Journal of Solid State Chemistry 238 (2016) 217–222

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Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Ionothermal synthesis, structures, properties of cobalt-1,4-

benzenedicarboxylate metal–organic frameworks
Zong-Hui Zhang a,b, Ling Xu a,n, Huan Jiao a,n
a
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062,
Shaanxi Province, PR China
b
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fsuzhou, Fujian 350002,
PR China

art ic l e i nf o a b s t r a c t

Article history: Eight kinds of 1-methyl-3-alkylimidazolium halide [RMI]X (R¼ ethyl (E), propyl (P), butyl (B) and amyl
Received 19 February 2016 (A); MI ¼ imidazolium; X¼ Cl  , I  ) ionic liquids (ILs) were used as reaction media and obtained a series
Received in revised form of 2D [RMI]2[Co3(BDC)3X2] frameworks through the ionothermal reactions of 1,4-benzenedicarboxylic
14 March 2016
acid (H2BDC) with Co(NO3)2  6H2O. The 2D [RMI]2[Co3(BDC)3X2] frameworks exhibit a same (3,6) to-
Accepted 16 March 2016
Available online 17 March 2016
pology network with [RMI] þ cations locating in the interlayer space. [RMI] þ cations play a template role
in the structure constructions, whose influence combining with the effect of X  anions pass to the TG
Keywords: behaviors. The decomposition temperatures of the [RMI]2[Co3(BDC)3X2] frameworks decrease with the
1,4-Benzenedicarboxylic acid alkyl chains in [RMI] þ cations, and the compounds containing Cl  show higher thermal stabilities than
Metal-organic framework
those with I  . However, compounds 1–8 exhibit two similar broad emissions at ca. 380 and 390 nm,
Crystal structure
assigned to ILCT. The RMI þ templates and the X  anions do not exert their influence on the fluorescence.
Ionothermal synthesis
& 2016 Elsevier Inc. All rights reserved.

1. Introduction hydrophobicity or nucleophilicity/basicity behaviors [19c,20c]. The

Metal-organic frameworks (MOFs) materials with structural
diversities have gained considerable attention due to the appli-
cations in many fields, such as catalysis, [1,2] ion-exchange, [3]
drug-delivery, [4] gas sorption and separation, [5,6] and so forth
[7,8]. Ionothermal synthesis is a new emerging environmental
friendly synthesis method, [9–11] in which ionic liquids (ILs) be-
have as reaction media, structural templates or charge-compen-
sating groups [12,13]. ILs possess many distinguished features
compared to the traditional solvents: high ionic conductivity, non-
flammability and negligible vapor pressure [14–16]. Therefore,
ionothermal synthesis is reasonably expected to offer significantly
different reaction environments to produce new-type MOF mate-
rials. A great of effort has been devoted to ionothermal synthesis
applied in MOF materials [17–19]. Based on our previous work on
M-BTC (M ¼ Zn, Cd, Ni; H3BTC ¼benzene-1,3,5-tricarboxylic acid)
[20] and M-BDC (M ¼Zn, Co; H2BDC ¼ 1,4-benzenedicarboxylic
acid) [21], a combination effect of ionic liquid cationic and anionic
parts was demonstrated, in which RMI þ cation exhibits structural
template and the halide anion controls the structural fashion and
the property regulation through their hydrophilicity/
n
Corresponding authors.
E-mail addresses: xuling@snnu.edu.cn (L. Xu), jiaohuan@snnu.edu.cn (H. Jiao).
present work is an ongoing part of our work. Herein, we explored
the effect of ILs on the structural formation and properties of Co-
BDC system, especially the roles of the IL anionic parts plays. We
selected Co(NO3)2 reacting with simple H2BDC ligand under two
kinds of 1-methyl-3-alkylimidazolium halide [RMI]X (R ¼ ethyl to
amyl; MI ¼ imidazolium; X¼Cl  , I  ) ILs to eliminate the effect of
metal center and ligands on the structure. Eight 2D compounds,
[RMI]2[Co3(BDC)3X2], were obtained from the above synthetic
processes, which show the same negative 2D [Co3(BDC)3X2]2 
skeletons. With the observation on single crystal structure, pow-
der X-ray diffraction (PXRD), thermogravimetric analysis (TGA),
fluorescence and FT-IR, our work clearly indicates a combinational
effect of RMI þ cations and X  anions on the MOF structures and
the TG behaviors.
2. Experimental
2.1. Materials and physical measurements
The reagents and solvents were used directly as supplied
commercially without further purification except two kinds of
1-methyl-3-alkylimidazolium halide ILs synthesized from the re-
actions of 1-alkyl halide with 1-methylimidazole according to the
literature processes. [22] Degassed alkyl halide (alkyl ¼ ethyl to

