A Metal-Organic Framework to CuO Nanospheres of Uniform Morphology for the Synthesis of α-Aminonitriles under Solvent-Free Condition along with Crystal Structure of the Framework

Article abstract of DOI:10.1021/acs.cgd.7b01085

Herein, we have reported the synthesis, crystal structure, thermogravimetric property, and photoluminescence activity of a new Cu-based metal organic framework (MOF): {[Cu₂(2,5-pdc)₂(ald-4)(H₂O)₂]·3H₂

Full text of DOI:10.1021/acs.cgd.7b01085

Subscriber access provided by Gothenburg University Library
Article
A MOF to CuO Nanospheres of Uniform Morphology
for Synthesis of #-Aminonitriles under Solvent-Free
Conditions along with Crystal Structure of the MOF
Soumen Singha, Arijit Saha, Somen Goswami, Sanjoy Kumar Dey,
Soumen Payra, Subhash Banerjee, Sanjay Kumar, and Rajat Saha
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01085 • Publication Date (Web): 09 Nov 2017
Downloaded from http://pubs.acs.org on November 15, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155
Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
MOF derived CuOꢀNPs for the green synthesis of αꢀaminonitriles via Strecker reaction in solid state.
92x38mm (96 x 96 DPI)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 2 of 42
1
2
3
4
5
6
7
8
9
A MOF to CuO Nanospheres of Uniform Morphology for Synthesis of α-
Aminonitriles under Solvent-Free Conditions along with Crystal Structure of
the MOF
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Soumen Singha,† Arijit Saha,‡ Somen Goswami,† Sanjoy Kumar Dey,† Soumen Payra,‡ Subhash
Banerjee,*,‡ Sanjay Kumar,*,† and Rajat Saha*,§
†Department of Physics, Jadavpur University, Jadavpur, Kolkata-700032, India
‡Department of Chemistry, Guru Ghasidas Vishwavidyalaya, Bilaspur, C.G.-495009, India
§Department of Chemistry, Kazi Nazrul University, Asansol, WB-713340, India
ABSTRACT:
Herein, we have reported the synthesis, crystal structure, thermogravimetric property and
photoluminescence activity of a new Cu-based metal organic framework (MOF): {[Cu2(2,5-
pdc)2(ald-4)(H2O)2]•3H2O,MeOH}n (where 2,5-pdc = 2,5-pyridine-dicarboxylate, ald-4 =
aldrithiol-4) along with catalytic activity of CuO nanopaticles (Cu-NPs) derived from the MOF
for green synthesis of organic molecules having biological relevance. The regular arrangement of
metal centers and presence of oxygen and carbon in metal-organic frameworks (MOF) enable us
to utilize them as template/precursor for synthesis of monodispersed metal-oxide and metal-
carbide nanoparticles having high surface area with well defined and uniform morphology. The
MOF derived oxide nanoparticles generally exhibit improved catalytic activities and product
selectivity and significantly reduce the chemical waste production. The structural analysis has
revealed that in the complex under investigation, the 2,5-pdc bridges the Cu(II) centers to form
both left handed and right handed infinite 1D helical chains and the complex is a 3D achiral
1
ACS Paragon Plus Environment

Page 3 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
framework composed of neighboring 2D sheets of opposite chirality. The thermogravimetric
study suggests that the framework is stable up to 500 ºC. Single phase, highly crystalline, nearly
monodispersed and spherical CuO-NPs having average paticle size ~27.9 nm has been
synthesized by heating the framework at 650 ºC for 4 hrs. The CuO-NPs are characterized by
using powder x-ray diffraction, high resolution transmission electron microscopic, selected area
electron diffraction, energy dispersive x-ray spectroscopic and dynamic light scattering
techniques. Further, the crystal structure of the CuO-NPs has also been illustrated by Rietveld
refinement of powder pattern. Finally, the as-synthesized CuO-NPs were employed in the one-
pot three component Strecker synthesis of α-aminonitriles via the condensation of benzaldehyde,
aniline and trimethylsilyl cyanide under solvent-free condition. This work will be helpful in
utilizing the MOF derived oxide nanoparticle for development of sustainable chemical processes.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
KEYWORDS
1) 2D coordination polymer, 2) Helicity and Chirality, 3) MOF-derived CuO-nanoparticles, 4)
Strecker synthesis and 5) Solvent free catalytic reaction
2
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 42
1
2
3
4
INTRODUCTION
5
6
7
8
9
Over past two decades, metal organic frameworks (MOFs) have attracted substantial
attention due to their aesthetically pleasing architecture, topological diversity, high porosity with
large surface area and remarkable functional properties.1-4 MOFs are considered as excellent
candidates for application in gas and solvent adsorption, storage and separation, catalysis,
sensing/recognition, magnetic devices, proton conduction, drug delivery, fuel storage, water
splitting, electrode material of lithium ion batteries, supercapacitor, solar cell, fuel cell and so
on.5-10 Beyond these conventional applications, owing to their structural robustness and regular
arrangement of atoms within the framework, MOFs are used as self-sacrificing
precursor/template for synthesis of easily customizable nano/micro-structured materials (porous
carbon, metals, metal oxides and carbides) with the morphological inheritance of the MOFs’
architecture.11-43
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Porosity and secondary building units (SBUs) formed by metal and coordinated atoms are
two intriguing features of MOFs. Up till now, a little attention has been paid to the use of SBUs
of the MOFs. Recently, the SBUs of the MOFs are utilized for synthesizing nanostructured
materials with diverse type of morphology, wherein, the MOF behaves as self-sacrificing
precursor in which metal centers are used as an intrinsic metal source and organic linkers act as
resource of carbon, oxygen, nitrogen etc.11-13 The porous carbon nanoparticles (NPs),14-16 multi-
walled carbon nanotubes,17 mesoporous carbon,18 nitrogen-doped porous carbon,19 metal/metal
oxide nanoparticles11-13 (nanoparticles of transition metal oxide, main group metal oxide,
lanthanide oxide etc.), core-shell nanoparticles of Au@ZnO,20 Fe3O4@Fe5C2,21 Co@Co3O4@C,22,23
and Fe2O3/N-doped carbon hollow sphere,24 double-shelled nanocages of Co3O4/NiCo2O4,25
nanocomposites of Pt/ZnO,26 LiFePO4/carbon networks,27 Fe3O4/C,28 Fe2O3/TiO2,29 and
3
ACS Paragon Plus Environment

