kinetics of CPs was
distinguished from other organic solvents, and well defined rhombic lamellas were
obtained within 1 minute (Fig. S2, a-c). However, as shown in Fig. S12c1-S12c4, the
thickness of samples quickly increased with proceeding of the reaction, and the
rhombic lamellas were replaced by rhombic lumps soon afterwards. The PXRD
patterns and FT-IR spectra (Fig. S13d and Fig. S14d) showed that the rhombic
lamellas and lumps had the same crystalline phase and chemical structure, which
confirmed the intercalating of DMSO happened successively during the crystal
growth. Moreover, it also proved that the continuous growth of new crystalline phase
determined the morphology of the CPs when using DMSO.
Above all, whatever the organic solvents used, the CPs could get its embryonic
form within a short time (1 min). Moreover, they possessed the same crystalline phase
and chemical structure to their final products. Thus it is proposed that the organic
solvents played their roles early in the nucleation stage, and decided the morphology
and structure of CPs during subsequent crystal growth process.
References:
3 A. Cabot, M. Ibáñez, P. Guardia and A. P. Alivisatos, J. Am. Chem. Soc., 2009, 131, 11326.
4 J. Huo, L. Wang, E. Irran, H.-J. Yu, J.-M. Gao, D.-S. Fan, B. Li, J.-J. Wang, W.-B. Ding, A. M.
Amin, C. Li and L. Ma, Angew. Chem., Int. Ed., 2010, 49, 9237.
Fig. S16 The SEM images of Co-pydc CPs using different volume ratios of organic
solvents as the capping agents including: THF/H2O: (a) 10:15, (b) 5:20; DMF/H2O: (c)
10:15, (d) 5:20; DMSO/H2O: (e) 10:15, (f) 5:20. The total volume of reaction solution
is 25 mL.
a
Intensity/a.u.
THF/H2O=5/20
THF/H2O=10/15
THF/H2O=15/10
0
10
20
30
40
50
2 Theta/deg.
b
Intensity/a.u.
DMF/H2O=5/20
DMF/H2O=10/15
DMF/H2O=15/10
0
10
20
30
40
50
2 Theta/deg.
c
Intensity/a.u.
DMSO/H2O=5/20
DMSO/H2O=10/15
DMSO/H2O=15/10
0
10
20
30
40
50
2 Theta/deg.
Fig. S17 PXRD patterns of Co-pydc CPs using different volume ratios of organic
solvents as the capping agents including: (a) THF/H2O, (b) DMF/H2O, (c)
DMSO/H2O.
Fig. S18 The SEM images of Co-pydc CPs using different volume ratios of organic
solvents as the capping agents including: EtOH/H2O: (a) 10:15, (b) 5:20; DMA/H2O:
(d) 10:15, (e) 5:20. The total volume of reaction solution is 25 mL. PXRD patterns of
S-EtOH (c) and S-DMA (f).
Fig. S19 PXRD patterns of metal carboxylic acids CPs micro/nanostructures obtained
at ambient conditions, including: (a) Co-BTC5,6; (b) Zn-pydc7; (c) Eu-pydc8.
Fig. S20 The crystal structures of metal carboxylic acids CPs micro/nanostructures
obtained at ambient conditions, including: (a) Co-BTC (simulated-1)5; (b) Co-BTC
(simulated-2)6; (c) Zn-pydc7; (d) Eu-pydc8. Colorcode: Co, sapphire; O, red; N, bule;
C, gray; S, yellow; Mn, aubergine; Eu, green.
References:
5 O. M. Yaghi, H. Li and T. L. Groy, J. Am. Chem. Soc., 1996, 118, 9096.
6 S. Chatterjee, V. R. Pedireddi, A. Ranganathan and C. N. R. Rao, J. Mol. Struct. 2000, 520, 107.
7 H. Xu, N. Zheng, H. Xu, Y. Wu, R. Yang, E. Ye and X. Jin, J. Mol. Struct. 2002, 610, 47.
8 Q. Shi, S. Zhang, Q. Wang, H. Ma, G. Yang and W. H. Sun, J. Mol. Struct. 2007, 837, 185.