Development of a porous bifunctional metal-organic framework for cyanosilylation of aldehydes and ablation of human laryngocarcinoma cells

Article abstract of DOI:10.1080/10426507.2018.1550643

This work presents the synthesis and properties study of a new dual-functional metal-organic framework (MOF) with the chemical formula of [Cu₇(nbpt)₄(H₂O)₂(OH)₄]·(DMF)₅(H₂O) (1,

Full text of DOI:10.1080/10426507.2018.1550643

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Development of a porous bifunctional metal-
organic framework for cyanosilylation
of aldehydes and ablation of human
laryngocarcinoma cells
Jie Zhou, Jun-Wei Xiong & Yu Zhao
To cite this article: Jie Zhou, Jun-Wei Xiong & Yu Zhao (2018): Development of a porous
bifunctional metal-organic framework for cyanosilylation of aldehydes and ablation of human
laryngocarcinoma cells, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2018.1550643
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1550643
Development of a porous bifunctional metal-organic framework for
cyanosilylation of aldehydes and ablation of human laryngocarcinoma cells
Jie Zhoua, Jun-Wei Xiongb, and Yu Zhaoc
b
aENT Department, Chongqing Qianjiang National Hospital, Chongqing, China; ENT Department, Chongqing General Hospital, Chongqing,
c
China; ENT Department, Fuling Center Hospital of Chongqing City, Chongqing, China
ABSTRACT
ARTICLE HISTORY
Received 20 June 2018
Accepted 17 November 2018
This work presents the synthesis and properties study of a new dual-functional metal-organic
framework (MOF) with the chemical formula of [Cu7(nbpt)4(H2O)2(OH)4]ꢀ(DMF)5(H2O) (1,
DMF ¼ N,N-dimethylformamide) based on a Y-shaped tricarboxylic ligand 30-nitro-[1,10-biphenyl]-
3,40,5-tricarboxylic acid (H3nbpt). This compound has been characterized by elemental analysis, FT-
IR spectroscopy, thermogravimetric and X-ray diffraction analyses. The crystal structure analysis
reveals that compound 1 is composed of a {Cu7(OH)4}10þ secondary building unit that is con-
nected by the nbpt3- ligands into a 3D framework with 1D nanosized channels running along the
b axis. Compound 1 was investigated for its heterogeneous catalytic activities towards the cyano-
silylation of aldehydes under solvent-free conditions, which shows that it catalytic activities could
be greatly enhanced by removing the coordinated solvents, indicating that the exposed open
metal sites in the activated 1 (1a) is beneficial to the cyanosilylation reaction. In addition, the anti-
cancer activates of 1 has been evaluated on four human laryngocarcinoma cells (TU212, Hep-2,
M4E and TU686) via the MTT assay.
KEYWORDS
Metal-organic framework;
nitro-tricarboxylic acid
ligand; solvothermal
reaction; cyanosilylation
reaction; anticancer activity
GRAPHICAL ABSTRACT
Introduction
inherent stability and ease of recovery, allowing for more effi-
cient separation and recycling. Hence, the development of
efficient heterogeneous catalysts for cyanosilylation of car-
bonyl compounds with TMSCN is a very important subject in
current research, and several efficient catalysts have been
developed so far. However, from the point of green chemistry,
it is a pressing challenge to seek an efficient heterogeneous
catalyst under environmentally friendly conditions.[5, 6] Thus
there is a great need for the developing efficient and environ-
mental friendly catalysts for cyanohydrin reaction.