Page 5 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
ZnFe2O4/Carbon nanotubes,30 meso-porous α-Fe2O3,31 α-Fe2O3 spindles,32 carbon coated ZnO
quantum dots33 etc. are among some of the remarkable MOF derived nanostructure. These
nanostructures have huge application potential11-13 in combating environment and energy related
problems by virtue of their wide spread applications in solar cell,11 hydrogen adsorption15, gas-
sensing,12,13 catalysis11-13,23,34,35 radionuclide separations36, extraction of heavy metals from
nuclear waste,37 supercapacitors,38 and electrode material for lithium ion batteries39-43. MOF
derived metal oxide nanoparticles (MDMO-NPs) exhibit excellent electrocatalytic,11-13,34
photocatalytic12,13,35 and common catalytic23 activity with high selectivity and very good
reusability in water splitting, removal of hazardous heavy metals/waste water treatment and
green synthesis of fine chemicals, respectively. MDMO-NPs display uniform morphology,
Lewis acidic-basic, red-ox properties and high reactivity of the surface which are the prime
requirement for having good catalytic response in general.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
To the best our knowledge, up till now no attempt has been made to synthesize metal
oxide nanoparticles (MO-NPs) from the MOF composed of 1D helical chain. However, MO-NPs
with narrow size distribution and uniform morphology can be easily produced through thermal
decomposition of 3D homochiral or achiral frameworks in open air or oxygen atmosphere
utilizing the metal oxygen bonds and uniform spatial distribution of atoms in such frameworks.
Several 3D chiral and achiral frameworks have been designed to testify the manner in which
chiral message is exchanged between adjacent chiral SBUs and then to the whole framework and
the conditions that lead to the formation of either the 3D chiral or achiral frameworks.44-52 If the
entire “chirality transfer” process from lower to higher dimension occurs in homochiral fashion,
the resultant 3D framework will be chiral. Earlier investigation on structural properties of
[M(HIDC)(H2O)(prz)0.5]n (M= Fe, Mn, Cd),44 [Co(HIDC)(H2O)(pyz)0.5]n,44 [Mn(HIDC)
4
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 42
1
2
3
4
(H2O)]n,44 [Cu2(pda)2(phen)2(H2O)2].6H2O,45 {[Zn2(L-trp)2(bpe)2(H2O)2]·2H2O·2NO3}n,46 {[Co
5
6
(L-trp)(bpe)(H2O)]·H2O·NO3}n,46
{[Co(L-trp)-(bpa)(H2O)]·H2O·NO3}n,46
(H3O)2[Cd8((S)-
7
8
9
TMTA)6(bipy)3(H2O)4]47 and (H3O)2[Cd8((R)-TMTA)6(bipy)3(H2O)4],47 where H3IDC =
imidazole-4,5-dicarboxylic acid, prz = piperazine, pyz = pyrazine, H2pda = 1,3-
phenylenediacetic acid, phen = 1,10-phenanthroline, LHtrp = L-tryptophan, bpe = 1,2-bis(4-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
pyridyl)ethylene and
bpa
=
1,2-bis(4-pyridyl)ethane, (R/S)-H3TMTA
=
(R/S)-
trimesoyltrialanine frameworks composed of 1D chiral SBUs having two linkers has helped in
understanding the mechanism of chiral crystal formation through spontaneous resolution,
however, the detail of it is yet to be fully understood.
Further, we have reported the crystal structure, supramolecular structure and physical
properties of chiral 3D [{Co(2,5-pdc)(H2O)2}H2O]n (2,5-pdc = 2,5-pyridine dicarboxylate)
framework.48 It may be noted that non-centrosymmetric 2,5-pdc is fairly rigid ligand and it
exhibits twenty three coordination modes.53,54 On the other hand, flexible aldrithiol (ald-4) can
be used as a very efficient linker for synthesizing organometallic complexes together with
carboxylate ligands.55,56 Thus, from the standpoint of rational design of new solid state structure,
synthesizing a Cu containing 3D MOF built up with 1D helical SBUs having both 2,5-pdc and
ald-4 linkers appears to be very much promising. Further, if this attempt becomes successful
then it will be interesting to explore the possibility of synthesizing CuO nanoparticles through
thermal decomposition of the obtained framework.
Given this background, preliminary aims of the present work are: (i) to synthesize a Cu-
based MOF composed of 1D chiral SBUs having both 2,5-pdc and ald-4 spacers (ii) to study the
“chirality transfer” mechanism in the framework from the structural viewpoint (iii) to
characterize the residue obtained after decomposition of the MOF for exploring the further
5
ACS Paragon Plus Environment

Page 7 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
possibility of synthesizing CuO-NPs from this MOF. Here, we have synthesized a Cu-based
MOF, {[Cu2(2,5-pdc)2(ald-4)(H2O)2].3H2O, MeOH}n, by solvent diffusion process and
characterized it by single crystal x-ray diffraction (SC-XRD) technique. The thermogravimetric
(TGA) analysis revealed that the framework decomposes at 550 ºC. The powder x-ray diffraction
(PXRD), high resolution transmission electron microscopy (HRTEM), selected area electron
diffraction (SAED), energy dispersive x-ray spectroscopy (EDS) and dynamic light scattering
(DLS) technique were employed to characterize the decomposed material obtained by sintering
the MOF at 650 ºC. It has been found that the decomposed material is CuO-NPs of uniform size
(~27.9 nm) and spherical shape. Thus, the present MOF under investigation can be used as self-
sacrificing precursor for synthesizing CuO-NPs. It is noteworthy that catalytic activity of
MDMO-NPs toward green synthesis of organic compounds with biological relevance is yet to be
explored. The main objective of the present work is to study the catalytic performance of the
MOF derived CuO-NPs in the one-pot three component synthesis of α-aminonitriles (Scheme 1)
under solvent-free condition.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 1. MOF derived CuO-NPs for the green synthesis of α-aminonitriles via Strecker
reaction under solvent free condition
6
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 42
1
2
3
4
EXPERIMENTAL SECTION
5
6
7
8
9
Materials and Methods. Out of the reagents used Copper (II) acetate monohydrate
(99.99 %); pyridine-2,5-dicarboxylic acid (98 %) and aldrithiol-4 (98 %) were purchased from
Sigma-Aldrich. All other chemicals used were AR grade. All chemicals were used as received
without any further purification. Elemental analysis (C, H, N) was carried out using a Perkin-
Elmer 240C elemental analyzer. The thermogravimetric analysis was carried out using a Mettler
Toledo TG-DTA 85 thermal analyzer under constant flow of N2 (30 ml/min). The sample was
heated at a rate of 10 ºC/min in an inert alumina crucible. The FTIR spectrum of the complex
between 400 and 4000 cm-1 was recorded by a Nicolet Impact 410 spectrometer using the KBr
pellet method. Photoluminescence spectrum of the complex was collected by a Shimadzu RF-
5301PC spectrophotometer. The transmission electron micrographs and the selected area
diffraction (SAED) pattern were recorded by Jeol 2100 high resolution transmission electron
microscope (HRTEM). The dynamic light scattering (DLS) experiment was performed by using
SZ 100 nano Partica instrument. The FESEM micrographs were recorded by FEI INSPECT F50
field emission scanning electron microscope (FESEM). Elemental analysis for CuO-NPs was
performed by BRUKER energy dispersive x-ray spectrometer (EDS) attached with the FEI
FESEM equipment.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Sample Preparation.
Synthesis of {[Cu2(2,5-pdc)2(ald-4)(H2O)2]•3H2O,MeOH}n. The complex under
investigation was synthesized via layering technique. Metal solution was prepared by dissolving
1 mmol Cu(OAc)2 in 50 ml water and 50 ml (30 ml MeOH and 20 ml H2O) ligand solution
containing 1 mmol disodium salt of ligand 2,5-pyridine dicarboxylic acid and 0.5 mmol
7
ACS Paragon Plus Environment