http://dx.doi.org/10.1016/j.jssc.2016.03.028
0022-4596/& 2016 Elsevier Inc. All rights reserved.
218 Z.-H. Zhang et al. / Journal of Solid State Chemistry 238 (2016) 217–222
amyl; X ¼Cl  , I  ) were refluxed with the distilled 1-methylimi-
dazole to give the two kinds of eight ILs. The ILs were washed with
ethyl acetate, and then dried under a vacuum at least for 10 h
([EMI]Cl: white solid, [PMI]Cl: colorless oil, [BMI]Cl: white solid,
[AMI]Cl: colorless oil, [EMI]I: yellow solid, [PMI]I: yellow oil, [BMI]
I: yellow oil, [PMI]I: yellow oil). Elemental analysis of C, H and N
was carried out on a Vario EL III elemental analyzer. FT-IR spectra
were collected from KBr pellets (Aldrich, 499%, FT-IR grade) with
a Bruker Tensor 27 FT-IR spectrometer in the range of 4000–
400 cm–1. TGA were carried out in N2 atmosphere on a SDT Q600
V8.3 Build 101 instrument with a heating rate of 10 °C  min  1 and
a N2 flow rate of 20 cm3  min  1. PXRD data for the materials were
collected at ambient temperature with a Rigaku D/Max–3c (Japan)
diffractometer (Cu-Kα1,2 X-radiation, λ1 ¼1.540598 Å and
λ2 ¼1.544426 Å), equipped with an X'Celerator detector and a
flatplate sample holder in a Bragg–Brentano para-focusing optics
configuration (40 kV, 50 mA). Intensity data were collected by the
step counting method (step being 0.02°) in continuous mode in
the range of 5 r2θ r 60°. Fluorescence spectra were acquired on a
Hitachi F-4600 fluorescence spectrophotometer with the excita-
tion and emission slits setted to 5 nm.
2.2. Synthesis of the compounds
Synthesis of [EMI]2[Co3(BDC)3Cl2] (1). 2.0 mmol, 0.5825 g Co
(NO3)2  6H2O and 0.50 mmol, 0.0831 gH2BDC were placed in a
crystallisation vial placed in a 25 mL teflon-lined stainless-steel
autoclave mixed with 1.005 g [EMI]Cl. The mixture was kept inside
the furnace at 160 °C for 5 days, and then naturally cooled to
ambient temperature. The blue crystals of 1 suitable for single
crystal X-ray diffraction were collected after soak clearing with
acetone. IR data (in KBr, cm–1) for 1: 3703(w), 3325(w), 3145(m),
3097(s), 2989(m), 1583(s), 1383(s), 1306(m), 1167(s), 1018(w), 825
(m), 740(s), 624(w), 557(m). Elemental analysis (%), Found (calcd):
C, 45.05(44.93); H, 3.31(3.56); N, 5.75(5.82).
Synthesis of compounds 2–8. Compounds 2–8 were synthesized
from the similar preparation process as described in compound 1.
[PMI]2[Co3(BDC)3Cl2] (2): 2.5 mmol, 0.7275 g Co(NO3)2  6H2O
and 0.50 mmol, 0.0833 g H2BDC mixed with 0.8 mL (ca. 0.93 g)
[PMI]Cl. IR data (in KBr, cm  1) for 2: 3660(w), 3138(w), 3082(w),
2966(w), 1601(s), 1389(s), 1308(s), 1166(m), 1014(w), 825(m), 744
(s), 557(m). Elemental analysis (%), Found (calcd): C, 46.05(46.08);
H, 3.91(3.87); N, 5.69(5.66).
[BMI]2[Co3(BDC)3Cl2] (3): 1.5 mmol, 0.4365 g Co(NO3)2  6H2O
and 0.50 mmol, 0.0834 g H2BDC mixed with 1.0026 g [BMI]Cl. IR
data (in KBr, cm  1) for 3: 3666 (w), 3298(w), 3142(m), 3088(m),
2963(m), 1963(w), 1841(w), 1593(s), 1385(s), 1307(s), 1160(m),
1010(w), 825(s), 742(s), 625(w), 543(s). Elemental analysis (%),
Found (calcd): C, 47.02(47.17); H, 3.97(4.16); N, 5.61(5.50).
[AMI]2[Co3(BDC)3Cl2] (4). 1.5 mmol, 0.4359 g Co(NO3)2  6H2O
and 0.50 mmol, 0.0832 g H2BDC mixed with 0.9 mL (ca. 0.99 g)
[AMI]Cl. IR data (in KBr, cm–1) for 4: 3718(w), 3282(w), 3133(m),
3087(m), 2961(m), 1944(w), 1682(m), 1597(s), 1392(s), 1296(s),
1164(m), 1010(w), 740(s), 625(w), 555(s). Elemental analysis (%),
Found (calcd): C, 48.15(48.20); H, 4.40(4.43); N, 5.42(5.35).
[EMI]2[Co3(BDC)3I2] (5). 1.0 mmol, 0.2914 g Co(NO3)2  6H2O and
0.50 mmol, 0.0833 g H2BDC mixed with 1.0031 g [EMI]I. IR data (in
KBr, cm  1) for 5: 3722(w), 3408(w), 3151(m), 3103(m), 2974(w),
1591(s), 1156(m), 1385(s), 1302(m), 1164(m), 1018(w), 825(s), 746
(s), 555(s). Elemental analysis (%), Found (calcd): C, 38.15(37.75);
H, 3.11(2.99); N, 4.78(4.89).
[PMI]2[Co3(BDC)3I2] (6). 1.0 mmol, 0.2915 g Co(NO3)2  6H2O and
