Postfunctionalized Metalloligand-Based Catenated Coordination Polymers: Syntheses, Structures, and Effect of Labile Sites on Catalysis

Article abstract of DOI:10.1021/acs.cgd.8b01848

In this work, pyridyl-appended Co³⁺ complexes (1 and 2) have been postfunctionalized by using 4-(bromomethyl)benzoic acid, thus changing the functionalities from pyridyl-N donors to carboxylate-O donors. Using two such postfunctionalized metalloligands (3 and 4), several homo and heterometallic coordination polymers (HCPs) have been synthesized. Single crystal structural analyses revealed that all HCPs presented intriguing one-dimensional catenated architectures. Postsynthetic modification induced flexibility was found to be responsible for the nearly identical architectures for two sets of HCPs starting from two different postfunctionalized metalloligands, 3 and 4. Two sets of HCPs differed by the presence (3a-3d) or absence (4a-4b) of labile coordinated water molecules that demonstrated a profound effect on the heterogeneous catalysis of Knoevenagel condensation reactions and cyanation reactions.

Full text of DOI:10.1021/acs.cgd.8b01848

Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE
Article
Post-functionalized Metalloligands Based Catenated Coordination
Polymers: Syntheses, Structures and Effect of Labile Sites on Catalysis
Saurabh Pandey, Girijesh Kumar, and Rajeev Gupta
Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 26 Mar 2019
Downloaded from http://pubs.acs.org on March 27, 2019
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 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 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.
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 15
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Post-functionalized Metalloligands Based Catenated Coordination
Polymers: Syntheses, Structures and Effect of Labile Sites on
Catalysis
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
Saurabh Pandey,† Girijesh Kumar‡ and Rajeev Gupta†*
†Department of Chemistry, University of Delhi, Delhi 110007, India
‡Department of Chemistry, Panjab University, Chandigarh, India
ABSTRACT: In this work, pyridyl-appended Co3+ complexes (1 and 2) have been post-functionalized by using 4-
(bromomethyl)benzoic acid thus changing the functionalities from pyridyl-N donors to carboxylate-O donors. Using two such post-
functionalized metalloligands (3 and 4), several homo- and heterometallic coordination polymers (HCPs) have been synthesized.
Single crystal structural analyses revealed that all HCPs presented intriguing one-dimensional catenated architectures. Post-
synthetic modification induced flexibility was found to be responsible for the nearly identical architectures for two sets of HCPs
starting from two different post-functionalized metalloligands 3 and 4. Two sets of HCPs differed by the presence (3a – 3d) or
absence (4a – 4b) of labile coordinated water molecules that demonstrated profound effect on the heterogeneous catalysis of
Knoevenagel condensation reactions and cyanation reactions.
synthetic modification approach induced flexibility has resulted in
INTRODUCTION
nearly identical structures of two sets of CPs starting from two
different post-functionalized metalloligands. Two sets of CPs
differ by the presence (3a – 3d) or absence (4a – 4b) of labile
coordinated water molecules that illustrate profound effect on the
heterogeneous catalysis of Knoevenagel condensation reactions
and cyanation reactions.
Design and synthesis of coordination polymers (CPs) are
important due to their well-defined architectures1–10 and potential
applications in catalysis,11–17 gas sorption,18–22 optics,23–25
magnetism,26,27 and devices.28–30 In recent time, extensive efforts
have been devoted to design next-generation CPs with fascinating
structural features and topologies.31–36 Constructing an organized
and well-designed framework material has always been a
challenging task.37 One of the landmark achievements in this field
is the utilization of a metalloligand as a well-defined building
EXPERIMENTAL SECTION
Materials
Commercially available reagents of analytical grade were used as
received without further purification. Solvents were purified using
the standard literature procedures. The ligands H2L3py and H2L4py
and their Co3+ complexes 1 and 2 were synthesized according to
our previous report.46
block for the construction of
a desirable and ordered
architecture.2,8,38–55 Today, the focus is to design improved
metalloligands that can generate next-generation CPs with tunable
architectures for various custom-made applications.36,38,39
Notably, majority of the applications in CPs are related to the
porosity such materials offer and therefore continuous efforts
have been placed to enhance their porosity.56,57 Such a feat can be
achieved primarily by introducing lengthened or extended organic
linkers those can coordinate to the secondary metals to afford
extended architectures of increased porosity.56–62 Similarly, one
could utilize metalloligands having extended appended groups to
potentially coordinate secondary metal ions to generate desirable
CPs with enhanced porosity. In this context, a very few examples
are available in literature wherein organic ligands containing
extended functional groups have been used.61,62 However, one
could also think about introducing extended functional groups by
the mean of post-synthetic modification, an approach recently
developed in CP research.63,64 In this work, efforts have been
made to lengthen the appended functional groups by post–
synthetic modification of already known metalloligands.46
Physical Measurements
FTIR spectra were recorded with Perkin Elmer Spectrum-two
spectrometer having Zn-Se ATR. NMR spectral measurements
were carried out with a Jeol 400 MHz spectrometer. Absorption
spectra were recorded either with PerkinElmer Lambda25 or
Lambda35 spectrophotometers. Elemental analysis data were
obtained with an Elementar Analysen Systeme GmbH Vario EL-
III instrument. Thermal gravimetric analysis (TGA) was carried
out with DTG 60 Shimadzu at 5 °C min−1 heating rate under the
nitrogen atmosphere. Inductively coupled plasma mass
spectroscopy (ICP-MS) measurements were carried out using
Thermo Scientific iCAP Q. Powder X-ray diffraction (PXRD)
studies were performed either with an X’Pert Pro from Panalytical
or Bruker AXS D8 Discover instrument (Cu Kα radiation, λ =
1.54184 Å) with a slow scan rate at room temperature. Brunauer–
Emmett–Teller (BET) surface area measurements were carried
out by using nitrogen adsorption-desorption technique in an
automated surface area and porosity analyzer (Quantachrome).
In particular, we have used two pyridyl-appended cobalt-
based metalloligands46 for the post-functionalized modification
using 4-bromomethylbenzoic acid, thus changing the
functionalities from pyridyl-N donors to carboxylate-O donors.
The resultant post–functionalized metalloligands after reaction
with secondary metal ions produced one-dimensional CPs with
intriguing catenated architectures, 3a – 3d and 4a – 4b. Post-
Synthesis of Post-Functionalized Metalloligands (PFMLs)
PFML 3. Complex 1 was treated (100 mg, 0.121 mmol) with 4-
bromomethylbenzoic acid (114 mg, 0.534 mmol) in dimethyl
ACS Paragon Plus Environment