Page 9 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
aldrithiol-4 was prepared separately. The metal and the ligand solution (v/v) were kept isolated
in a layering tube by pouring a buffer solution of methanol and water in between them. After
seven days deep blue needle shaped crystals suitable for single crystal x-ray diffraction study
were obtained and collected. The product was characterized by single crystal x-ray diffraction
(SCXRD) technique, C, H, N analysis and FTIR measurement. Yield ~70%. Anal. cald. for
C25H28Cu2N4O14S2 revealed C: 37.52% (37.54% theo), H 3.54% (3.504% theo) and N: 7.1%
(7.008% theo). IR (KBr pellet, cm-1): 3238(s), 1667(s), 1565(s), 1473(w), 1396(s), 1372(s),
1280(w), 1130(w).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Synthesis of CuO and other metal oxide nanoparticles. The CuO-NPs were derived by
heating the as synthesized {[Cu2(2,5-pdc)2(ald-4)(H2O)2]•3H2O,MeOH}n at 650 °C for 4 hrs in
a muffle furnace in presence of air. Herein, the MOF acts as a self-sacrificing precursor for
synthesizing CuO-NPs. It is pertinent to mention that we have tried to reduce the particle size by
decreasing the sintering temperature but upon decreasing the sintering temperature the
morphological uniformity gets lost while particle size reduces by 2-3 nm which is insignificant.
The CuO NPs were characterized by FTIR, PXRD, HRTEM, SAED, EDS and DLS techniques.
The IR bands (KBr pellet method) were obtained at 601(s), 508(s), 487(s) cm-1 due to the
vibrations of Cu(II)-O bonds. The details of synthesis procedure adopted for preparation of NiO,
ZnO, Co3O4, SiO2 and Fe3O4 NPs have been depicted in the supplementary information file. The
PXRD patterns and the FESEM micrographs of these NPs are presented in Figures S1 to S10.
Methodology of Catalysis Test.
Materials. Aryl aldehydes, aryl amines, trimethylsilyl cyanide (TMSCN) and all other
chemicals used in catalytic experiments were purchased from Merck chemical company and used
8
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 42
1
2
3
4
5
6
7
8
9
without further purification. All the products were characterized by measuring their melting
points along with 1H/13C NMR studies. The 1H and 13C NMR studies were carried out by using a
300 MHz Bruker NMR spectrometer.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Catalytic Strecker reaction, Catalyst Separation and Product Isolation. A mixture of the
aryl aldehyde (1 mmol), aryl amine (1 mmol), TMSCN (1.2 mmol) and CuO-NPs (10 mmol) was
stirred at room temperature under solvent-free condition for appropriate time until the reactants
got solidified (also indicated by thin layer chromatography (TLC)). All the as-synthesized α-
aminonitrile derivatives were solid. It may be noted that α-aminonitrile derivatives dissolve in
ethanol while CuO does not. Therefore, after the completion of the reaction, 10 ml of ethanol
was added to the reaction mixture to dissolve the solid product and this mixture was then
ultracentrifuged. Finally, the solid part at the bottom of the ultracentrifuge tube and the liquid in
the upper part of it were carefully separated by decanting. Afterwards, the product was isolated
from the liquid part while the catalyst (CuO-NPs) was recovered from the solid residue. For
getting the product the liquid part collected by decanting the centrifuged mixture was filtered
again and vigorously sonicated to check the presence of any solid residue in it but no trace of any
dispersed/suspended solid particles were found in the filtrate. Thereafter, this filtrate was kept in
undisturbed condition up till (for few hours) the solvent (ethanol) got completely evaporated and
pure crystals of the desired products were obtained. Thus, column chromatography is not
required for the purification of the compounds produced in the catalytic reaction. On the other
hand, to recover the catalyst the solid part settled at the bottom of the centrifuge tube during
separation of the solid residue (in the first step of product and catalyst separation through
ultracentrifugation) and the dissolved product was collected and then washed several times with
9
ACS Paragon Plus Environment

Page 11 of 42
Crystal Growth & Design
1
2
3
4
5
6
ethanol and water, respectively. After that it was dried in vacuum oven keeping the temperature
at 110 ºC to recover the CuO-NPs for reusability test.
7
8
9
Primarily, the products obtained in catalytic reaction were identified by checking their
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
melting points. Further, the compounds were analyzed by H/13C NMR studies. The melting
points and NMR data of all the compounds were in accordance with the corresponding results
reported previously.
SCXRD Data Collection and Refinement. The SCXRD data of the complex was
recorded by mounting a suitable single crystal of the complex on a Bruker SMART
diffractometer equipped with a graphite monochromator, Mo-Kα (λ= 0.71073 Å) radiation and
CCD camera. The structure was solved by the Patterson method and followed by successive
Fourier and difference Fourier synthesis. Full matrix least-squares refinements were performed
on F2 using SHELXL-97 with anisotropic displacement parameters for all non-hydrogen atoms.
The hydrogen atoms were refined anisotropically and their locations were determined from the
difference Fourier map. All calculations were carried out using SHELXS 97,57 SHELXL 97,58
PLATON 99,59 ORTEP-3260 and WinGX61 system Ver-1.64.
PXRD Data Collection and Refinement: The PXRD data of CuO-NPs were collected at
ambient temperature (20 °C) by a Bruker D8 Advance diffractometer operating in the reflection
geometry using Cu-Kα radiation having wavelength 1.5418 Å. The generator voltage and current
were set at 40 kV and 40 mA, respectively. The PXRD data were collected within 2θ range of
20°−90° (step size 0.02°) at scan speed 6 s/step. The PXRD pattern of the sample was indexed
by DICVOL0662 and TREOR9063 of Fullprof.2 k64 package. The Rietveld refinement of PXRD
pattern was carried out using the GSAS65 program with EXPGUI66 interface. The peak shapes
10
ACS Paragon Plus Environment