The cyanosilylation of carbonyl compounds with trimethyl-
silyl cyanide (TMSCN), as a direct and efficient method for
the formation of C–C bonds in organic synthesis, has recently
received tremendous attention as cyanohydrins are key inter-
mediates in the synthesis of biologically important com-
pounds such as a-hydroxy acids, a-hydroxyl ketones and
a-amino acids.[1–3] The majority of these studies have revealed
that the reaction is catalyzed by homogeneous catalysts i.e.
metallic Lewis acids/bases, inorganic solid acids/bases, and
nonmetallic organic molecules, whose performance is still
limited with a large difficulty in separation and recyclable
use.[4] From an economic point of view, the strong industrial
Metal organic frameworks (MOFs) are exciting hybrid
materials with a plethora of potential applications including
gas storage, gas separation, catalysis, and drug delivery.[7–12]
They are crystalline nanoporous materials comprised of
preference for heterogeneous catalysts arises from their ordered networks formed from organic electron donor
ꢁ
CONTACT Yu Zhao
yu_zhao666@126.com
ENT Department, Fuling Center Hospital of Chongqing City, Chongqing, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
ß 2018 Taylor & Francis Group, LLC

2
J. ZHOU ET AL.
Figure 1. (a) View of the coordination environments of Cu(II) ions in 1 (b) The coordination modes of the organic ligand. (c) The 3D framework of compound 1
with the 1D nano-sized channels. (d) The schematic representation of the simplified topological network for compound 1.
linkers and metal cations or clusters, whose pore size and compounds of different metals other than Pt are entering
surroundings could be designed and controlled via elabor- clinical studies. Recent studies have shown that the Cu(II)-
ately selection of the building blocks. In particular, MOFs based coordination compounds show promising results.[21]
have been widely studied as size- and shape-selective hetero- For instance, Guo and co-works have successfully prepared
geneous catalysts due to their large pore size, high BET sur- a lanthanide MOF which shows high cytotoxicity toward the
face areas and diverse functionalizations.[13–15] For the human lung cancer cell A549[22]; Mukherjee and coworkers
optimal catalytic activity, two types of strategies are used: (i) have reported that the have studied the cytotoxic activity of
introduction of organic groups to provide guest-accessible the nanostructured MOFs on human colorectal carcinoma
functional organic sites and (ii) formation of coordinatively cell lines, and found that some of them could significantly
unsaturated metal sites. If the metal is coordinatively satu- lead to the cancer cell death.[23] Although there are many
rated, the organic moiety incorporating functionality for MOFs have been shown to be capable of catalyzing cyanosi-
non-covalent interactions can bind the reactant(s) through lylation or inhibiting human cancer cells, none of them can
H-bonding, p–p stacking, as examples., leading to their acti- achieve the above mentioned two functions simultaneously.
vation. In another case, metal ions bound to one or more In this study, a new dual-functional metal-organic frame-
solvent molecules can be heated to remove the solvent mole- work with the chemical formula of [Cu7(nbpt)4(H2O)2
cules exposing the metal ion to the reactants that can dir- (OH)4]ꢀ(DMF)5(H2O) (1, DMF ¼ N,N-dimethylformamide)
ectly bind the metal ion and hence can be activated. Since based on a Y-shaped tricarboxylic ligand 30-nitro-[1,10-
the first discovery by Fujita et al, many papers concerning biphenyl]-3,40,5-tricarboxylic acid (H3nbpt) has been
the MOFs-based catalysts for cyanosilylation have been achieved under solvothermal conditions. This compound
reported.[16–18] For instance, Kaskel and coworkers have has been characterized by elemental analysis, FT-IR spec-
revealed that MIL-101-Cr is an efficient catalyst for the cya- troscopy, thermogravimetric and X-ray diffraction analyses.
nosilylation of benzaldehyde after the removal of the coordi- The crystal structure analysis reveals that compound 1 is
nated water molecules.[17] On the other hand, coordination composed of a {Cu7(OH)4}10þ secondary building unit that
chemistry has a great potential to offer a wide variety of is connected by the nbpt3ꢂ ligands into a 3D framework
compounds with different geometry, redox reactivity and a with 1D nanosized channels running along the b axis.
