Electronic Supplementary Material
High proton conductivity in metalloring-cluster based
metal-organic nanotubes Quanjie Lin1, Yingxiang Ye1, Lizhen Liu1,
Zizhu Yao1, Ziyin Li1, Lihua Wang1, Chulong Liu1 (), Zhangjing
Zhang1,2 (), and Shengchang Xiang
1,2 ()
1 Fujian Provincial Key Laboratory of Polymer Materials, College
of Chemistry and Materials Science, Fujian Normal University, 32
Shangsan
Road, Fuzhou 350007, China 2 State Key Laboratory of Structural
Chemistry, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou
350002, China Supporting information to
https://doi.org/10.1007/s12274-020-2785-x
Experimental Section All reagents and solvents were commercially
available and directly used without further purification. Organic
ligands 9H-carbazole-3,6-dicarboxylic acid (H2cdc) was synthesized
according to the reported procedure[1]. A PerkinElmer 240C
elemental analyzer was used to obtain elemental analyses of C, H,
and N. A Fourier-transform infrared spectrum (FTIR, KBr pellets)
was recorded on a Thermo Nicolet 5700 FT-IR instrument from 400 to
4000 cm-1. Thermogravimetric analysis (TGA) was carried out under
an air atmosphere from room temperature to 600 °C using a Shimadzu
TGA-50 analyzer at a heating rate of 5 °C min-1. Powder X-ray
diffraction (PXRD) patterns were recorded by a PANalytical X’Pert3
powder diffractometer equipped with a Cu sealed tube (λ = 1.54184
Å) at 40 kV and 40 mA over the 2θ range of 5-30°. The simulated
pattern was produced using the Mercury V1.4 program and
single-crystal diffraction data.
Synthesis of FJU-105 A mixture of In(NO3)3·xH2O (200 mg,
0.666 mmol), 9H-carbazole-3,6-dicarboxylate acid (H2cdc, 230 mg,
0.9 mmol) and 2,5-thiophene carboxylic acid (H2thb, 35 mg, 0.2
mmol) sealed in a 20 mL of Teflon-lined stainless steel vessel with
5 ml DMF (N,N-dimethylformamide) and 1mL H2O. The mixture was
heated to 120 oC in 1 h and kept this temperature for 5 d. Then the
reaction system was cooled slowly to room temperature. The
colorless hexagonal prismatic crystals of FJU-105 were collected,
washed with DMF, and dried in air (yield 30% based on In
(NO3)3·xH2O. Elemental analysis calcd. (%) for C30H50InS1N5O19.5
(938): C 38.37, H 5.33, N 7.46; found: C 36.45, H 4.95, N 7.16.
Synthesis of FJU-106 A mixture of In(NO3)3·xH2O (200 mg,
0.666 mmol), 9H-carbazole-3,6-dicarboxylate acid (H2cdc, 200 mg,
0.9 mmol) and 1,3,5- benzene tricarboxylic acid (H3btc, 42.5 mg,
0.2 mmol) sealed in a 20 mL of Teflon-lined stainless steel vessel
with 5 ml DMA (N,N-dimethylacetamide) and 1mL H2O. The mixture was
heated to 120 oC in 1 h and kept this temperature for 5 d. Then the
reaction system was cooled slowly to room temperature. The
colorless hexagonal prismatic crystals of FJU-106 were collected,
washed with DMA, and dried in air (yield 23% based on In
(NO3)3·xH2O. Elemental analysis calcd. (%) for C35H59InN5O23
(1031): C40.74, H 5.72, N 6.78 found: C 40.83, H 5.49, N 7.07.
Single-Crystal X-ray Diffraction (SCXRD) Studies Data
collection and structural analysis of crystals were collected on
the Rigaku Oxford single-crystal diffractometer equipped with
graphite monochromatic Cu Kα radiation (λ = 1.54184 Å). The crystal
at 150 K during data collection. Using Olex2 [2], the structure was
solved with the Superflip [3] structure solution program using
charge flipping and refined with the ShelXL [4] refinement package
using least-squares minimization. All nonhydrogen atoms were
refined with anisotropic displacement parameters. The hydrogen
atoms on the ligands were placed in idealized positions and refined
using a riding model. We employed PLATON [5] and SQUEEZE [6] to
calculate the diffraction contribution of the solvent molecules and
now produce a set of solvent-free diffraction intensities. The
tailed crystallographic data and structure refinement parameters
are summarized in Table S1 (CCDC 1976828-1976829)
Proton conductivity measurement Firstly, the as-synthesized
sample was finely ground to a powder and compressed into a homemade
cylindrical closed glass container with an inner diameter of 0.4
cm. The sample thickness is 1.75 cm and 1.89 cm, for FJU-105 and
FJU-106. Impedance analysis was performed on the pellets using a
two-probe method with a Solartron SI 1260 Impedance/Gain-Phase
Analyzer and 1296 Dielectric Interface Impedance Analyzer from 100
Hz-10 MHz with an input voltage 100 mV. The temperature and dry
environment was controlled using an XK-CTS80Z humidity control
chamber. Measurements were done at thermal equilibrium by
Address correspondence to Shengchang Xiang, [email protected];
Zhangjing Zhang, [email protected]; Chulong Liu,
[email protected]
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Figure S7 Speculative proton pathway conduction for
FJU-105 and FJU-106.