Crystal Growth & Design
Page 12 of 42
1
2
3
4
5
6
7
8
9
were assessed by pseudo-Voigt functions. The background was fitted by the shifted Chebyshev
function of first kind with 20 points regularly distributed over the entire 2θ range. Initially, the
values of atomic coordinate and site occupancy were provided in accordance with JCPDS no. 80-
0076 for CuO. In the beginning, the lattice parameters, profile parameters and background were
refined. After few cycles of refinement, the atomic coordinates and isotropic thermal parameters
were refined. At the final stage, preferred orientation correction was applied using the
generalized spherical harmonic model. The Rietveld refinement yielded good fit with Rp = 0.030,
Rwp = 0.038 and χ2 = 1.04. Further, the crystalline size and micro-strain of CuO-NPs have been
obtained by analyzing PXRD pattern of the sample using MAUD 2.7067 software package.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
RESULTS AND DISCUSSION
Crystal Structure and Supramolecular of the MOF. Analysis of SCXRD data of the
complex under investigation has revealed that it crystallizes in achiral P21/n space group. Data
collection conditions, refinement and structural parameters of the complex are provided in Table
1 and the values of selected coordination bond lengths and bond angles are listed in Table S1.
The ORTEP diagram showing the asymmetric unit is presented in Figure 1. Each asymmetric
unit contains two independent Cu(II) ions, two 2,5-pdc linkers, one aldrithiol-4 moiety and two
coordinated water molecules together with guest water molecules and methanol. Each Cu atom
shows five coordinated square pyramidal geometry. The N1 and O3 atoms of the 2,5-pdc ligand,
N2 atom of the aldrithiol-4 ligand and O2 carboxylic oxygen atom of another 2,5-pdc ligand
form the basal plane and the coordinated water molecule O1W is at the axial position for the Cu1
atom. Similarly, for Cu2, N4 and O5 atoms of one 2,5-pdc ligand, N3 atom of the aldrithiol-4
ligand and O7 carboxylic oxygen atom of another 2,5-pdc ligand form the basal plane and O2W
water molecule is at the axial position. Here, the τ values of Cu1and Cu2 are 0.09 and 0.02,
11
ACS Paragon Plus Environment

Page 13 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
respectively. This indicates a slight distortion in the square-pyramidal environment of Cu1 and
Cu2 centers. The Cu-O bond distances vary in the range of 1.930 - 1.973 Å and Cu-N bond
distances lie between 2.002 - 2.035 Å. The Cu1-O1W and Cu2-O2W bond distances are 2.241 Å
and 2.225 Å, respectively.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The complex is a 2D coordination polymer. All carboxylate ligands of the complex bind
two metal centers in μ2-bridging pattern. In both cases, the 2,5-pdc ligands bind one Cu(II) centre
by using one nitrogen and one carboxylic oxygen atom as a chelating ligand and also connects a
different Cu(II) center by its another donor carboxylic oxygen atom and in turn two different
infinite 1D helical coordination chains, one pertaining to Cu1 and other pertaining to Cu2, are
formed along crystallographic b-axis. The bidentate aldrithiol-4 links the adjacent Cu-2,5-pdc
helical chains to form 2D coordination sheet, shown in Figure S11. The Cu•••Cu distances
separated by aldrithiol-4 and 2,5-pdc are 10.581 Å and 7.49 Å, respectively. The π•••π
interactions among the pyridyl groups further stabilize the 2D coordination sheets (Figure S12).
The π•••π interaction parameters are presented in Table S2. These 2D coordination sheets are
further connected by guest mediated supramolecular hydrogen bonding interactions (mainly
O2W-H2W2···O6 and O1W-H2W1···O4) to form 3D supramolecular structure (Figure S13). The
dimensions of hydrogen bonds are given in Table S3.
Helicity and Chirality. According to the space group consideration, this complex is
achiral but composed of two neighboring 2D sheets of opposite chirality. The 2,5-pdc bridges
the Cu(II) centers to form both 1D left handed and right handed infinite helical chains of
[Cu(pdc)]∞ along b-axis with the pitch of 8.4867Å (Figure 2A and 3A). The dihedral angle
between two dicarboxylato groups of 2,5-pdc ligands for Cu1 is 13.0°(9) and for Cu2 is 25.4°(8).
The 2,5-pdc ligands help in formation of 1D helical chains. The aldrithiol-4 molecules join two
12
ACS Paragon Plus Environment

Crystal Growth & Design
Page 14 of 42
1
2
3
4
5
6
7
8
9
adjacent chains in zigzag way to form 2D homochiral coordination sheets. Interestingly, only the
left handed helical chains are connected by aldrithiol-4 ligands to form homochiral 2D
coordination sheets (A) of left handed helicity, shown in Figure 2B. Similarly, another set of
homochiral sheets (B) containing only right handed helical chains are formed. Thus, linear
covalent interactions transfer similar stereochemical information between two neighboring chiral
units. It is interesting to note that A and B sheets are related by inversion symmetry, Figure S14.
The sheets are connected by linear hydrogen bonding interactions to form achiral 3D
supramolecular structure. Therefore the linear supramolecular interactions develop inversion
symmetry to transfer opposite chirality between adjacent homochiral sheets, and thus overall
stereochemical property of the MOF becomes achiral in nature. In the 3D supramolecular
framework sheets A and B are adjacent to each other and they are arranged in alternative
manner.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Thermogravimetric Investigation. Thermogravimetric (TGA) analysis was carried out
to study the thermal stability of the complex. The result shows that the complex is very stable in
air at ambient temperature. The sample was heated up in flowing N2 with a heating rate of 10
ºC/min within the temperature range of 25 to 500 ºC. The complex shows weight loss in three
steps. The weight loss occurring between 50 and 135 ºC corresponds to loss of solvent water,
methanol and coordinated water molecules, loss of weight in the temperature range of 260 - 370
ºC takes place due to loss of ligand (aldrithiol-4) and weight loss observed between 390 and 470
ºC can be attributed to the release of 2,5-pdc (Figure S15).
Photoluminescence Study. The emission spectra of the complex were studied in solid
state at room temperature. The complex shows emission maxima at ~ 377 nm with a shoulder at
291 nm (Figure S16) due to π-π* transition between the aromatic π-rings.
13
ACS Paragon Plus Environment

Page 15 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Characterization of MOF Derived CuO-NPs. Herein, we have synthesized CuO-NPs
of ~27.9 nm size by sintering the MOF at 650 ºC for 4 hrs in a furnace in presence of air. Upon
heating the blue compound turns to deep black powder which has been characterized by PXRD,
HRTEM, SAED, DLS and EDS techniques (Figure 4, 5 and 6). Indexing of the PXRD pattern of
the black powder suggests that it is single phase CuO belonging to monoclinic C2/c space group.
The Rietveld refinement of the PXRD data has been carried out to analyze the crystal structure of
this sample. The final Rietveld plot is displayed in Figure 4. The experimental and simulated
patterns match well with each with good enough values of reliability parameters and the
difference between the two curves is negligible. The results indicate that CuO-NPs are
crystallized in monoclinic C2/c space group. The Miller indices and the space group obtained by
the Rietveld structure refinement method are in good agreement with JCPDS data base (JCPDS
No. 80-0076). The final crystallographic data, refinement parameters and fractional coordinates
are given in Table S4 and S5. The Cu-O bonding network is shown in Figure S17.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The HRTEM micrograph of the NPs, presented in Figure 5, highlights well-defined NPs
of spherical shape. The size of individual particles was found to be between 20 and 34 nm. The
particle size distribution follows the log normal distribution function (Figure 6a) with σ ~ 0.16.
The average particle size obtained by fitting the distribution histogram is ~ 27.5 nm which
corroborates with the crystallite size (~ 26.7 nm) obtained by analyzing the PXRD pattern using
MAUD 2.70 program. In the high magnification HRTEM image, well-defined lattice fringes
indicating the highly crystalline nature of the sample have been clearly observed. The lattice
fringes with lattice spacing 0.0277 nm corresponding to the {110} plane of CuO-NPs were seen
in magnified HRTEM image. We have also carried out DLS study to assess the nature of particle
size distribution. The results indicate that particle size ranges between 15 - 39 nm and the
14
ACS Paragon Plus Environment