diversity of mechanisms related to DNA binding, some of Compound 1 was investigated for its heterogeneous catalytic
them unique to metals.[19] The usefulness of coordination activities towards the cyanosilylation of aldehydes under
metal complexes in cancer chemotherapy has been demon- solvent-free conditions, which shows that it catalytic activ-
strated by Cisplatin and other platinum coordination com- ities could be greatly enhanced by removing the coordinated
pounds which are amongst the most successfully used solvents, indicating that the exposed open metal sites of in
anticancer drugs.[20] As a result of an intense and continued the activated 1 (1a) is beneficial to the cyanosilylation reac-
research on coordination complexes with antitumor activity, tion. In addition, the anticancer activates of 1 and 1a has

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
except that the four O atoms come from three carboxylic O
atoms. The Cu(II)-O bond distances range from 1.920(2) Å
to 2.197(3) Å, which locate in the normal range among the
Cu(II)-O bond distances of the reported Cu(II)-carboxylate
MOFs in the literature.[24–26] Cu1, Cu3, Cu4 and their sym-
metry-related ones are held together via four l3-OH groups
and the Cu2 atom to give rise to the {Cu7(OH)4}10þ cluster,
which serves as the secondary building unit in the formation
of the network of 1. In the {Cu7(OH)4}10þ cluster, As for
the nbpt3- ligands, they reveal the same five-connected
mode but with their carboxylic groups showing different
coordination modes which are shown in the Figure 1b. The
connection of the {Cu7(OH)4}10þ cluster with the nbpt3-
ligands generates a porous three-dimensional framework
with 1D rhombus channels running along the b axis. The
window size for the 1D channel is 10.4ꢃ;8.2 Å2, which fills
with water occupied open metal sites and the uncoordinated
nitro-groups (Figure 1c). The l3-OH group forms H-bond-
ing interaction with the carboxylic O atom and the donor-
acceptor distance is 2.165 Å (O1-H1ꢀꢀꢀO13, Figure S1). With
omitting the coordinated water molecules, PLATON analysis
revealed that the 3D framework was composed of voids of
978 Å3, which represent 40.1% per unit cell volume. TOPOS
software was used to simplify this framework. In this 3D
framework, the {Cu7(OH)4}10þ cluster could be treated as
12-connected node, and the nbpt3- ligands could be consid-
ered as 3-connected nodes, so the whole framework of 1
could be viewed as a llj-type 3,12-connected net with a
point symbol of {4ꢄ20.6ꢄ28.8ꢄ18}{4ꢄ3}4 (Figure 1d).
Scheme 1. The cyanosilylation reaction in the presence of selected complexes.
Table 1. The results for the catalytic cyanosilylation of aldehydes in the pres-
ence of 1 and 1a.
Aldehyde
blanka
1 conversiona
1a conversiona
15.45%
55.13%
99.32%
16.89%
11.56%
9.12%
67.57%
53.15%
44.85%
99.82%
99.32%
96.43%
6.82%
18.34%
24.25%
aConversion determined by GC, and the NMR spectra for the products are
shown in the Figure S4.
been evaluated on four human laryngocarcinoma cells
(TU212, Hep-2, M4E and TU686) via the MTT assay.
