Influential factors on assembly of first-row transition metal coordination polymers

Article abstract of DOI:10.1016/j.ica.2013.03.042

Herein, twenty-seven coordination polymers were synthesised using Mn ²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn ²⁺ in organic solvents. Structural analyses show that metal ions are the most important factor that inf

Full text of DOI:10.1016/j.ica.2013.03.042

Inorganica Chimica Acta 403 (2013) 53–62
Contents lists available at SciVerse ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Influential factors on assembly of first-row transition metal
coordination polymers
Shi-Yao Yang a, , Hong-Bo Yuan a,b, Xiao-Bin Xu a,c, Rong-Bin Huang a
⇑
a Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
b Shandong Career Development College, Shandong, Jining 272021, China
c North Fujian Vocational and Technical College, Fujian, China
a r t i c l e i n f o
a b s t r a c t
Herein, twenty-seven coordination polymers were synthesised using Mn2+, Co2+, Ni2+, Cu2+ and Zn2+ in
organic solvents. Structural analyses show that metal ions are the most important factor that influences
coordination polymer assembly. Metal ions determine the type of metal centre and structural topology.
The organic ligand benzene dicarboxylic acid is the second most influential factor. Synthetic conditions
are not key factors in this research system.
Article history:
Available online 6 April 2013
Coordination Polymers Special Issue
Keywords:
Metal centre
Ó 2013 Elsevier B.V. All rights reserved.
Ion radius
Benzene dicarboxylic acid
Metal–organic framework
Crystal engineering
1. Introduction
form discrete SBUs and when the infinite rod-shaped SBU (Second-
ary Building Unit) will be formed [19].
Coordination polymers have attracted intense research interest
in recent years not only for their importance in chemistry [1–3] but
also for their potential application in many areas [4–10]. Their
most promising application is to be used as porous materials
[11–15].
Most research has concentrated on design and synthesis of
bridging ligands, which are the organic portion of coordination
polymers [20–24]. Benzene polycarboxylic acids have been widely
used for such studies. They can adopt various coordination modes,
which have certain consequences for the product’s structures and
properties, and they often form highly stable MOFs [25–27]. Syn-
thetic conditions, including pH value [28,29], temperature [30–
33], solvents [34], and counter ions [35], also play an important
role in synthesis. Polar organic solvents with a high boiling point,
such as DMF (N,N-dimethylformamide), DEF (N,N-diethylforma-
mide), and DMSO (dimethyl sulfoxide), are excellent solvents for
reactants and can act as space-filling solvent molecules for porous
MOFs [36,37]. We found that solvents and mixed solvent ratios can
be used as media for adjusting the metal centres and structures in
coordination polymers [38–41].
What is the decisive influential factor for assembly of first-row
transition metal coordination polymers, and why are Cu2+ and Zn2+
over other metal ions so common in porous materials? To answer
the above questions and to synthesise coordination polymers, we
used the first-row transition metal ions Mn2+, Co2+, Ni2+ and Cu2+
as well as Zn2+ as the inorganic components; benzene dicarboxylic
acids were the bridging ligands; and polar high-boiling-point or-
ganic compounds were the solvents (Table 1). Here, we report
structural analyses for the twenty-seven products generated as
well as the conclusions for our research.
Coordination polymers comprise two parts: metal ions (inor-
ganic) and ligands (in most cases, organic). Numerous metal ions
are involved in coordination polymer assembly, and the first row
transition metal ions are the best candidates because they are
abundant and cheap with low toxicity. Such metal ions are also
suitable for design and synthesis of low density porous materials
given their relatively low atomic weight. Many highly porous coor-
dination polymers (PCPs; also referenced as open metal-organic
frameworks, MOFs) are assembled using Cu2+ or Zn2+ (a main
group d10 ion) [16]. Moreover, most magnetic MOFs can be assem-
bled by incorporating paramagnetic divalent first-row transition
metals (Mn, Fe, Co, Ni and Cu) within distances sufficient for inter-
action [17]. The metal centre’s structure and properties are extre-
mely important in designing coordination polymers with various
features [18]. It is critical to know when the metal ions tend to
⇑
Corresponding author. Tel.: +86 592 2186175; fax: +86 592 2183047.
E-mail address: syyang@xmu.edu.cn (S.-Y. Yang).
0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2013.03.042

54
S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
Table 1
Ligands and solvents used in this work.
Ligand or solvent
Name
Short name
Length (Å) and angle (°)
between two carboxyls
Short ligands
isophthalic acid
H2ip
5.94, ꢀ120
HO
HO
O
O
O
O
OH
5-aminoisophthalic acid
H2aip
6.03, ꢀ119
NH2
OH
5-tert-butylisophthalic acid
H2tbip
5.93, ꢀ119
HO
HO
O
O
OH
thiophenedicarboxylic acid
H2tdc
6.44, ꢀ153
O
S
OH
O
O
Medium ligands
terephthalic acid
H2tp
6.93
6.92
HO
O
O2N
HO
OH
2-nitroterephthalic acid
H2ntp
O
O
OH
1,4-naphthalenedicarboxylic acid
tetramethylterephthalic acid
H21,4-ndc
6.98, ꢀ175
HO
O
O
OH
O
H2tmtp
7.02
HO
O
OH
Long ligands
2,6-naphthalenedicarboxylic acid
biphenyldicarboxylic acid
H22,6-ndc
H2bpdc
9.15
HO
O
O
OH
11.22
HO
O
O
OH
Solvents
N,N-dimethylformamide
N,N-dimethylacetamide
N-methyl-2-pyrrolidone
DMF
DMA
NMP
N
O
N
O

S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
55
Table 1 (continued)
Ligand or solvent
Name
Short name
Length (Å) and angle (°)
between two carboxyls
N
O
dimethylsulfoxide
pyridine
DMSO
PY
S
O
N
(2.66)%. IR (cmÀ1): 3446, 1575 (s), 1528 (s), 1373 (vs), 1315, 996,
940, 793, 772 (w), 677 (w), 475.