Crystal Growth & Design
Page 16 of 42
1
2
3
4
5
6
7
8
9
average size of CuO-NPs is ~29.7 nm which is also in good agreement with the results of
HRTEM analysis. Structural information about CuO-NPs has also been acquired from the SAED
pattern. SAED image of the sample exhibits prominent rings confirming good crystalline nature
of CuO-NPs. In the EDS survey spectrum of the sample (Figure S18), the only characteristic
peaks for constituent elements (Cu and O) of the CuO-NPs were obtained. Thus, the results of
PXRD, HRTEM and DLS studies together with confirmed that the sample obtained by
decomposition of the MOF is single phase, highly crystalline, nearly mono-dispersed and
spherical CuO-NPs.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Catalytic activity of the MOF Derived CuO-NPs. Synthesis of α-aminonitriles via
Strecker reactions have achieved enormous importance as α-aminonitriles are very important
intermediates in synthesis of various peptides and pharmaceutical products (e.g. saframycin A,
ecteinascidin 743 and phthalascidin).68-73 Here, we have examined the catalytic activity of CuO-
NPs toward synthesis of α-aminonitriles via one pot three component condensation of aldehyde,
amines and trimethylsilyl cyanide.
When a mixture of benzaldehyde (1 mmol), aniline (1 mmol) and TMSCN (1.1 mmol)
was stirred with CuO-NPs (10 mol %) in ethanol at room temperature – a high yield (84%) was
obtained in 15 min, (Table 3, entry 2). The yield was decreased (72%) when the same reaction
was carried out in water (Table 3, entry 3) and interestingly, higher yield (94%) of desired
product was obtained within 4 minutes when the reaction was carried out under solvent-free
condition (Table 3, entry 4). Lower yield of the product was obtained when the same reaction
was carried out in acetonitrile, DCM, toluene and DMF (45-68%, Table 3, entry 5, 6, 7 and 8). In
absence of the catalyst, no desired product was obtained even after 1 hour (Table 3, entry 1).
Further, we have examined the catalytic response of NiO, ZnO, Co3O4, SiO2 and Fe3O4
15
ACS Paragon Plus Environment

Page 17 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
nanoparticles (synthesized by common chemical methods) under same reaction conditions to
compare the catalytic response of CuO-NPs with these NPs. It has been found that the MOF
derived CuO-NPs exhibit better catalytic activity compared to that of the other oxide NPs like
NiO, ZnO, Co3O4, SiO2 and Fe3O4 under the same reaction conditions (Table 3, entry 10, 11, 12,
13 and 14).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Further, using the optimized reaction conditions, we have explored the utility of this
methodology by synthesizing various α-aminonitrile derivatives using a variety of substituted
aryl aldehydes and anilines (Table 2, entry 1-10). A number of aryl aldehydes with electron
donating (e.g. –OMe, –Me, –Cl etc.) and electron withdrawing (e.g. –NO2) groups were found to
participate in the Strecker synthesis and no significant electronic effect was observed. All the
reactions listed in Table 2 were very fast (culminates within 4-12 min) and produced well to
excellent yield of desired products (87-94 %).
The formation of the desired compounds was initially tested by determining their melting
points (Table 2). Further, all the compounds were characterized by spectroscopic (1H NMR)
method to confirm whether the desired product has been obtained or not (Figure S19 and S20).
Physicochemical properties of all the products of catalytic reaction are well known. It has been
found that the values of melting points of those compounds are identical with the reported values
1
of the corresponding compounds and the H NMR spectra of the compounds match perfectly
with those of the same compound reported in literature. In order to compare the catalytic
efficiency of CuO-NPs for the synthesis of α-aminonitrile derivatives, a comparative study of
catalytic performance of the present catalyst with the reported ones is presented in Table 4 and it
clearly indicates that the CuO-NPs mediated synthesis is better alternative to the existing
protocols.
16
ACS Paragon Plus Environment

Crystal Growth & Design
Page 18 of 42
1
2
3
4
5
6
7
8
9
A plausible mechanism for the CuO-NPs catalyzed synthesis of α-aminonitriles has been
presented in Scheme 2, where CuO-NPs promoted the in-situ formation of the imine intermediate
(I) through activating the oxygen and nitrogen atom of the carbonyl and amine groups,
respectively, followed by nucleophilic addition of cyanide to imine to give the desired product
(Scheme 2).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Finally, the catalyst stability was investigated by checking its reusability. The reusability
study was performed using the model reaction for the synthesis of 1a (see Table 2) keeping the
reaction condition unaltered. After each cycle, the CuO-NPs were recovered from the product
following the procedure described in experimental section. The recovered catalyst (CuO-NPs)
was successively reused for subsequent reactions. The results of reusability studies are presented
in Figure 7. It was observed that even after the 10th cycle, the catalytic efficiency remained intact
and a marginal (18%) loss in activity was observed.
Scheme 2. Plausible mechanism for CuO-NPs catalyzed synthesis of α-aminonitriles.
17
ACS Paragon Plus Environment

Page 19 of 42
Crystal Growth & Design
1
2
3
4
CONCLUSIONS
5
6
7
8
9
In summary, (i) we have successfully synthesized a Cu based MOF viz., {[Cu2(2,5-
pdc)2(ald-4)(H2O)2]•3H2O,MeOH}n by layering technique and characterized it by SCXRD, TGA
and photoluminescence studies, (ii) the crystal structure and supramolecular structure of the
MOF has been investigated in detail, (iii) highly defined spherical CuO-NPs were synthesized
through combustion of the MOF, (iv) we have shown that these CuO-NPs serves as an excellent
catalyst in green synthesis of α-aminonitriles – precursors of several important bio-molecules
and (v) the MOF derived NPs exhibit superior catalytic activity compared to other common
catalysts and MO-NPs synthesized by common chemical methods. Structural study on the
complex have revealed that each discrete Cu-centers are connected by 2,5-pdc ligands to form
both left handed and right handed infinite helical chains of [Cu(pdc)]∞ along crystallographic b-
axis. These 1D chains are bridged by ald-4 ligands to form 2D coordination polymers and these
2D polymers are further extended by guest dependent hydrogen bonding interactions to form 3D
supramolecular structure. Each 2D sheet is homochiral in nature whereas the structure contains
two different types of 2D sheets of opposite chirality. Thus, the overall framework is achiral in
nature. Here, the linear supramolecular hydrogen bonding interactions transfer opposite stereo-
chemical information of adjacent coordination sheets to 3D framework. The regular arrangement
of Cu within the MOF and presence of CuO bonds in the 1D helical chains of it allowed us to
fabricate the single phase, highly crystalline, nearly monodisperse and spherical CuO-NPs
utilizing the Cu-based MOF as self-sacrificing precursor. The PXRD, HRTEM, DLS and EDS
were employed to characterize the CuO-NPs obtained by decomposition of the MOF at 650 ºC.
These MOF derived CuO-NPs are used for the catalytic synthesis of α-aminonitriles by Strecker
reaction for the first time. By optimizing the reaction conditions, it has been established that the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18
ACS Paragon Plus Environment