PXRD and thermogravimetric analysis for compound 1
Results and discussion
The simulated and experimental PXRD patterns of 1 are
shown in Figure S 2a (Supplemental Materials). A good
match between the experimental and theoretical PXRD pat-
terns was observed, which is the evidence for the phase pur-
ity and structural consistency of the bulky products for
crystalline 1. In addition, the thermal stability of 1 was also
analyzed on crystalline samples from 30-800 ꢄC under N2
atmosphere (Figure S2b). The TGA curve of 1 shows that it
has a weight loss of 19.4% in the temperature range of
30–210 ꢄC, which is consistent with the removal of two
coordinated H2O, five free DMF molecules and one lattice
H2O molecules (calcd 19.6%). After taking off the solvent
molecules, the framework of 1 can be stable up to 250 ꢄC,
after which the framework began to collapse. The permanent
porosity of the activated 1 (1a) was unambiguously estab-
lished by its N2 sorption isotherm at 77 K. The activated
sample 1a was prepared by exchanging in dichloromethane
overnight and then activated under dynamic vacuum at
110 ꢄC for 6 h. The framework integrality has been charac-
terized by PXRD measurement, which shows a good match
between the PXRD patterns of 1 and 1a, indicating that the
framework was maintained because the broadened peaks
positions remained (Figure S 2a). The full activation of the
framework has been confirmed via the TGA curve, which
reveals that there is no obvious weight loss before the tem-
Crystal structure of compound 1
Compound
1
was synthesized by reaction of
Cu(NO3)2ꢀ6H2O and H3nbpt in a mixed solvent of DMF
and H2O in the presence of HNO3. It should be noted that
only white deposition was obtained without the presence of
HNO3, indicating the HNO3 might be a pH regulator which
is very important for the crystallization. It has been shown
that the addition of HNO3 plays a vital role in the formation
of the MOF-505 series. Single crystal X-ray diffraction ana-
lysis revealed that compound 1 crystallizes in triclinic P-1
space group and features a three-dimensional framework
based on the {Cu7(OH)4}10þ secondary building unit. The
asymmetric unit of 1 is composed of four crystallographic-
ally independent Cu(II) ions, two nbpt3ꢂ ligand, two l3-OH
groups and two coordinated water molecules. As shown in
Figure 1a, the Cu1 atom is four-coordinated by four O
atoms from three carboxylic O atoms and one l3-OH group,
forming a distorted tetrahedral coordination environment;
The distorted octahedral coordination surrounding of Cu2 is
finished by four l3-OH groups and two carboxylic O atoms;
Cu3 shows a similar coordination surrounding with Cu2
expect the six O atoms come from three carboxylic O atoms,
two l3-OH groups and one coordinated water; Cu4 atom
show the similar four-coordinated surrounding with Cu1 perature of 251 ꢄC. The N2 sorption isotherms of the

4
J. ZHOU ET AL.
Scheme 2. Proposed mechanism for the cyanosilylation reaction of carbonyl compounds catalyzed by 1a.
activated sample at 77 K revealed a completely reversible
type-I behavior, a characteristic of microporous materials
(Figure S 3). Based on the N2 adsorption data, the
Brunauer–Emmett–Teller (BET) surface area and Langmuir
Table 2. Growth inhibitory effects on TU212, Hep-2, M4E and TU686 cells.
IC50 (lM)
Compounds
Ligand
TU212
Hep-2
M4E
TU686
>100
>100
25
>100
>100
25
>100
>100
35
>100
>100
40
surface area of 1a were calculated to be 821 m2gꢂ1 and Cu(NO3)2ꢀ3H2O
953 m2gꢂ1, respectively with a corresponding pore volume
1
Vinorebine
35
25
30
45
of 0.36 cm3 gꢂ1. The pore size distribution centers around
8.36 Å (as determined using the Horvath–Kawazoe method),
which are basically similar to the results from the single-
crystal X-ray diffraction study (Figure S 3 inset).
sites.[27–29] It is noteworthy that the catalytic activity of 1a is
higher than that of compound 1. This can be attributed to
more open metal sites of Cu2þ in 1a, which can effective
enhance the catalytic activity. The stability of compound 1a
was examined after the catalytic study by PXRD, which
reveals the same PXRD pattern as the as-synthesized phase,
indicating that the compound was stable (Figure S 2a). In
addition, the parallel experiment without a catalyst was also
done, and the conversion of benzaldehyde and its derivative
is below 20%. These results indicate that compound 1a can
be used as an efficient catalyst for the cyanosilylation reac-
tion under mild conditions. To further explore whether the
activation of the carbonyl species occurs inside the pores or
on the surface of the solid catalyst, substrates of increasing
dimensions were tested, a significant size-selectivity effect is
observed with catalyst, when the substrate was 1-naphthalde-
hyde with dimensions 9.7 ꢃ 8.4 Å2, the conversion was
reduced to 24.25% for 1a.