2. Experimental
2.1. Methods
2.1.5. [Mn(tp)(dmf)]n
5
A mixture comprising a Mn(NO3)2 50% aqueous solution (0.30 g,
1.7 mmol) and H2tp (0.166 g, 1.0 mmol) in a mixed solvent of 6 mL
DMF and 4 mL ethanol was heated at 90 °C for 4000 min. Pale yel-
low crystals were obtained (0.187 g, 64% based on H2tp). Elemental
analysis, Anal. (Calc.) for C22H22Mn2N2O10: C, 45.20 (45.18); H, 2.65
(2.64); N, 4.78 (4.79)%. IR (cmÀ1): 3069 (w), 2929 (s), 2886, 1662
(vs), 1627 (vs), 1578 (vs), 1385 (vs), 1153, 1104 (s), 1020, 891
(w), 866 (w), 819 (s), 752 (vs), 673.
The synthesis procedure for the compounds was as follows. A
solution comprising the metal salt and ligand in an organic solvent
(or mixed solvent) was placed at room temperature or heated
0.2 °C minÀ1 to a temperature in the range 70–140 °C and main-
tained at that temperature for approximately 4 days. Generally,
the synthetic conditions for Mn or Zn compounds are similar, while
Cu compounds are generated at lower temperatures. The products
were collected by filtration and washed with pure solvents. The
crystals produced were characterised using single X-ray crystallog-
raphy, elemental analysis and Infrared spectrometry. IR spectra
2.1.6. [Mn(tmtp)(dmf)]n
6
show strong bands in the range 1690–1500 cmÀ1
vibrations) and 1447–1340 cmÀ1
ms stretching vibrations) for
(mas stretching
A
mixture comprising a Mn(NO3)2 50% aqueous solution
(
(0.036 g, 0.20 mmol) and H2tmtp (0.044 g, 0.20 mmol) in a mixed
solvent of 2 mL DMF and 1 mL ethanol was heated at 90 °C for
4000 min. Colorless crystals were obtained (0.033 g, 48% based
on H2tmtp). There was not enough product for elemental analysis
and IR measurement.
coordinated carboxylato groups, respectively. IR spectra also show
weak bands at about 2930 for saturated C–H and 3100 for aromatic
C–H vibrations, and broad peaks at about 3300 cmÀ1 for water
molecules.
2.1.1. [Mn(ip)(dma)]n
1
2.1.7. {[Co(ntp)(H2O)]Á1.25H2O}n
7
A mixture comprising a Mn(NO3)2 50% aqueous solution (0.77 g,
4.3 mmol) and H2ip (0.249 g, 1.5 mmol) in 8 mL DMA was heated
at 90 °C for 4500 min. Colourless block crystals were generated
(0.350 g, 76% based on H2ip). The elemental analysis (Anal. Calc.)
for C12H13MnNO5 is as follows: C, 47.23 (47.07); H, 4.19 (4.28);
N, 4.72 (4.57)%. IR (cmÀ1): 3408, 2909 (w), 1592 (s), 1537, 1374
(s), 740 (w), and 720 (w).
A mixture comprising Co(NO3)2Á6H2O (0.146 g, 0.50 mmol) and
H2ntp (0.105 g, 0.50 mmol) in a mixed solvent of 10 mL DMF and
3 mL H2O was heated at 100 °C for 5000 min. Red crystals were ob-
tained (0.132 g, 87%). Elemental analysis, Anal. (Calc.) for C8H7.5-
CoNO8.25: C, 32.66 (31.14); H, 2.23 (2.45); N, 4.79 (4.54)%. IR
(cmÀ1): 3447, 2928 (w), 1618 (s), 1537(w), 1387 (s), 1011, 773,
607 (w), 541 (s).
2.1.2. [Mn(tdc)(dma)]n
2
2.1.8. [Zn(1,4-ndc)(dmf)]n 8
A mixture comprising a Mn(NO3)2 50% aqueous solution (0.30 g,
1.7 mmol) and H2tdc (0.086 g, 0.50 mmol) in a mixed solvent of
8 mL DMA and 2 mL ethanol was heated at 100 °C for 5000 min.
Pale yellow crystals were obtained (0.128 g, 82%). Elemental anal-
ysis, Anal. (Calc.) for C10H11MnNO5S: C, 38.39 (38.47); H, 3.58
(3.55); N, 4.51 (4.49)%. IR (cmÀ1): 3371, 1624, 1551 (vs), 1508
(s), 1452 (w), 1372 (vs), 1126 (w), 1044, 779 (s), 681 (w), 540
(w), 496 (w).
A mixture comprising ZnCl2 (0.136 g, 1.0 mmol) and H2(1,4-
ndc) (0.216 g, 1.0 mmol) in a mixed solvent of 10 mL DMF and
3 mL H2O was heated in a 20 mL Teflon lined vessel at 120 °C for
4320 min. Purple block crystals were obtained (0.330 g, 94%). Ele-
mental analysis, Anal. (Calc.) for C8H7.5CoNO8.25: C, 51.45 (51.04);
H, 3.58 (3.69); N 3.93 (3.97)%.
2.1.9. [Cu2(tdc)2(NH3)4]n
9
A mixture comprising Cu(NO3)2Á2H2O (0.121 g, 0.50 mmol) and
H2tdc (0.086 g, 0.50 mmol) in a mixed solvent of 8 mL DMA (or
NMP) and 2 mL aqueous ammonia was left to stand at room tem-
perature for 1 month. Blue crystals were obtained (0.073 g, 55%).
Elemental analysis, Anal. (Calc.) for C8H6CuN2O4S: C, 33.16
(33.03); H, 2.09 (2.10); N, 9.67 (9.71)%. IR (cmÀ1): 3355, 2989
(w), 1634, 1586 (s), 1552, 1523, 1384 (s), 1361 (vs), 823 (w),
767, 476 (w).
2.1.3. [Mn(tdc)(nmp)]n
3
Same procedure for 2 was applied with NMP in place of DMA.
Pale yellow crystals were obtained (0.134 g, 83%). Elemental anal-
ysis, Anal. (Calc.) for C11H11MnNO5S: C, 40.66 (40.75); H, 3.44
(3.42); N, 4.33 (4.32)%. IR (cmÀ1): 3429, 1618 (s), 1583 (s), 1527
(s), 1383 (s), 1367 (vs), 1312, 1050 (w), 772 (s), 676 (w), 476(w).