0.50 mmol, 0.0830 g H2BDC mixed with 1.0 mL (ca. 1.51 g) [PMI]I.
IR data (in KBr, cm  1) for 6: 3830(w), 3737(w), 3415(w), 3133(m),
3101(m), 2962(w), 1631(s), 1592(s), 1383(s), 1302(s), 1160(m), 1018
(m), 902(w), 825(s), 746(s), 555(s). Elemental analysis (%), Found
(calcd): C, 38.95(38.90); H, 3.41(3.26); N, 4.85(4.77).
[BMI]2[Co3(BDC)3I2] (7). 1.0 mmol, 0.2911 g Co(NO3)2  6H2O and
0.50 mmol, 0.0836 g H2BDC mixed with 1.0 mL (ca. 1.52 g) [BMI]I.
IR data (in KBr, cm  1) for 7: 3581(w), 3384(w), 3141(m), 3102(m),
1592(s), 1492(m), 1387(s), 1302(s), 1167(m), 1014(m), 890(w), 819
(s), 740(s), 554(s). Elemental analysis (%), Found (calcd): C, 39.93
(40.06); H, 3.40(3.36); N, 4.74(4.67).
[AMI]2[Co3(BDC)3I2] (8). 1.0 mmol, 0.2915 g Co(NO3)2  6H2O and
0.50 mmol, 0.0834 g H2BDC mixed with 1.2 mL (ca. 1.83 g) [AMI]I.
IR data (in KBr, cm  1) for 8: 3591(w), 3149(m), 3102(m), 2952(m),
1600(s), 1500(m), 1388(s), 1301(s), 1166(m), 1007(m), 871(w), 831
(s), 740(s), 628(w), 540(s). Elemental analysis (%), Found (calcd): C,
41.28(41.03); H, 3.87(3.77); N, 4.63(4.56).
2.3. Single crystal X-ray diffraction
Single crystals of compounds 1–8 were manually harvested
from crystallisation vials and mounted on Hampton Research
CryoLoops using FOMBLIN Y perfluoropolyether vacuum oil (LVAC
25/6, purchased from Aldrich) [23] with the help of a Stemi 2000
stereomicroscope equipped with Carl Zeiss lenses. Data were col-
lected on a Rigaku Mercury CCD diffractometer equipped with a
graphite-monochromated Mo-Kα radiation (λ ¼0.71073 Å) at 293
(2) Kolpotocheirodon the intensity data were collected by the ω
scan technique and were reduced using CrystalClear program. [24]
The crystal structures of compounds 1–8 were solved by direct
method using SHELXTL™ package of crystallographic software
[25] and refined by fullmatrix least-squares technique on F2. All
non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were located at geometrically calculated positions to their
carrier atoms and refined with isotropic thermal parameters in-
cluded in the final stage of the refinement. The summaries of the
structural determination and refinement for 1-8 are listed in
Supporting Information (Tables 1 and 2). The selected bond dis-
tance and angles are listed in Supporting Information (Table S1).
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Center (the deposition CCDC
numbers 1452374-1452381 for compounds 1–8 respectively).
These data can be obtained free of charge from The Cambridge
Crystallographic Data Center via www.ccdc.cam.ac.uk/data_re
quest/cif.
3. Results and discussion
3.1. Crystal structures of compounds 1–8
With the corresponding RMI þ cations anchoring in the inter-
layer spaces and X  anions as the terminal ligand, similar 2D
layered compounds 1–8, [RMI]2[Co(BDC)3X2] (X ¼ Cl, RMI ¼ EMI
(1), PMI (2), BMI (3), AMI (4); X ¼I, RMI ¼ EMI (5), PMI (6), BMI
(7), AMI (8)), were obtained. These structures possess the same
[Co3(BDC)3X2]2  skeleton framework (Fig. 1), including the same
coordination spheres of the Co(II) centers (Fig. 2 and Fig. S1) and
the coordination fashions of the BDC2  ligands. Therefore, only the
structure of compound 1 will be discussed in detail. The asym-
metric unit of compound 1 comprises of one and a half Co(II)
centers, one and a half BDC2  ligands, one Cl  and one EMI þ
(Fig. 2). The total four positive charges on one and a half Co(II)
centers and EMI þ cation are neutralized by one and half BDC2 
ligands and one Cl  to keep charge balance. BDC2  ligands in
compound 1 exhibit two kinds of μ4 coordination fashions: bis-
bidentate and bis-bridging monodentate coordination fashions
(Scheme 1). Two independent Co1 and Co2 centers show different
coordination geometries: a distorted tetrahedron coordination
 Z.-H. Zhang et al. / Journal of Solid State Chemistry 238 (2016) 217–222 219