Crystal Growth & Design
Page 20 of 42
1
2
3
4
5
6
7
8
9
MOF derived CuO-NPs exhibit excellent catalytic efficiency under solvent-free condition (in
solid state) at a very fast reaction rate. Thus the MOF derived MO-NPs can be beneficially
utilized in chemical industries as an excellent catalyst for synthesizing organic molecule of
biological importance with enhanced productivity and reduced amount of chemical waste at low
cost. In future, the alternative approach of deriving nanoparticles from MOF can be extended for
fabrication of functional nanostructured ferrite from bimetallic-MOFs.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at
DOI:…………
Synthesis procedure and characterization of NiO, ZnO, Co3O4, SiO2 and Fe3O4 NPs, 2D-sheet,
weak interactions and supramolecular architecture of the MOF, thermogravimetric and
photoluminescence plots of the MOF, Cu-O bonding network and EDS spectrum of the CuO-
NPs; results of NMR study, crystallographic data.
Accession Codes
CCDC no. of complex is 787145. The data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. This material is available free of charge via the Internet at
http://pubs.acs.org.
The CCDC number 787145 is solely for the crystal structure of the compound reported in
this article. This CCDC number (787145) has no relation with our earlier papers having DOI:
19
ACS Paragon Plus Environment

Page 21 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10.1007/s10870-013-0449-3 and 10.1039/C0CE00505C wherein it was mentioned
inadvertently. Correction in this regard for the first article has been published (please see: J
Chem Crystallogr, DOI 10.1007/s10870-017-0702-2) and the correction for DOI:
10.1039/C0CE00505C will be published by the concerned journal very soon.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
AUTHOR INFORMATION
Corresponding Author
*E-mail: kumars@phys.jdvu.ac.in (S. K.); rajatinorg1@gmail.com (R.S.); ocsb2006@gmail.com
(S.B.)
ORCID
Sanjay Kumar: 0000-0002-0584-0901
Soumen Singha: 0000-0002-6178-8562
Notes
The authors declare no competing financial interest.
The catalytic test and recording of HRTEM morphograph were performed by Arijit Saha and
Soumen Payra under the supervision of Subhash Banerjee (one of the corresponding authors).
ACKNOWLEDGMENT
SS gratefully acknowledges Department of Science and Technology (DST), Government
of India for providing research fellowship under DST INSPIRE programme. The PURSE and
FIST programs of DST, Govt. of India are also acknowledged. Financial support from the
University Grants Commission, New Delhi, and the Department of Science and Technology,
Government of India, through DRS (SAP-I) and FIST programs to Department of Physics,
Jadavpur University, for purchasing the x-ray powder diffractometer and FESEM instrument is
gratefully acknowledged.
20
ACS Paragon Plus Environment

Crystal Growth & Design
Page 22 of 42
1
2
3
4
REFERENCES
5
6
7
8
1. Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and
Applications of Metal-Organic Frameworks. Science 2013, 341, 1230444: 1–12.
2. Li, A. -L.; Gao, Q.; Xu, J.; Bu, X. -H. Proton-conductive metal-organic frameworks:
Recent advances and perspectives. Coord. Chem. Rev. 2017, 344, 54–82.
3. Gangu, K. K.; Maddila, S.; Mukkamala, S.B.; Jonnalagadda, S. B. A Review on
contemporary Metal-Organic Framework materials. Inorg. Chim. Acta 2016, 446, 61–74.
4. Kuppler, R. J.; Timmons, D. J.; Fang, Q.-R.; Li, J.-R.; Makal, T. A.; Young, M. D.;
Yuan, D.; Zhao, D.; Zhuang, W.; Zhou, H. -C. Potential applications of metal-organic
frameworks. Coord Chem Rev 2009, 253, 3042–3066.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5. Narayan, T. C.; Miyakai, T.; Seki, S.; Dincă, M. High Charge Mobility in a
Tetrathiafulvalene-Based Microporous Metal–Organic Framework. J. Am. Chem. Soc.
2012, 134, 12932−12935.
6. Chen, B.; Xiang, S.; Qian, G. Metal−Organic Frameworks with Functional Pores for
Recognition of Small Molecules. Acc. Chem. Res. 2010, 43, 1115–1124.
7. Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Duyne, R. P. V.; Hupp, J. T.
Metal–Organic Framework Materials as Chemical Sensors. Chem. Rev. 2012, 112, 1105–
1125.
8. Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, K.; Pham,
T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Porous materials with
optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 2013, 495,
80–84.
21
ACS Paragon Plus Environment

Page 23 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
9. Saha, R.; Joarder, B.; Roy, A. S.; Islam, S. M.; Kumar, S.Simultaneous Presence of Both
Open Metal Sites and Free Functional Organic Sites in a Noncentrosymmetric Dynamic
Metal–Organic Framework with Bimodal Catalytic and Sensing Activities. Chem. Eur. J.
2013, 19, 16607–16614.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
10. Yoon, M.; Suh, K.; Natarajan, S.; Kim, K. Proton conduction in metal-organic
frameworks and related modularly built porous solids. Angew. Chem. Int. Ed. 2013, 52,
2688–2700.
11. Wang, H.; Zhu, Q. -L.; Zou, R.; Xu, Q. Metal-Organic Frameworks for Energy
Applications. Chem 2017, 2, 52–80.
12. Yap, M. H.; Fow, K. L.; Chen, G. Z. Synthesis and applications of MOF-derived porous
nanostructures. Green Energy Environ. 2017, 2, 218-245.
13. Sun, J. -K.; Xu, Q. Functional materials derived from open framework
templates/precursors: synthesis and applications. Energy Environ Sci 2014, 7, 2071-2100.
14. Liu, B.; Shioyama, H.; Akita, T.; Xu, Q. Metal-Organic Framework as a Template for
Porous Carbon Synthesis. J. Am. Chem. Soc. 2008, 130, 5390–5391.
15. Jiang, H. -L.; Liu, B.; Lan, Y. -Q.; Kuratani, K.; Akita, T.; Shioyama, H.; Zong, F.; Xu,
Q. From Metal–Organic Framework to Nanoporous Carbon: Toward a Very High
Surface Area and Hydrogen Uptake. J. Am. Chem. Soc. 2011, 133, 11854–11857.
16. Torad, N. L.; Hu, M.; Kamachi, Y.; Takai, K.; Imura, M.; Naitoa, M.; Yamauchi, Y.
Facile synthesis of nanoporous carbons with controlled particle sizes by direct
carbonization of monodispersed ZIF-8 crystals. Chem. Commun. 2013, 49, 2521-2523.
22
ACS Paragon Plus Environment