2.1.4. [Mn(tdc)(dmso)]n
4
Same procedure for 2 was applied with DMSO in place of etha-
nol. Pale yellow crystals were obtained (0.099 g, 65%). Elemental
analysis, Anal. (Calc.) for C8H8MnO5S2: C, 31.63 (31.69); H, 2.65
2.1.10. [Cu2(tbip)2(dma)2]n 10
A mixture comprising Cu(NO3)2Á2H2O (0.072 g, 0.30 mmol) and
H2tbip (0.067 g, 0.30 mmol) in 10 mL DMA was heated at 70 °C for

56
S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
5760 min. Blue crystals were obtained (0.115 g, 58%). Elemental
analysis, Anal. (Calc.) for C16H21NO5Cu: C, 51.92 (51.81); H, 5.69
(5.71); N, 3.81 (3.78)%. IR (cmÀ1): 3427 (vs), 2956, 1612 (vs),
1382 (vs), 1267(w), 787, 730.
2.1.19. [Mn3(bpdc)3(dma)4]n 19
A mixture comprising MnCl2Á4H2O (0.050 g, 0.25 mmol) and H2-
bpdc (0.061 g, 0.25 mmol) in 10 mL DMA was heated at 100 °C for
4320 min. Yellow crystals were obtained (0.050 g, 49%). Elemental
analysis, Anal. (Calc.) for C58H60N4O16Mn3: C, 56.93 (56.46); H,
4.83(4.90); N, 4.68 (4.54)%. IR (cmÀ1): 3388 (s), 2926 (w), 1576
(vs), 1524 (vs), 1386 (vs), 1180 (w), 796 (vs), 672(w).
2.1.11. {[Cu2(ip)2(nmp)2{Cu2(ip)2(H2O)2}2]Á5NMPÁ2H2O}n 11
A mixture comprising Cu(NO3)2Á2H2O (0.048 g, 0.20 mmol) and
H2ip (0.033 g, 0.20 mmol) in a mixed solvent of 4 mL NMP and
6 mL ethanol was left to stand at room temperature for 4 months.
Blue crystals were obtained (0.018 g, 26%). Elemental analysis,
Anal. (Calc.) for C83H99Cu6N7O37: C, 47.96 (45.98); H, 4.32 (4.60);
N, 4.89 (4.52)%. IR (cmÀ1): 3427 (s), 2925 (w), 1633(vs), 1575
(w), 1443 (w), 1388 (vs), 1065, 746 (w), 723(w), 485(s).
2.1.20. [Co3(2,6-ndc)3(dma)4]n 20
A mixture comprising Co(NO3)2Á6H2O (0.146 g, 0.50 mmol) and
H2(2,6-ndc) (0.054 g, 0.50 mmol) in a mixed solvent of 10 mL DMA
and 2 mL ethanol was heated at 100 °C for 2880 min. Red crystals
were obtained (low yield). There was not enough product for ele-
mental analysis and IR measurement.
2.1.12. [Zn2(tp)2(nmp)2]n 12
2.1.21. [Mn3(tp)3(nmp)4]n 21
A mixture comprising Zn(NO3)2Á6H2O (0.297 g, 1.0 mmol) and
H2tp (0.166 g, 1.0 mmol) in 10 mL NMP was heated at 90 °C for
6000 min. Colorless block crystals were obtained (0.192 g, 59%).
Elemental analysis, Anal. (Calc.) for
(47.51); H, 4.70 (3.99); N, 5.18 (4.26)%.
A
mixture comprising a Mn(NO3)2 50% aqueous solution
(0.090 g, 0.50 mmol) and H2(2,6-ndc) (0.108 g, 0.50 mmol) in
10 mL NMP was heated at 90 °C for 4000 min. Colorless block crys-
tals were obtained (0.267 g, 76%). Elemental analysis, Anal. (Calc.)
for C44H48Mn3N4O16: C, 50.17 (50.15); H, 4.53 (4.59); N, 5.29
(5.32)%. IR (cmÀ1): 3056 (w), 2944, 1648 (vs), 1604 (vs), 1557
(vs), 1506 (s), 1382 (vs), 1304 (s), 1260 (s), 1172 (w), 1114 (w),
1018, 984 (w), 885 (w), 843, 815, 748 (vs), 666 (w).
C13H13NO5Zn: C, 47.40
2.1.13. [Zn2(2,6-ndc)2(dmf)2]n 13
A mixture comprising Zn(NO3)2Á6H2O (0.297 g, 1.0 mmol) and
H2(2,6-ndc) (0.216 g, 1.0 mmol) in 15 mL DMF was heated in a
20 mL Teflon lined vessel at 120 °C for 4000 min. Pale yellow block
crystals were obtained (0.276 g, 78%). Elemental analysis, Anal.
(Calc.) for C15H13NO5Zn: C, 51.45 (51.09); H, 3.56 (3.72); N, 3.93
(3.97)%.
2.1.22. {[Co3(bpdc)3(dma)2]Á4DMA}n 22
A mixture comprising Co(NO3)2Á6H2O (0.073 g, 0.25 mmol) and
H2(2,6-ndc) (0.054 g, 0.25 mmol) in 10 mL DMA was heated at
100 °C for 4320 min. Red crystals were obtained (0.151 g, 64%). Ele-
mental analysis, Anal. (Calc.) for C66H78Co3N6O18: C, 57.24 (55.82);
H, 5.38 (5.54); N, 6.11 (5.92)%. IR (cmÀ1): 3603(w), 3427 (w),
1684(vs), 1594(vs), 1540(s), 1396 (vs), 1295, 1178 (w), 843, 773
(s), 676 (w).
2.1.14. [Zn2(tdc)2(dma)2]n 14
A mixture comprising Zn(NO3)2Á6H2O (0.149 g, 0.50 mmol) and
H2tdc (0.086 g, 0.50 mmol) in 10 mL DMA was heated at 90 °C for
7000 min. Colorless crystals were obtained (0.110 g, 56%). IR
(cmÀ1): 3421, 1635 (s), 1577, 1528 (w), 1383 (vs), 1261, 771 (w),
686(w), 494.
2.1.23. {[Zn3(bpdc)3(dmf)2]Á4DMFÁ0.5H2O}n 23
A mixture comprising Zn(NO3)2Á6H2O (0.297 g, 1.0 mmol) and
H2bpdc (0.242 g, 1.0 mmol) in 20 mL DMF was filtrated and heated
at 80 °C for 8000 min. Colorless crystals were obtained (0.177 g,
39%). There was not enough product for elemental analysis and
IR measurement.