Table 1
Crystal and structure refinement data for compounds 1-4.

Compounds 1 2 3 4

Empirical formula C36H34Cl2Co3N4O12 C38H38Cl2Co3N4O12 C40H42Cl2Co3N4O12 C42H46Cl2Co3N4O12

Color and habit blue prism blue block blue block blue block
Crystal size (mm3) 0.15  0.11  0.10 0.10  0.08  0.060 0.20  0.10  0.10 0.15  0.10  0.06
Crystal system Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21/n P21/n P21/n P21/n
a (Ǻ) 12.7664(5) 12.8090(9) 12.7532(5) 13.8593(19)
b (Ǻ) 9.5245(4) 9.6002(5) 9.5146(3) 9.8845(11)
c (Ǻ) 18.0566(7) 18.0191(9) 18.0341(7) 18.253(3)
β (°) 107.986(4) 108.042(7) 107.919(4) 112.263(18)
V (Ǻ3) 2088.27(2) 2096.97(16) 2082.14(13) 2314.2(5)
Z 2 2 2 2
Fw 962.36 990.41 1008.39 1046.52
Dcalcd (Mgm  3) 1.530 1.561 1.988 1.502
μ (mm  1) 1.369 1.359 1.608 1.242
F (000) 978 1010 1022 1074
θ (°) 3.85–25.03 3.45–25.03 3.44–25.03 3.59–25.03
Reflections measured 8118 8542 19,427 9168
Independent reflections 3661 (Rint ¼ 0.0227) 3702 (Rint ¼0.0319) 3634 (Rint ¼ 0.0423) 3998 (Rint ¼0.0334)
Observed reflection [I42s(I)] 3251 3100 3311 2859
Final R1, wR2 indices (obs.) 0.0389, 0.0991 0.0399, 0.0932 0.0727, 0.1984 0.0867, 0.2258
R1, wR2 indices (all) 0.0452, 0.1040 0.0524, 0.1027 0.0775, 0.2031 0.1122, 0.2381
S 1.069 1.058 1.043 1.091
(Δ/s)max/min 0.001, 0.000 0.000, 0.000 3.834, 0.131 0.000, 0.000
(Δρ)max/min (eǺ  3) 1.035, 0.347 0.884,  0.671 2.707, 1.159 1.753,  0.572