Catalytic activity
As is well-known, the cyanosilylation reaction is an effective
chemical method to obtain cyanohydrins. Complex 1 pos-
sesses 1D open channels and unsaturated metal sites after
the removal of coordinated water molecules, indicating its
potential properties as a heterogeneous catalyst. Therefore,
the cyanosilylation of aromatic aldehydes with different sub-
stituent groups were selected to test the catalytic ability of
1a (Scheme 1). Under N2 atmosphere, a solution of aldehyde
(0.5 mmol) and cyanotrimethylsilane (1 mmol) was added to
activated the samples of complex 1a (10 mg) at room tem-
perature. After the reaction was stirred for 4 h, the mixtures
were separated by a centrifuge. The liquid part was utilized
to analyze the conversions by gas chromatograph-mass spec-
trometry and the results are summarized in Table 1. Using
1a as the catalyst, the conversion of benzaldehyde and its
derivatives can reach above 97–99% under the given condi-
tions, while the yields are only about 45-67% for 1 under
the same conditions. The cyanosilylation yield of 1a is much
higher than that of many MOFs used for the cyanosilylation
study under similar conditions, which might be ascribed to
Based on the experimental results and previously reported
results, a plausible reaction mechanism is proposed to illus-
trate the process of 1a catalyzed cyanosilylation reac-
tion.[27–29] The labile water molecules in the channels of
compound 1 were removed by heating to expose the unsat-
urated metal sites previously. The aldehydes were activated
by the coordinatively unsaturated Cu centers to react with
its large inner spaces and high density of exposed metal TMSCN (Scheme 2). The products were replaced by

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Table 3. Crystal data and structure refinements for 1.
Elemental analyses (C, H and N) were determined with
Perkin-Elmer 240 elemental analyzer. Thermogravimetric
analysis was carried out on a NETSCHZ STA–449C thermo-
analyzer with a heating rate of 10 ꢄC/min under a nitrogen
atmosphere. Infrared spectra were measured on a Nicolet
Magna 750 FT-IR spectrometer in the range of
400–4000 cmꢂ1 using the KBr pellets. Powder X-ray diffrac-
tion (PXRD) analyses were recorded on a Bruker AXS D8
advanced automated diffractometer with Cu-Ka radiation.
Empirical formula
C60H32Cu7N4O38
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
1861.67
293(2)
triclinic
P-1
11.8251(4)
13.6676(4)
17.527(3)
70.019(4)
c/Å
a/ꢄ
b/ꢄ
90.137(4)
68.262(3)
2445.8(4)
c/ꢄ
Volume/Å3
Z
1
qcalcg/cm3
1.264
1.565
927.0
Synthesis of compound
[Cu7(nbpt)4(H2O)2(OH)4]ꢀ(DMF)5(H2O) (1)
l/mm-1
F(000)
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I> ¼2r (I)]
Final R indexes [all data]
Largest diff. peak/hole/e Åꢂ3 CCDC
43112
A mixture of Cu(NO3)2ꢀ3H2O (0.2 mmol, 0.048 g), H3nbpt
(0.1 mmol, 0.033 g), DMF (4 mL), H2O (1 mL) and three
drops of concentrated nitric acid was sealed in a 20 mL glass
vial, and then the mixture was heated to 90 ꢄC and kept at
that temperature for 3 d. After cooling slowly to room tem-
perature, colorless block crystals were isolated with 45%
yield based on H3nbpt ligand. Anal. Calcd. (%) for 1
C75H69Cu7N9O44: C, 40.12; H, 3.10; N, 5.61. Found: C,
39.91; N, 5.42; H, 3.14. IR (KBr, cmꢂ1): 3426(w), 2993(w),
1680(s), 1651(s), 1563(s), 1477(s), 1381(s), 1274(s), 1221(s),
1108(m), 1061(w), 942(w), 845(s), 782(m), 716(w), 672(m).