2.1.15. [Zn2(tdc)2(py)2]n 15
A mixture comprising Zn(NO3)2Á6H2O (0.149 g, 0.50 mmol) and
H2tdc (0.086 g, 0.50 mmol) in a mixed solvent of 8 mL DMA (or
NMP) and 2 mL pyridine was heated at 90 °C for 7000 min. Color-
less crystals were obtained (0.118 g, 75%). IR (cmÀ1): 3440, 1607
(s), 1573, 1528, 1384 (vs), 1218 (w), 770, 501(w).
2.1.24. {[Zn3(bpdc)3(nmp)2]Á4NMP}n 24
Same procedure for 23 was applied with NMP instead of DMF.
Colorless crystals were obtained (low yield). There was not enough
product for elemental analysis and IR measurement.
2.1.16. [Mn3(2,6-ndc)3(dmf)4]n 16
A
mixture comprising a Mn(NO3)2 50% aqueous solution
2.1.25. {[Ni(2,6-ndc)(H2O)4]Á2NMPÁ2H2O}n 25
(0.50 mmol) and H2(2,6-ndc) (0.108 g, 0.50 mmol) in 15 mL DMF
was heated at 90 °C for 4000 min. Colorless block crystals were ob-
tained (0.222 g, 43%). Elemental analysis, Anal. (Calc.) for C48H46-
Mn3N4O16: C, 52.17 (52.42); H, 4.17 (4.21); N 5.16 (5.09)%.
A mixture comprising Co(NO3)2Á6H2O (0.073 g, 0.25 mmol) and
H2(2,6-ndc) (0.054 g, 0.25 mmol) in 5 mL NMP was microwave
heated at 120 °C for 10 min then cooled down to room tempera-
ture. Green block crystals were obtained (0.068 g, 47%). Elemental
analysis, Anal. (Calc.) for C22H36N2O12Ni: C, 44.36 (45.62); H, 6.41
(6.26); N, 4.96 (4.84)%. IR (cmÀ1): 3423, 2928 (w), 1642 (s), 1564,
1390 (s), 1189 (w), 793, 774, 476.
2.1.17. [Mn3(2,6-ndc)3(dma)4]n 17
A
mixture comprising a Mn(NO3)2 50% aqueous solution
(0.50 mmol) and H2(2,6-ndc) (0.108 g, 0.50 mmol) in 15 mL DMA
was heated at 100 °C for 4320 min. Orange block crystals were ob-
tained (low yield). There was not enough product for elemental
analysis and IR measurement.
2.1.26. [Mn(Haip)2(H2O)2]n 26
A mixture comprising Mn(NO3)2 50% aqueous solution (0.090 g,
0.50 mmol) and H2aip (0.091 g, 0.50 mmol) in a mixed solvent of
4 mL DMA and 4 mL H2O was heated at 110 °C for 4000 min. Col-
orless block crystals were obtained (low yield). There was not en-
ough product for elemental analysis and IR measurement.
2.1.18. [Mn3(2,6-ndc)3(nmp)4]n 18
A
mixture comprising a Mn(NO3)2 50% aqueous solution
(0.50 mmol) and H2(2,6-ndc) (0.108 g, 0.50 mmol) in a mixed sol-
vent of 8 mL NMP and 8 mL ethanol was heated at 100 °C for
4000 min. Yellow block crystals were obtained (low yield). There
was not enough product for elemental analysis and IR
measurement.
2.1.27. [Zn(aip)(dma)]n 27
A mixture comprising Zn(NO3)2Á6H2O (0.297 g, 1.0 mmol) and
H2aip (0.091 g, 0.50 mmol) in a mixed solvent of 7 mL DMA and
2 mL ethanol was heated at 95 °C for 3000 min. Brown block crys-

S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
57
Table 2
Crysltal data for 1–27.
1
2
3
4
5
6
7
Empirical formula
Formula weight
Crystal system
Space group
F(000)
C
12H13MnNO5
C10H11MnNO5S
312.20
monoclinic
C2/c
C11H11MnNO5S
324.21
monoclinic
C2/c
C8H8MnO5S2
303.20
monoclinic
C2/c
C22H22Mn2N2O10
584.30
monoclinic
P21/c
C15H19MnNO5
348.25
tetragonal
I41/a
C8H7.50CoNO8.25
308.58
orthorhombic
Imma
306.17
monoclinic
C2/c
1256
1272
1320
1224
1192
2896
622
T/K
297(2)
299(2)
296(2)
296(2)
296(2)
223(2)
173(2)
a (Å)
b (Å)
c (Å)
12.6006(8)
16.3414(10)
12.6527(8)
11.8527(6)
18.2900(7)
11.4991(6)
11.7729(2)
18.2439(4)
11.7165(2)
11.2759(4)
18.4795(4)
11.2782(4)
13.5792(6)
10.1898(4)
17.6223(7)
20.324(1)
17.9930(6)
7.2497(3)
11.5979(4)
15.2571(7)
a
(°)
b (°)
107.792(1)
99.020(5)
99.6134(19)
96.217(4)
90.738(1)
c
(°)
V (Å3)
2480.7(3)
8
1.640
2462.0(2)
8
1.685
2481.17(8)
8
1.736
2336.25(13)
8
1.724
2438.18(17)
4
1.592
6302.3(4)
16
1.468
1512.87(10)
4
1.355
Z
Dcalc. (g cmÀ3
)
l
(mmÀ1
)
1.080
1.253
1.247
1.487
1.094
0.860
1.162
Reflection collected/unique
Data/restraints/parameters
Rint
S
9112/2928
2928/0/197
0.0271
11022/4108
4108/6/165
0.0759
11389/4164
4164/0/175
0.0229
7540/2740
2740/0/151
0.0240
20635/5806
5806/0/361
0.0307
26550/3807
3807/0/203
0.0313
3587/992
992/0/78
0.0178
1.197
0.847
1.085
1.135
1.046
1.209
1.059
R1 [I > 2
wR2 (all data)
(e AÀ3
r
(I)]
0.0556
0.1194
0.542/À0.445
0.0456
0.1780
0.904/À0.778
0.0315
0.1169
0.642/À0.650
0.0574
0.1829
0.717/À0.911
0.0406
0.1009
0.522/À0.389
0.0542
0.1177
0.587/À0.402
0.0411
0.1343
1.067/À0.689
D
q
)
8
9
10
11
12
13
14
Empirical formula
Formula weight
Crystal system
Space group
F(000)
C
30H26N2O10Zn2
C6H8CuN2O4S
267.74
monoclinic
C2/c
C16H21CuNO5
370.88
monoclinic
P21/c
C83H99Cu6N7O37
2167.93
monoclinic
C2/c
C13H13NO5Zn
328.61
monoclinic
P21/c
C15H13NO5Zn
352.63
Monoclinic