Table S1 Crystallographic data for FJU-105 and FJU-106.
Compounds FJU-105 FJU-106 Empirical formula C30H50InS1N5O19.5
C35H59InN5O23
Formula weight 948.5 1157.5 Temperature/K 150(10) 150(2) Crystal
system trigonal trigonal
Space group R-3m R-3m a/Å 46.0197(6) 45.936(8) b/Å 46.0197(6)
45.936(8) c/Å 10.1850(2) 10.032(3) α/° 90 90 β/° 90 90 γ/° 120
120
Volume/Å3 18680.1(6) 18332(8) Z 18 18
ρcalcg/cm3 0.861 0.983 μ/mm-1 5.240 0.613 F(000) 4770.0
5112.0
Radiation CuKα (λ = 1.54184) CuKα (λ = 1.54184)
Data/restraints/parameters 3453/30/144 3012/91/171
Goodness-of-fit on F2 1.135 0.965
Final R indexes [I>=2σ (I)] R1= 0.1615, wR2= 0.4288
R1=0.0959, wR2=0.2341 Final R indexes [all data] R1= 0.1683, wR2=
0.4501 R1=0.1466, wR2= 0.2727
Table S2 Compare the diameter of the metalloring in FJU-105 and
FJU-106 with that of reported MROF materials.
Compounds Ligands Cluster type Diameter(Å)a Ref. CAU-1 NH2-H2BDC
Al8(OH)4(OCH3)8 8.11 [7]
MIL-125 H2BDC Ti8(O)8(OH)4 8.25 [8] MIL-125-NH2 NH2-BDC
Ti8(O)8(OH)4 8.27 [9]
MOF-520 H3BTB Al8(OH)8 (HCOO)4 8.67 [10] Be12(OH)12(BTB)4 H3BTB
Be12(OH)12 8.99 [11] CAU-3-BDC-NH2 NH2-H2BDC Al12(OCH3)24 10.44
[12]
CAU-3-BDC H2BDC Al12(OCH3)24 10.77 [13] MROF-1 H2THB, H2BPDC
In6(thb)6 20.99 [14]
MROF-12 H2NDI Cu12(μ2-OH)12(Pz)12 12.20 [15] FJU-105 H2cdc,
H2thb In6(cdc)6 22.85 FJU-106 H2cdc, H3btc In6(cdc)6 22.85
This work
a The diameter of the metalloring cluster for the above MROF
materials, as shown in the following figure, corresponding to the
diagonal distance.
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H2BDC = terephthalic acid; NH2-H2BDC = 2-aminoterephthalic
acid; H2NDC = 2,6-naphthalene dicarboxylic acid; H3BTC =
1,3,5-benzenetricarboxylic acid; H3BTB = 1,3,5-benzenetribenzoic
acid; pz = pyrazol; H2thb = 2,5-thiophenedicarboxylic acid; H2pbdc
= 4,4'-biphenyldicarboxylic acid; H2NDI =
2,7-bis(3,5-dimethylpyrazol-4-yl)-1,4,5,8-naphthalene-tetracarboxydiimide;
H2cdcc = 9H-carbazole-3,6-dicarboxylic acid.
Table S3 Proton conductivity of FJU-105 and FJU-106 at different
temperatures.
FJU-105 FJU-106
σ (S cm-1) σ (S cm-1) t (oC)
Heat Cool Heat Cool
-20 1.94 × 10-5 1.01 × 10-5 6.45 × 10-4 6.02 × 10-4
-10 3.43× 10-5 2.17 × 10-5 1.15 × 10-3 1.04 × 10-3
0 6.21 × 10-5 4.32 × 10-5 1.94 × 10-3 1.78 × 10-3
10 1.02 × 10-4 7.71 × 10-5 2.96 × 10-3 2.68 × 10-3
20 1.66 × 10-4 1.40 × 10-4 3.73 × 10-3 3.49 × 10-3
30 2.59 × 10-4 2.14 × 10-4 5.27 × 10-3 4.88 × 10-3
40 4.13 × 10-4 3.16 × 10-4 7.45× 10-3 6.68 × 10-3
50 6.28 × 10-4 4.57 × 10-4 1.00 × 10-2 9.13 × 10-3
60 9.22 × 10-4 6.67 × 10-4 1.59 × 10-2 1. 27 × 10-2
70 1.22 × 10-3 1.80 × 10-2
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J. Mater. Chem. A 2018, 6, 19681-1968