Crystal Growth & Design
Page 24 of 42
1
2
3
4
5
6
7
8
9
17. Wang, Y.; Chen, B.; Zhang, Y.; Fu, L.; Zhu, Y.; Zhang, L.; Wu, Y. ZIF-8@MWCNT-
derived carbon composite as electrode of high performance for supercapacitor.
Electrochim. Acta 2016, 213, 260–269.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18. Liang, Y.; Feng, X.; Zhi, L.; Kolb, U.; Müllen, K. A simple approach towards one-
dimensional mesoporous carbon with superior electrochemical capacitive activity. Chem.
Commun. 2009, 809, 809–811.
19. Dai, R.; Sun, W.; Wang, Y. Ultrasmall Tin Nanodots Embedded in Nitrogen-Doped
Mesoporous Carbon: Metal-Organic-Framework Derivation and Electrochemical
Application as Highly Stable Anode for Lithium Ion Batteries. Electrochim. Acta 2016,
217, 123−131.
20. Li, W.; Wu, X.; Hana, N.; Chen, J.; Tang, W.; Chen, Y. Core-shell Au@ZnO
nanoparticles derived from Au@MOF and their sub-ppm level acetone gas-sensing
performance. Powder Technol. 2016, 304, 241–247.
21. An, B.; Cheng, K.; Wang, C.; Wang, Y.; Lin, W. Pyrolysis of Metal−Organic
Frameworks to Fe3O4@Fe5C2 Core−Shell Nanoparticles for Fischer−Tropsch Synthesis.
ACS Catal. 2016, 6, 3610−3618.
22. Bak, W.; Kim, H. S.; Chun, H.; Yoo, W. C. Facile synthesis of metal/metal oxide
nanoparticles inside nanoporous carbon matrix (M/MO@C) through morphology-
preserved transformation of metal-organic framework. Chem. Commun. 2015, 51, 7238-
7241.
23. Xia, W.; Zou, R.; An, L.; Xia, D.; Guo, S. A metal–organic framework route to in situ
encapsulation of Co@Co3O4@C core@bishell nanoparticles into a highly ordered porous
carbon matrix for oxygen reduction. Energy Environ Sci 2015, 8, 568–576.
23
ACS Paragon Plus Environment

Page 25 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
24. Zheng, F. C.; He, M. N.; Yang, Y.; Chen, Q. W. Nano electrochemical reactors of Fe2O3
nanoparticles embedded in shells of nitrogen doped hollow carbon spheres as high
performance anodes for lithium-ion batteries. Nanoscale 2015, 7, 3410−3417.
25. Qu, F.; Jiang, H.; Yang, M. MOF-derived Co3O4/NiCo2O4 double-shelled nanocages with
excellent gas sensing properties. Mater. Lett. 2017, 190, 75–78.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
26. Liu, B.; Han, S.; Tanaka, K.; Shioyama, H; Xu, Q. Metal Organic Framework (MOF) as
a Precursor for Synthesis of Platinum Supporting Zinc Oxide Nanoparticles. Bull. Chem.
Soc. Jpn. 2009, 82, 1052–1054.
27. Liu, Y. Y.; Gu, J. J.; Zhang, J. L.; Yu, F.; Dong, L. T.; Nie, N.; Li, W. Metal organic
frameworks derived porous lithium iron phosphate with continuous nitrogen-doped
carbon networks for lithium ion batteries. J. Power Sources 2016, 304, 42−50.
28. Meng, W. J.; Chen, W.; Zhao, L.; Huang, Y.; Zhu, M. S.; Huang, Y.; Fu, Y. Q.; Geng, F.
X.; Yu, J.; Chen, X. F. Porous Fe3O4/carbon composite electrode material prepared from
metal-organic framework template and effect of temperature on its capacitance. Nano
Energy 2014, 8, 133−140.
29. deKrafft, K. E.; Wang, C.; Lin, W. Metal-Organic Framework Templated Synthesis of
Fe2O3/TiO2 Nanocomposite for Hydrogen Production. Adv. Mater. 2012, 24, 2014–2018.
30. Wu, J.; Song, Y.; Zhou, R.; Chen, S.; Zuo, L.; Hou, H.; Wang, L. Zn–Fe–ZIF-derived
porous ZnFe2O4/C@NCNT nanocomposites as anodes for lithium-ion batteries. J. Mater.
Chem. A. 2015, 3, 7793−7798.
31. Xu, X.; Cao, R.; Jeong, S.; Cho, J. Spindle-like Mesoporous α-Fe2O3 Anode Material
Prepared from MOF Template for High-Rate Lithium Batteries. Nano Lett. 2012, 12,
4988−4991.
24
ACS Paragon Plus Environment

Crystal Growth & Design
Page 26 of 42
1
2
3
4
5
6
7
8
9
32. Banerjee, A.; Aravindan, V.; Bhatnagar, S.; Mhamane, D.; Madhavi, S.; Ogale, S.
Superior lithium storage properties of α-Fe2O3 nano-assembled spindles. Nano Energy
2013, 2, 890−896.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
33. Yang, S. J.; Nam, S.; Kim, T.; Im, J. H.; Jung, H.; Kang, J. H.; Wi, S.; Park, B.; Park, C.
R. Preparation and Exceptional Lithium Anodic Performance of Porous Carbon-Coated
ZnO Quantum Dots Derived from a Metal–Organic Framework. J. Am. Chem. Soc. 2013,
135, 7394–7397.
34. Wu, H. B.; Xia, B. Y.; Yu, L.; Yu, X. -Y.; Lou, X. W. Porous molybdenum carbide nano-
octahedrons synthesized via confined carburization in metal-organic frameworks for
efficient hydrogen production. Nature Comm. 2015, 6:6512, 1−8.
35. Hasan, Z.; Cho, D. -W.; Islam, G. J.; Song, H. Catalytic decoloration of commercial azo
dyes by copper-carbon composites derived from metal organic frameworks. J. Alloys
Compd. 2016, 689, 625-631.
36. Abney, C. W.; Taylor-Pashow, K. M. L.; Russell, S. R.; Chen, Y.; Samantaray, R.;
Lockard, J. V.; Lin, W. Topotactic Transformations of Metal−Organic Frameworks to
Highly Porous and Stable Inorganic Sorbents for Efficient Radionuclide Sequestration.
Chem. Mater. 2014, 26, 5231−5243.
37. Abney, C. W.; Gilhula, J. C.; Lu, K.; Lin, W. Metal-Organic Framework Templated
Inorganic Sorbents for Rapid and Efficient Extraction of Heavy Metals. Adv. Mater.
2014, 26, 7993–7997.
38. Du, W.; Liu, R.; Jiang, Y.; Lu, Q.; Fan, Y.; Gao, F. Facile synthesis of hollow Co3O4
boxes for high capacity supercapacitor. J. Power Sources 2013, 227, 101-105.
25
ACS Paragon Plus Environment