Table 2
Crystal and structure refinement data for compounds 5–8.

Compounds 5 6 7 8

Empirical formula C36H34Co3I2N4O12 C38H38Co3I2N4O12 C40H40Co3I2N4O12 C42H46Co3I2N4O12

Color and habit blue block blue prism blue block blue block
Crystal size (mm3) 0.20  0.15  0.03 0.18  0.15  0.13 0.15  0.12  0.10 0.15  0.08  0.06
Crystal system Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21/n P21/c P21/c P21/c
a (Ǻ) 13.2922(4) 13.2753(5) 13.4078(6) 13.4089(12)
b (Ǻ) 9.4019(3) 9.4165(5) 9.6411(5) 9.8436(10)
c (Ǻ) 18.6159(6) 18.7760(8) 18.5041(10) 18.275(3)
β (°) 110.139(3) 110.276(4) 108.572(5) 109.405(12)
V (Ǻ3) 2201.69(17) 2201.69(17) 2267.4(2) 2275.2(4)
Z 2 2 2 2
Fw 1145.26 1173.31 1201.37 1229.42
Dcalcd (Mgm  3) 1.741 1.770 1.760 1.795
μ (mm  1) 2.600 2.582 2.509 2.503
F (000) 1122 1154 1186 1218
θ (°) 3.75–25.03 3.76–25.03 3.84–25.03 3.68–25.02
Reflections measured 20,564 8576 9791 9522
Independent reflections 3822 (Rint ¼ 0.0332) 3825 (Rint ¼ 0.0397) 3960 (Rint ¼0.0357) 3945 (Rint ¼ 0.0553)
Observed reflection [I42s(I)] 3284 2549 2967 1808
Final R1, wR2 indices (obs.) 0.0548, 0.1637 0.0700, 0.1782 0.0877, 0.2511 0.1564, 0.3880
R1, wR2 indices (all) 0.0634�0.1748 0.0916, 0.1889 0.1111, 0.2812 0.1931, 0.4059
S 1.075 1.027 1.054 1.078
(Δ/s)max/min 0.003 0.000 0.006, 0.000 0.010, 0.000 0.014, 0.001
(Δρ)max/min (eǺ  3) 1.683�  1.969 1.763,  1.134 2.550,  2.636 4.303,  1.701

R1 ¼(Σ||Fo|-|Fc ||/Σ |Fo|). wR2 ¼[Σ (w(Fo2-Fc2)2)/Σ (w |Fo2|2)]1/2

sphere of Co1 center is shaped by three carboxylic oxygen atoms
and one monodentate terminal Cl  ligand; while a distorted oc-
tahedron of Co2 center consists of six carboxylic oxygen atoms.
Co2 center as a central symmetric point connects Co1 center and
its symmetric atom through two pairs of μ2-bidentate COO 
groups and one μ2-bridging monodentate COO  group into a
linear trinuclear [Co3(COO)6Cl2] SBU with Co∙∙∙Co separations of
3.2501(2) Å. Such four [Co3(COO)6Cl2] SBUs are further bridged by
four rest benzene moieties from BDC2  ligands of μ4-bis-bidentate
mode into a 36-membered quadrilateral, and grow into a layered
(4,4) sheet along the bc-plane. With the benzene rings from BDC2 
ligands of μ4-bridging monodentate fashion embed into the 36-
membered quadrilateral along the b-direction, a (3,6) topological
layer is finally constructed by dummying [Co3(COO)6Cl2] SBUs and
benzene rings as 6-and 2-connecting nodes (Fig. 3).
3.2. Characterizations
3.2.1. PXRD
The experimental PXRD patterns for compounds 1–8 match
well with those simulated from single crystal structure data
(Supporting Information, Fig. S2), indicating that bulk samples of
compounds 1–8 were isolated as single crystal pure phases (Fig. 4).
3.2.2. FT-IR spectra
The characteristic absorption peaks of the main functional
groups for compounds 1–8 are listed in Table 3. The asymmetric
220 Z.-H. Zhang et al. / Journal of Solid State Chemistry 238 (2016) 217–222