8583 [Rint ¼ 0.1379, Rsigma ¼ 0.1141]
8583/102/562
1.031
R1 ¼ 0.0571, wR2 ¼ 0.1305
R1 ¼ 0.1076, wR2 ¼ 0.1518
0.64/ꢂ0.67 1878531
aldehydes, and the catalysts were continued to activate the
aldehydes in the next catalytic cycle.
Antitumor activity
The cytotoxicity of the organic ligand H3nbpt and 1 and the
reference drug vinorebine were evaluated by MTT (3-(4,5-
X-ray crystallography
Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
bromide)
Single crystal X-ray crystal data of 1 was collected on a com-
puter–controlled Oxford Xcalibu E diffractometer with
graphite–monochromated Mo–Ka radiation (k ¼ 0.71073 Å)
at room temperature. Absorption corrections were applied
using SADABS. The structures were solved by direct meth-
ods by the SHELXS-2014 package and refined by full–matrix
least–square methods on F2 by using the SHELXL-2014/6.
All non–hydrogen atoms were refined anisotropically and all
assay method against four human laryngocarcinoma cells
(TU212, Hep-2, M4E and TU686). Compounds were dis-
solved in DMSO and blank samples containing the same
volume of DMSO were taken as controls to identify the
activity of solvent in this cytotoxicity experiment. The anti-
cancer drug Vinorebine was used as a positive control to
assess the cytotoxicity of the test compounds. The results
were analyzed by means of cell inhibition expressed as IC50
values and they are shown in Table 2. The organic ligand
was inactive against all of these cell lines (IC50 > 100 lM).
At this concentration, it should exert high cytotoxicity
against these cells, so we concluded that it exerted no inhab-
itation selectivity towards these cell lines. However, after the
tumor cells were incubated in the presence of compound 1
for 72 h, the IC50 value ranged from 25 to 40 lM, some of
which were even lower than those of vinorebine, indicating
that compound 1 exhibited antitumor activity against all of
these cell lines in different degrees. It is to be noted that the
ligand and Cu(NO3)2 did not show any significant activity
on all the four cancer cells, which confirmed that the chela-
tion of the ligand with the Cu(II) ion is the only responsible
factor for the observed cytotoxic properties of the
new compounds.
H
atoms were generated in their ideal locations.
Crystallographic data and refinement details are summarized
in Table 3, and the selected bond distances and angles for
compound 1 are given in Table S 1 (Supplemental
Materials). The H-bond details are listed in the Table S2.
Antitumor activity
The anticancer activity of compound 1 was evaluated against
four human laryngocarcinoma cells (TU212, Hep-2, M4E
and TU686) via the MTT assay. The two cancer cells were
seeded in a 96-well plate in which cells density is 5000 cells
per test well, and cultured overnight at 37 ꢄC in a 5% CO2
incubator. The tested compounds were dispersed in DMSO
and diluted in the respective medium containing 1% fetal
bovine serum (FBS). After 24 h, the medium was replaced
with the respective medium with 1% FBS containing the
compound 1 at various concentrations. After 48 h, 10 lL of
MTT (5 mg/mL) in phosphate buffered saline (PBS) was
added to each well and incubated at 37 ꢄC for 4 h. The
Experimental
Materials and instrumentation
All reagents and solvents employed in this work were com- medium with MTT was then flicked off, and the formed for-
mercially available and used without further purification. mazan crystals were dissolved in 100 lL of DMSO. The

6
J. ZHOU ET AL.
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Conclusion
In summary, a new porous Cu(II)-organic framework based
on a Y-shaped tricarboxylic ligand 30-nitro-[1,10-biphenyl]-
3,40,5-tricarboxylic acid (H3nbpt) has been synthesized under
solvothermal condition. Crystal structure analysis reveals
that compound 1 is composed of {Cu7(OH)4}10þ secondary
building unit that connected by the nbpt3ꢂ ligands into a
3D framework with 1D nanosized channels running along
the b axis. The activated 1 could be used as a dual-func-
tional material for effective cyanosilylation of aldehydes
under solvent-free conditions and inhibition of human can-
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