Page 27 of 42
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
39. Liu, B.; Zhang, X.; Shioyama, H.; Mukai, T.; Sakai, T.; Xu, Q. Converting cobalt oxide
subunits in cobalt metal-organic framework into agglomerated Co3O4 nanoparticles as an
electrode material for lithium ion battery. J. Power Sources 2010, 195, 857–861.
40. Hu, L.; Huang, Y.; Zhang, F.; Chen, Q. CuO/Cu2O composite hollow polyhedrons
fabricated from metal–organic framework templates for lithium-ion battery anodes with a
long cycling life. Nanoscale, 2013, 5, 4186–4190.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
41. Guo, H.; Li, T. T.; Chen, W. W.; Liu, L. X.; Qiao, J. L.; Zhang, J. Self-assembly
formation of hollow Ni-Fe-O nanocage architectures by metal-organic frameworks with
high-performance lithium storage. J. Sci. Rep. 2015, 5:13310, 5−10.
42. Pang, H.; Guan, B.; Sun, W.; Wang, Y. Metal-Organic-Frameworks Derivation of
Mesoporous NiO Nanorod for High-Performance Lithium Ion Batteries. Electrochim.
Acta. 2016, 213, 351− 357.
43. Yang, X.; Tang, Y. -B.; Huang, X.; Xue, H. T.; Kang, W. P.; Li, W. Y.; Ng, T. -W.; Lee,
C. -S. Lithium ion battery application of porous composite oxide microcubes prepared via
metal-organic frameworks. J. Power Sources 2015, 284, 109−114.
44. Lu, W. -G.; Gu, J. -Z.; Jiang, L.; Tan, M. -Y.; Lu, T. -B. Achiral and Chiral Coordination
Polymers Containing Helical Chains: The Chirality Transfer Between Helical Chains.
Cryst. Growth Des. 2008, 8, 192-199.
45. Zhang, M.; Wu, Y.; Wang, J.; Ren, Y.; Hou, X. Crystal Structure and Magnetic
Properties of a Novel Helical Coordination Polymer [Cu2(pda)2(phen)2(H2O)2].6H2O. J.
Inorg. Organomet. Polym. 2010, 20, 862–866.
26
ACS Paragon Plus Environment

Crystal Growth & Design
Page 28 of 42
1
2
3
4
5
6
7
8
9
46. Mendiratta, S.; Usman, M.; Luo, T. -T.; Chang, B. -C.; Lee, S. -F.; Lin, Y. -C.; Lu, K. -L.
Anion-Controlled Dielectric Behavior of Homochiral Tryptophan-Based Metal−Organic
Frameworks. Cryst. Growth Des. 2014, 14, 1572−1579.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
47. Wu, X.; Zhang, H. -B.; Xu, Z. -X.; Zhang, J. Asymmetric induction in homochiral MOFs:
from interweaving double helices to single helices. Chem. Commun. 2015, 51, 16331-
16333.
48. Saha, R.; Dey, S. K.; Biswas, S.; Jana, A. D.; Kumar, S. Transformation of a Mother
Crystal to a Daughter Crystal through Amorphous Phase: De-assembly of Coordination
Helices upon Heating and Re-assembly through Aquation. Cryst. Growth Des. 2013, 13,
2135-2142.
49. Cai, S. -L.; Zheng, S. -R.; Wen, Z. -Z.; Fan, J.; Zhang, W. -G. Assembly of
Chiral/Achiral Coordination Polymers Based on 2-(Pyridine-3-yl)-1H-4,5-
imidazoledicarboxylic Acid: Chirality Transfer between Chiral Two-Dimensional
Networks Containing Helical Chains. Cryst. Growth Des. 2012, 12, 2355−2361.
50. Ma, L.; Abney, C.; Lin, W. Enantioselective catalysis with homochiral metal–organic
frameworks. Chem. Soc. Rev. 2009, 38, 1248–1256.
51. Kesanli, B.; Lin, W. Chiral porous coordination networks: rational design and
applications in enantioselective processes. Coord. Chem. Rev. 2003, 246, 305–326.
52. Pérez-Garcíaa, L.; Amabilino, D. B. Spontaneous resolution under supramolecular
control. Chem. Soc. Rev. 2002, 31, 342–356.
53. Llano-Tomé, F.; Bazán, B.; Urtiaga, M. -K.; Barandika, G.; Lezamab, L.; Arriortua, M. -
I. CuII–PDC-bpe frameworks (PDC = 2,5- pyridinedicarboxylate,bpe = 1,2-di(4-
27
ACS Paragon Plus Environment

Page 29 of 42
Crystal Growth & Design
1
2
3
4
5
6
pyridyl)ethylene): mapping of herringbone-type structures. CrystEngComm 2014, 16,
8726–8735.
7
8
9
54. Llano-Tomé, F.; Bazán, B.; Urtiaga, M. -K.; Barandika, G.; Señarís-Rodríguez, M. A.;
Sánchez-Andújar, M.; Arriortua, M. -I. Cu-PDC-bpa solid coordination frameworks
(PDC = 2,5-pyrindinedicarboxylate; Bpa = 1,2-DI(4-pyridil)ethane)): 2D and 3D
structural flexibility producing a 3-c herringbone array next to ideal. J. Solid State Chem.
2015, 230, 191–198.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
55. Malaestean, I. L.; Ellern, A.; Leusen, J. V.; Kravtsov, V. C.; Kögerler, P.; Baca, S. G.
Cluster-based networks: assembly of a (4,4) layer and a rare T-shaped bilayer from
[MnIII MnII O2(RCOO)10] coordination clusters. CrystEngComm 2014, 16, 6523-6525.
2
4
56. Sanda, S.; Goswami, S.; Jena, H. S.; Parshamoni, S.; Konar, S. A family of three
magnetic metal organic frameworks: their synthesis, structural, magnetic and vapour
adsorption study, CrystEngComm 2014, 16, 4742–4752.
57. Sheldrick, G. M. SHELXS 97, Program for Structure Solution, University of Göttingen,
Germany, 1997.
58. Sheldrick, G. M. SHELXL 97, Program for Crystal Structure Refinement, University of
Göttingen, Germany, 1997.
59. Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl.
Crystallogr. 2003, 36, 7–13.
60. Farrugia, L. J. ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User
Interface (GUI). J. Appl. Crystallogr. 1997, 30, 565.
61. Farrugia, L. J. WinGX suite for small-molecule single-crystal crystallography. J. Appl.
Crystallogr. 1999, 32, 837–838.
28
ACS Paragon Plus Environment