Fig. 3. The (3,6) topological network.

stretching vibrations υas(COO  ) are observed in the rang 1556–

Fig. 1. Schematic representation the 2D [RMI]2[Co(BDC)3X2] structure (X ¼ Cl, RMI
¼ EMI (1), PMI (2), BMI (3), AMI (4); X¼I, RMI ¼ EMI (5), PMI (6), BMI (7), AMI (8)).
1682 cm  1 and symmetric stretching vibrations υs(COO  ) in
1296–1392 cm–1. Compared to the carbonyl frequencies of free
H2BDC ligand (υC ¼ O ¼ 1682 cm–1), the above stretchings shift to
lower wave numbers. The difference Δ(υas(COO  )-υs(COO  ))
were beyond 200 cm  1, indicating the carboxylate groups are in
coordinated situations, [26] in accordance with the single crystal
structural analysis. In the compounds 1–8, the peaks at ca.
3100 cm  1 related with C-H stretching of the imidazolium ring,
those from 2952 to 2989 cm–1 are from C-H stretching vibrations
of the alkyl chains, and the ones around 1160 cm  1 assigned to
C-N stretchings of the imidazolium ring.

3.2.3. TG analysis
The TG analyses of compounds 1–8 are measured to investigate
the thermal stabilities and the effect of ILs on the corresponding
products. The TGA results show the thermal stabilities of these
frameworks beyond 300 °C. in the Cl  series, the compounds 1–4
started to decompose at 420 °C for 1, 400 °C for 2, 380 °C for 3,
330 °C for 4 (Fig. 5a). With the increase of alkyl chain in RMI þ , the
decomposition temperatures decrease. This phenomenon also
appears in the compounds of I‒ series: the decomposition tem-
peratures are at 400 °C for 5, 390 °C for 6, 350 °C for 7, and 310 °C
Fig. 2. Coordination spheres of Co(II) centers in compound 1. for 8 (Fig. 5b). The decreasing orders of the thermal decomposition
temperatures of the compounds of Cl‒ and I‒ series are contrary to
Co Co Co that of the alkyl chains in RMI þ templates, which relates with the
electrostatic interactions between the negative 2D skeletons and
positive RMI þ cations. These electrostatic interactions are relevant
to the inductive effect between the positive imidazole ring and the
O O Co O O alkyl substituents in the RMI þ cations. The inductive effect can be
used to affect the stability of a molecule depending on the charge
present on the atom and the bonded groups. The imidazole ring
with delocalized positive charge is bonded to the electron-re-
leasing alkyl substituents, leading to þI inductive effect which
increases with the alkyl chain. Therefore, the positive charge in the
imidazole ring becomes'de-amplified’ and the electrostatic inter-
actions will be decreased with the alkyl chains, thus to make less
stable frameworks. As for the cases with same RMI þ templates,
the thermal stabilities of the compounds containing Cl  are 10–
30 °C higher than those with I  (Fig. 6). This phenomenon may be
explained by the factors of the electronegativity and the sizes of
halide: Cl  with stronger electronegativity offer stronger Co-Cl
bond. The combining effect of RMI þ templates and X  anions on
the structure results in the different TG behaviors.