P21/c
C10H11NO5SZn
322.63
monoclinic
P21/n
705.27
monoclinic
Pc
720
1080
772
4464
672
720
656
T/K
295(2)
173(2)
173(2)
173(2)
253(2)
295(2)
153(2)
a (Å)
b (Å)
c (Å)
7.1781(2)
14.0979(3)
16.0641(4)
7.6170(6)
12.6984(8)
19.1943(14)
12.1599(4)
10.6507(3)
14.7652(5)
30.528(5)
19.241(3)
20.103(4)
7.4479(5)
13.9477(9)
12.7644(8)
6.7716(4)
18.590(1)
11.6437(6)
8.4866(2)
14.8476(4)
10.1406(3)
a
(°)
b (°)
121.726(2)
100.373(8)
104.768(3)
128.611(3)
103.500(1)
97.383(1)
100.734(2)
c
(°)
V (Å3)
1382.71(6)
2
1.694
1826.2(2)
8
1.948
1849.09(10)
4
1.332
9227(3)
4
1.561
1289.34(14)
4
1.693
1453.60(14)
4
1.611
1255.41(6)
4
1.707
Z
Dcalc. (g cmÀ3
)
l
(mmÀ1
)
1.800
2.609
1.203
1.450
1.923
1.712
2.133
Reflection collected/unique
Data/restraints/parameters
Rint
S
11048/6641
6641/2/402
0.0474
8137/2217
2217/0/129
0.0608
10775/4320
4320/38/227
0.0318
27799/10781
10781/44/679
0.0976
14647/3087
3087/0/182
0.0474
11320/3343
3343/0/225
0.0220
8051/3095
3095/0/185
0.0298
0.944
1.175
0.966
1.061
1.252
1.054
0.938
R1 [I > 2
wR2 (all data)
(e AÀ3
r
(I)]
0.0500
0.1568
0.663/À1.197
0.0642
0.1985
1.676/À0.785
0.0430
0.1234
1.331/À0.405
0.0646
0.1901
2.238/À0.658
0.0666
0.1411
0.814/À0.893
0.0368
0.1011
0.457/À0.218
0.0340
0.0846
1.210/À0.628
D
q
)
15
11H7NO4SZn
314.61
monoclinic
P21/n
16
17
18
19
20
21
Empirical formula
Formula weight
Crystal system
Space group
F(000)
C
C48H46Mn3N4O16
1099.71
monoclinic
C2/c
C52H54Mn3N4O16
1155.81
monoclinic
C2/c
C56H54Mn3N4O16
1203.85
monoclinic
P21/c
C58H60Mn3N4O16
1233.92
monoclinic
P21/c
C52H54Co3N4O16
1167.78
monoclinic
C2/c
C44H48Mn3N4O16
1053.68
orthorhombic
P212121
632
2260
2388
1242
1278
2412
2172
T/K
173(2)
223(2)
298(2)
297(2)
173(2)
173(2)
173(2)
a (Å)
b (Å)
c (Å)
7.6939(2)
15.9643(4)
9.8577(3)
13.2373(6)
17.9155(8)
21.4035(10)
14.3217(3)
18.4222(4)
20.9869(4)
11.8731(4)
18.4743(7)
20.5194(5)
13.9430(4)
18.2501(6)
12.1687(4)
14.1239(3)
18.3243(4)
20.6657(3)
9.7175(4)
18.0168(8)
26.7918(11)
a
(°)
b (°)
97.670(3)
100.105(1)
99.570(2)
142.563(1)
113.169(4)
99.1218(18)
c
(°)
V (Å3)
1199.97(6)
4
1.741
4997.2(4)
4
1.462
5460.07(19)
4
1.406
2736.03(17)
2
1.461
2846.72(16)
2
1.440
5280.86(18)
4
1.469
4690.7(3)
4
1.492
Z
Dcalc. (g cmÀ3
)
l
(mmÀ1
)
2.224
0.820
0.754
0.756
0.728
1.004
0.869
Reflection collected/unique
Data/restraints/parameters
Rint
S
6642/2831
2831/0/163
0.0296
28344/5977
5977/29/334
0.0254
15834/6751
6751/1/383
0.0260
31189/6560
6560/10/380
0.0330
19451/7796
7796/0/373
0.0210
22412/6334
6334/16/383
0.0422
54343/11289
11289/1/606
0.0326
0.932
1.079
1.009
1.086
1.047
1.035
1.078
R1 [I > 2
wR2 (all data)
(e AÀ3
r
(I)]
0.0265
0.0574
0.648/À0.363
0.0519
0.1355
0.882/ À0.442
0.0376
0.1114
0.616/ À0.310
0.0531
0.1255
0.586/ À0.387
0.0297
0.0799
0.631/ À0.289
0.0401
0.0975
0.451/ À0.500
0.0487
0.1247
D
q
)
1.103/ À0.639
(continued on next page)

58
S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
Table 2 (continued)
22
23
24
25
26
27
Empirical formula
Formula weight
Crystal system
Space group
F(000)
C
66H78Co3N6O18
C120H132N12O37Zn6
2726.60
monoclinic
P21/n
C72H78N6O18Zn3
1511.51
monoclinic
P21/c
C22H36N2NiO12
579.24
C16H16MnN2O10
451.25
monoclinic
P2/c
C12H14N2O5Zn
331.62
monoclinic
P21/c
1420.13
monoclinic
P21/c
triclinic
ꢀ
P1
1482
2824
1572
306
462
680
T/K
173(2)
273(2)
223(2)
123(2)
173(2)
173(2)
a (Å)
b (Å)
c (Å)
12.2756(2)
14.1032(2)
25.8603(4)
20.0297(10)
14.8284(7)
22.9351(11)
12.1580(5)
14.0426(5)
25.9262(8)
7.1977(3)
7.2645(4)
12.8111(7)
81.631(4)
83.686(4)
78.332(4)
646.79(6)
1
6.9972(2)
10.0161(3)
13.8929(5)
10.1163(3)
7.7922(2)
16.0161(5)
a
(°)
b (°)
129.437(1)
111.256(1)
127.589(1)
124.842(2)
90.522(2)
c
(°)
V (Å3)
3457.74(9)
2
1.364
6348.5(5)
2
1.426
3507.5(2)
2
1.431
799.13(5)
2
1.875
1262.47(6)
4
1.745
Z
Dcalc. (g cmÀ3
)
1.487
0.816
l
(mmÀ1
)
0.783
1.199
1.092
0.896
1.967
Reflection collected/unique
Data/restraints/parameters
Rint
S
21817/8052
8052/0/452
0.0243
54359/15099
15099/0/816
0.0516
40257/8483
8483/0/450
0.0489
4612/2784
2784/30/214
0.0132
4044/1850
1850/2/152
0.0248
19861/3160
3160/2/192
0.0731
0.985
1.111
1.098
1.105
1.001
0.971
R1 [I > 2
wR2 (all data)
(e AÀ3
r
(I)]
0.0318
0.0793
0.463/À0.387
0.0739
0.2116
1.792/À0.636
0.0586
0.1355
0.797/À0.704
0.0284
0.0783
0.354/À0.395
0.0293
0.0794
0.322/À0.399
0.0325
0.0872
0.659/À0.611
D
q
)
Fig. 1. Rod-shaped SBUs in 1 (a), 2–4 (b), 5 (c), 6 (d), 7 (e), and 8 (f); pcu topology for the rod packing structure simplified from compound 4.