O O O O Co 3.2.4. Fluorescence
The emission spectra of the compounds 1–8 in the solid state
are recorded at ambient temperature. Free H2BDC ligand shows
Co Co Co two emission peaks at 399 and 415 nm with the excitation at
330 nm, which can be assigned to intraligand n∙∙∙π* of COOH and

(a) (b) π∙∙∙π* of benzene ring transfer (ILCT) respectively. Compounds 1–8
all exhibit two similar broad emissions at ca. 380 and 390 nm (381
and 390 nm for 1, 380 and 394 nm for 2, 382 and 393 nm for 3,
Scheme 1. The coordination fashions of BDC2  ligands in compound 1. 380 and 394 nm for 4, 382 and 393 nm for 5, 382 and 393 nm for
6, 382 and 394 nm for 7, 383 and 395 nm for 8) excited at ca.
320 nm (Fig. 6a-b). The similar fluorescence originates from the
structural similarities. Compared to those of free H2BDC ligand, the
 Z.-H. Zhang et al. / Journal of Solid State Chemistry 238 (2016) 217–222 221

Fig. 4. TG curves of compounds 1–4 (a) and 5–8 (b), the insert graphs are the decomposition temperatures of the compounds of Cl  and I  series.

Table 3
The main IR characteristic absorption peaks for compounds 1–8.

Compounds υas(COO–)/cm  1 υs(COO–)/cm  1 δ(C–H)(MI)/cm–1 δ(C–N)(MI)/cm–1 δ(C–H)(CH3CH2)/cm–1

1 1583 1384,1306 3145, 3097 1167 2989

2 1601 1389, 1308 3138, 3082 1166 2966
3 1593 1385, 1307 3142,3088 1160 2963
4 1682, 1597 1392,1296 3133, 3087 1164 2961
5 1591,1556 1385,1302 3153,3103 1164 2974
6 1631,1592 1383,1302 3133,3101 1160 2962
7 1592 1387,1302 3141,3102 1167 2960
8 1600 1388, 1301 3149, 3102 1166 2952

(B) and amyl (A); MI ¼ imidazolium; X¼ Cl–, I–), are synthesized

Fig. 5. The effect of cations and anions of ILs to the decomposition temperature.
coordination with Co(II) centers produces about 20 nm blue shifts,
whose emissions are assigned to ILCT. Therefore, the RMI þ tem-
plates and X  anions do not exert obvious influence on the
fluorescence.
with eight kinds of 1-methyl-3-alkylimidazolium halide [RMI]X
under ionothermal processes. The eight [RMI]2[Co3(BDC)3X2] fra-
meworks exhibit same negative 2D [Co3(BDC)3X2]2‒ skeletons
with RMI þ locating in the interlayer space. Because the þ I in-
ductive effect of the alkyl substituents exert on the positive imi-
dazole ring, the positive charge in the imidazole ring is de-am-
plified, resulting in the decreased electrostatic interactions be-
tween the negative 2D skeletons and positive RMI þ cations, thus
leading to less stable frameworks. This effect on the structure
construction passes to TG behaviors of compounds 1–8. With the
alkyl chain in RMI þ increasing, the decomposition temperatures
decrease, which is related with the þI inductive effect of the alkyl
substituents on the structures. Also, with the same RMI þ , com-
pounds 1–4 with Cl  show higher thermal stabilities than the
corresponding compounds 5–8 containing I  , which may concerns
with the fact that Cl  anion shows stronger electronegativity and
smaller size than I–. However, the combining effect of RMI þ
templates and halide anions do not play obvious role in fluores-
cence. Compounds 1–8 show similar two emissions at ca. 380 and
390 nm, which are assigned to ILCT. Our present work demon-
strates that it is feasibility to tune the properties through tailoring
the IL components. Further investigations on such systems may
give out more information from new MOF materials.
Acknowledgements

The Project was sponsored by the National Natural Science

4. Conclusion Foundation of China, China (21401122), the Natural Science
Foundation of Shaanxi province, China (2015JQ2041), Innovation
In the present work, a series of Co–BDC metal–organic frame- Funds of Graduate Programs of Shaanxi Normal University
works, [RMI]2[Co3(BDC)3  2] (R¼ethyl (E), propyl (P), butyl (2015CXS037).
222 Z.-H. Zhang et al. / Journal of Solid State Chemistry 238 (2016) 217–222
Fig. 6. The solid-emission spectra of compounds 1–4 with X  ¼Cl  (a), compounds 5–8 with X  ¼I  (b) and free H2BDC as comparison (λex ¼ 275 nm) recorded at ambient
temperature.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.jssc.2016.03.028.
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