tals were obtained (0.067 g, 40% based on H2aip). Elemental analy-
sis, Anal. (Calc.) for C12H14N2O5Zn: C, 42.64 (43.16); H, 5.53 (4.26);
N 8.93 (8.45)%.
3. Results and discussion
The compounds can be classified into six groups according to
their structural features.
2.2. X-ray structure determination
The data were collected on a Bruker SMART Apex CCD diffrac-
tometer or an Oxford Gemini S Ultra CrysAlis CCD diffractometer
3.1. Rod-packing pcu assembled with rod-shaped SBUs
with monochromatic graphite Mo K
a
radiation. Structure solutions
The structural topology for the following eight compounds is
rod-packing pcu (Fig. 1.) [7]: [Mn(ip)(dma)]n 1, [Mn(tdc)(dma)]n
2, [Mn(tdc)(nmp)]n 3, [Mn(tdc)(dmso)]n 4, [Mn(tp)(dmf)]n 5,
[Mn(tmtp)(dmf)]n 6, {[Co(ntp)(H2O)]Á1.25H2O}n 7 and [Zn(1,4-
ndc)(dmf)]n 8. These compounds were assembled using short li-
gands (e.g., H2ip and its derivatives ꢀ5.9 Å as well as H2tdc
ꢀ6.4 Å), and medium-length ligands (H2tp and its derivatives
ꢀ7 Å). Metal ions, such as Mn2+, Co2+ and Zn2+, form Mn metal cen-
tres or rod-shaped SBUs composed of corner-sharing octahedra,
while the Mn2+ ion with the largest size can also form edge-sharing
octahedral rod-shaped SBUs (Fig. 1a, d). Six of the eight compounds
in this group were formed using Mn2+ ions, which demonstrates
and full-matrix least-square refinements based on F2 were per-
formed using the SHELXS-97 and SHELXL-97 program packages, respec-
tively. All the non-hydrogen atoms were refined anisotropically.
The H atoms on ligands were positioned geometrically and were
allowed to ride on the C atoms in the subsequent refinement (aro-
matic C–H = 0.93 Å, U(H) = 1.2 Ueq(C), methyl C–H = 0.95 Å,
U(H) = 1.5 Ueq(C)). The water H-atoms were located and refined
with OÀH = 0.85 Å, U(H) = 1.5 Ueq(O) restraints. The water H-
atoms were set to proper positions so that more hydrogen bonds
can be formed. Crystal data for all the compounds are listed in
Table 2.

S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
59
Fig. 2. Dinuclear metal centres appear in 9 (a), 12 (b), and 11 (c, C–H hydrogen atom omitted); sql net for 9, 10, and 12–15 (d); kgm net for 11 (e).
Fig. 3. Trinuclear SBU for 16 (a) and structural topology pcu for 16–20 (b).
that Mn2+ has a strong tendency to form rod-shaped SBUs. Notably,
2, 3 and 4 were synthesised in different solvents and are isostruc-
tures, which demonstrates that the solvents did not influence the
structures. Compounds 5 and 6 were synthesised using H2tp and
tetramethyl-substituted H2tmtp, and their structures have same
topology.

60
S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
3.2. sql and kgm nets assembled with dinuclear metal centres
3.4. hxl net assembled with trinuclear metal centres
The following seven compounds contain dinuclear metal
centres with four coordination points: [Cu2(tdc)2(NH3)4]n 9, [Cu2(-
tbip)2(dma)2]n 10, {[Cu2(ip)2(nmp)2{Cu2(ip)2(H2O)2}2] Á5NMPÁ2H2-
O}n 11, [Zn2(tp)2(nmp)2]n 12, [Zn2(2,6-ndc)2(dmf)2]n 13,
[Zn2(tdc)2(dma)2]n 14 and [Zn2(tdc)2(py)2]n 15 (Fig. 2). When the
same ligands with short-medium lengths as for group 1 were used
(except for 13, which was assembled with the long ligand H2(2,6-
ndc), Cu2+ and Zn2+ tended to form dinuclear metal centres instead
of rod-shaped SBUs, and the topology of the structures were sql,
which is related to a node with four coordination points. Most of
the paddle-wheel M2 metal centres adopted a sql topology, while
the structure for 11 was assembled using a bent ligand, H2ip,
which adopted a kgm net [42].
The following four compounds also contain trinuclear metal
centres with six coordination points similar to the compounds dis-
cussed above, but their structures adopted a hxl net (Fig. 4.):
[Mn3(tp)3(nmp)4]n21, {[Co3(bpdc)3(dma)2]Á4DMA}n22, {[Zn3(bpdc)3
(dmf)2]Á4DMFÁ0.5H2O}n23, and {[Zn3(bpdc)3(nmp)2]Á4NMP}n24. The
compound 21 was assembled with the medium-long ligand H2tp,
but 22, 23 and 24 were assembled with the long ligand
H2bpdc. Furthermore, except for Mn2+ ion at the end of the Mn3 me-
tal centre, which combines two organic solvent molecules, each Co2+
or Zn2+ ion coordinated with only one solvent molecule. Clearly, Co2+
and Zn2+ are smaller than Mn2+ and can have a lower coordination
number. This coordination mode produced a large void in crystalline
structures. Guest solvent molecules occupied the voids and stabi-
lised the crystal structures. Compounds 23 and 24 were synthesised
in DMF and NMP, respectively, and are isostructures.
3.3. pcu net assembled with trinuclear metal centres
The following five compounds contain trinuclear metal centres
with six coordination points, and their structure topology is pcu
(Fig. 3): [Mn3(2,6-ndc)3(dmf)4]n 16, [Mn3(2,6-ndc)3(dma)4]n 17,
[Mn3(2,6-ndc)3(nmp)4]n 18, [Mn3(bpdc)3(dma)4]n 19, and
[Co3(2,6-ndc)3(dma)4]n 20. These compounds were assembled
using relatively long ligands (H2(2,6-ndc) 9.15 Å and H2bpdc
11.22 Å). Although the ligands are long, the structures contain no
voids for guest molecules. In the linear M3 metal centre, each metal
ion at the end was connected to two organic solvent molecules as
auxiliary ligands that occupy a potential vacancy in the crystal
structure. Although the compounds 16, 17 and 18 were synthes-
ised in DMF, DMA and NMP, respectively, their metal centre types
and structure topologies were the same.
3.5. 1D structure assembled with a mononuclear metal centre
In this group, there is only one compound, {[Ni(2,6-ndc)(H2-
O)4]Á2NMPÁ2H2O}n25, which was assembled with a Ni2+ ion and
bridging ligand H2(2,6-ndc) to form a 1D structure (Fig. 5a). Com-
pared with the other first-row transition metal elements, nickel
analogues are often difficult to generate or have not been reported.
Furthermore, the Ni2+ ion is often coordinated with more than one
water molecule, which prevents the Ni2+ ion from connecting to
more bridging ligands and formation of high dimensional struc-
tures. The coordination behaviour of the Ni2+ ion may be due to
the small ion radius.
Fig. 4. Trinuclear metal centres appear in 21 (a, CÀH hydrogen atom omitted), 22 (b), and the hxl net for 21–24 (c).

S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
61
Fig. 5. 1D structure for 25 (a) and 26 (b); coordination mode of the metal centre (c) and the hcb net for 27 (d).
Table 3
Summary of the structural features for coordination polymers 1–25 and metal ions/ligands.
Ligand
Metal centre (SBU)
Topology
Mn2+
6
Co2+
1
Ni2+
Cu2+
3
Zn2+
Short–medium
Rod-shaped
pcu
sql
pcu
hxl
1D
1
3
M2
M3
M3
M
Medium–long
Long
4
1
1
1
2
1
3.6. Two structures assembled using a protonated or tritopic ligand
low dimensional structures. This was also observed in coordination
polymer assemblies that were hydrothermally synthesised [44].
The size and coordination and assembly behaviours for Co2+ lie be-
[Mn(Haip)2(H2O)2]n26 and [Zn(aip)(dma)]n27 are different from
the compounds discussed above. In 26, the amino group is proton-
ated; thus, the Mn2+:Haip ratio should be 1:2, and Mn2+ ions were
bridged by pairs of Haip ligands to form a 1D structure (Fig. 5b). In
27, aip is a building block with three connections and amino
groups coordinated with a Zn2+ ion; each Zn2+ ion also coordinated
with three aip bridging ligands and one DMA (Fig. 5c). The result is
an hcb net (Fig. 5d).
tween Mn2+ and Ni2+
.
The different synthetic conditions in this research, such as tem-
perature, solvent and solvent mixture ratio, did not significantly
influence the assembly.
4. Conclusion
The relationships between the coordination polymers’ struc-
tural features (metal centre and topology) and metal ions or li-
gands are summarised in Table 3.
The metal ion used is the most important factor that influences
coordination polymer assembly. It determines the type of metal
centre, interaction between metal ions, and topology for the entire
structure. A carefully selected metal ion with the proper ion radius,
coordination number and electron configuration is vital for design
and synthesis of inorganic-organic hybrid crystalline materials.
The organic ligand is also important, but it is the second most
important influential factor in this context. Changes in ligand
shape and properties, including bend, length, and substituent,
can change the distances between the metal centres or SBUs, the
structure void, or level of guest solvent molecules in the structure;
however, such changes do not influence the inorganic portion of
the compounds or net topology. This is the foundation for many
design principles, such as the ‘‘expansion’’ strategy for porous
MOFs [45].
The data clearly show that Mn2+ tends to form rod-shaped SBUs
and densely packed structures, which are generated from the large
size and high coordination number of the Mn2+ ion. Given the po-
tential for more bridging and auxiliary ligands connected to the
metal centre, Mn2+ is a poor candidate for porous structures.
In contrast, Cu2+ and Zn2+ tend to form discrete metal centres
with a limited number of metal ions, especially the M2 metal cen-
tre (paddle-wheel-shaped). The M2 metal centre with four coordi-
nation points typically forms a sql topology when linked by linear
bridging ligands. Solvent molecules are often included in the crys-
tal structure voids.
It is difficult to react Ni2+ with benzene dicarboxylic acid to
yield coordination polymers, and Ni2+ PCPs are rare [43]. The pres-
ence of many coordinated water molecules on the Ni2+ ion pre-
vents it from connecting to more bridging ligands and produces
Synthetic conditions are not key factors in this research. Three
small groups of compounds synthesised in different solvents, for
example, 2–4, 16–18, 23 and 24, show that solvents also act as

62
S.-Y. Yang et al. / Inorganica Chimica Acta 403 (2013) 53–62
[17] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353.
[18] U. Schubert, Chem. Soc. Rev. 40 (2011) 575.
[19] N.L. Rosi, J. Kim, M. Eddaoudi, B. Chen, M. O’Keeffe, O.M. Yaghi, J. Am. Chem.
Soc. 127 (2005) 1504.
the auxiliary ligands but do not influence the assemblies. Temper-
ature also did not influence the structural features in this work.
[20] S.M. Cohen, Chem. Rev. 112 (2012) 970.
Acknowledgement
[21] K.K. Tanabe, S.M. Cohen, Chem. Soc. Rev. 40 (2011) 498.
[22] F.A.A. Paz, J. Klinowski, S.M.F. Vilela, J.P.C. Tomé, J.A.S. Cavaleiro, J. Rocha,
Chem. Soc. Rev. 41 (2012) 1088.
[23] D. Zhao, D.J. Timmons, D. Yuan, H.-C. Zhou, Acc. Chem. Res. 44 (2011) 123.
[24] D.-S. Zhou, F.-K. Wang, S.-Y. Yang, Z.-X. Xie, R.-B. Huang, CrystEngComm 11
(2009) 2548.
We thank the NNSFC (Grant Nos. 20471049 and 21071117) for
supporting the research. Thanks also to Mr. Chao Du, Mr. Dong-
Sheng Zhou and Ms. Fei-Fei Lan.
[25] H.L. Li, M. Eddaoudi, M. O’Keeffe, O.M. Yaghi, Nature 402 (1999) 276.
[26] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, Chem. Commun. (2002) 472.
[27] S.-Y. Yang, L.-S. Long, Y.-B. Jiang, R.-B. Huang, L.-S. Zheng, Chem. Mater. 14
(2002) 3229.
[28] L.-S. Long, CrystEngComm 12 (2010) 1354.
[29] H.-Y. Zang, Y.-Q. Lan, G.-S. Yang, X.-L. Wang, K.-Z. Shao, G.-J. Xu, Z.-M. Su,
CrystEngComm 12 (2010) 434.
[30] P. Kanoo, K.L. Gurunatha, T.K. Maji, Cryst. Growth Des. 9 (2009) 4147.
[31] F.-K. Wang, X.-X. Song, S.-Y. Yang, R.-B. Huang, L.-S. Zheng, Inorg. Chem.
Commun. 10 (2007) 1198.
[32] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, S.W. Ng, Inorg. Chim. Acta 358
(2005) 1882.
Appendix A. Supplementary material
CCDC 897845–897871 contain the supplementary crystallo-
graphic data for 1–27. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at http://
dx.doi.org/10.1016/j.ica.2013.03.042.
[33] P.M. Forster, A.R. Burbank, C. Livage, G. Férey, A.K. Cheetham, Chem. Commun.
(2004) 368.
[34] C.-P. Li, M. Du, Chem. Commun. (2011) 5958.
[35] R. Custelcean, Chem. Soc. Rev. 39 (2010) 3675.
[36] M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O.M. Yaghi,
Science 295 (2002) 469.
[37] J.L.C. Rowsell, O.M. Yaghi, Microporous Mesoporous Mater. 73 (2004) 3.
[38] H.-M. Li, S.-Y. Yang, J.-W. Wang, L.-S. Long, R.-B. Huang, L.-S. Zheng, Polyhedron
29 (2010) 2851.
[39] H.-B. Yuan, S.-Y. Yang, Z.-X. Xie, R.-B. Huang, S.R. Batten, Inorg. Chem.
Commun. 12 (2009) 755.
[40] F.-K. Wang, S.-Y. Yang, R.-B. Huang, L.-S. Zheng, S.R. Batten, CrystEngComm 10
(2008) 1211.
[41] S.-Y. Yang, L.-S. Long, R.-B. Huang, L.-S. Zheng, S.W. Ng, Acta Crystallogr., Sect. E
61 (2005) m1671.
[42] O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Phys. Chem. Chem. Phys. 9
(2007) 1035.
[43] P. Maniam, N. Stock, Inorg. Chem. 50 (2011) 5085.
[44] R.-F. Jin, S.-Y. Yang, H.-M. Li, L.-S. Long, R.-B. Huang, L.-S. Zheng,
CrystEngComm 14 (2012) 1301.
References
[1] M. O’Keeffe, O.M. Yaghi, Chem. Rev. 112 (2012) 675.
[2] C.B. Aakeröy, N.R. Champness, C. Janiak, CrystEngComm 12 (2010) 22.
[3] J.J. Perry IV, J.A. Perman, M.J. Zaworotko, Chem. Soc. Rev. 38 (2009) 1400.
[4] P. Dechambenoit, J.R. Long, Chem. Soc. Rev. 40 (2011) 3249.
[5] A. Corma, H. García, F.X.L. Xamena, Chem. Rev. 110 (2010) 4606.
[6] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P.V. Duyne, J.T. Hupp, Chem.
Rev. 112 (2012) 1105.
[7] C. Wang, T. Zhang, W. Lin, Chem. Rev. 112 (2012) 1084.
[8] G. Givaja, P. Amo-Ochoa, C.J. Gómez-García, F. Zamora, Chem. Soc. Rev. 41
(2012) 115.
[9] M.D. Allendorf, C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Chem. Soc. Rev. 38 (2009)
1330.
[10] A.U. Czaja, N. Trukhan, U. Müller, Chem. Soc. Rev. 38 (2009) 1284.
[11] N. Stock, S. Biswas, Chem. Rev. 112 (2012) 933.
[12] R.B. Getman, Y.-S. Bae, C.E. Wilmer, R.Q. Snurr, Chem. Rev. 112 (2012) 703.
[13] A. Dhakshinamoorthy, H. Garcia, Chem. Soc. Rev. 41 (2012) 5262.
[14] B. Chen, S. Xiang, G. Qian, Acc. Chem. Res. 43 (2010) 1115.
[15] M.P. Suh, H.J. Park, T.K. Prasad, D.-W. Lim, Chem. Rev. 112 (2012) 782.
[16] T. Uemura, N. Yanai, S. Kitagawa, Chem. Soc. Rev. 38 (2009) 1228.
[45] M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reinke, M. O’Keeffe, O.M. Yaghi,
Acc. Chem. Res. 34 (2001) 319.