Crystal Growth & Design
Page 2 of 15
sulfoxide (DMSO, 6 mL) at room temperature for 2 h under the
(C=O) cm-1. Diffused reflectance absorption spectra (λmax, nm):
663.
[(3)Zn]Br.6H2O (3d).65 HCP 3d was synthesized by layering a
MeOH solution of PFML 3 (100 mg, 0.067 mmol, 4 mL) over an
aqueous solution of Zn(OAc)2.2H2O (32.35 mg, 0.1474 mmol, 4
mL) with an intermediate layer of 1-butanol (4 mL). After a
period of 8–10 d, red crystalline product of 3d was obtained.
1
2
3
4
5
6
7
8
magnetic stirring. After completion of the reaction, solvent was
removed under reduced pressure to afford a sticky product which
upon triturating with acetone afforded a yellow product. This
product was separated, dried and was dissolved in methanol.
Vapor diffusion of diethyl ether at room temperature produced
crystalline product within 5-6 d. Yield: 0.148 g (80%). Anal.
Calcd. for C66H50Br3CoN10O122H2O: 52.50%; H, 3.60%; N,
9.28%; Found: C, 52.42%; H, 3.55%; N, 9.80%. FTIR spectrum
(Zn-Se ATR, selected peaks): 1708, 1641 and 1623 (C=O) and
3089, 2927 (C-H) cm-1. Absorption spectrum: (λ, nm, DMSO (ε,
M-1 cm-1): 665 (70). 1H NMR spectrum (DMSO-d6, 400 MHz) δ=
8.97 (s, 4H), 8.90 (d, J = 5.8 Hz, 4H), 8.07 (t, J = 7.8 Hz, 4H),
7.95 (d, J = 8.1 Hz, 8H), 7.76 – 7.71 (m, 2H), 7.65 (d, J = 7.8 Hz,
2H), 7.50 (d, J = 8.4 Hz, 4H), 7.43 (d, J = 8.0 Hz, 8H), 5.85 (s,
8H). 13C NMR spectrum (100 MHz, DMSO-d6) δ 167.28 (s,),
167.16 (s, J = 12.0 Hz), 153.80 (s), 145.02 (s), 143.93 (s), 143.99
(s), 143.23(s), 142.83 (s), 141.49 (s), 139.10 (s), 132.07 (s),
130.56 (s), 129.08 (s), 128.88 (s), 127.32 (s), 62.85 (s).
Yield:
74
mg
(75%).
Anal.
Calcd.
for
C66H46CoN10O12ZnBr.6H2O: C, 53.44%; H, 3.94%; N, 9.44%;
Found: C, 53.12%; H, 3.93%; N, 9.29%. FTIR spectrum (Zn-Se
ATR, selected peaks): 3070 (C–H; asymm.), 2928 (C–H; symm.),
1630 (COO), 1619 (C=O) cm-1. Diffused reflectance absorption
spectra (λmax, nm): 668.
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
[(4)Mn].8H2O (4a). HCP 4a was synthesized by the reaction of
PFML 4 (100 mg, 0.0666 mmol) with Mn(OAc)2.4H2O (35.94
mg, 0.1467 mmol) in DMF (5 mL) at room temperature for 2 h.
After completion of the reaction, solvent was removed under the
reduced pressure and the crude product was isolated after washing
with diethyl ether. This product was dissolved in water and vapor
diffusion of acetone afforded red crystalline material within 8–10
PFML 4. PFML 4 was synthesized using a similar method as
followed for PFML 3 however using complex 2. Yield: 155 mg
(92%). Anal. Calcd. for C66H48CoN10O12Br4H2O: C, 57.27%; H,
4.08%; N, 10.12%; Found: C, 56.87%; H, 3.95%; N, 10.05%.
FTIR spectrum (Zn-Se ATR, selected peaks): 3100 (C–H; asym.),
2929 (C–H; sym.) 1705, and 1621 (C=O). Absorption spectrum
(λ, nm, DMSO (ε, M-1 cm-1): 697 (230). 1H NMR spectrum(400
MHz, DMSO-d6) δ 8.59 (d, J = 6.6 Hz, 8H), 8.29 (t, J = 7.8 Hz,
2H), 8.05 (d, J = 8.0 Hz, 8H), 7.88 (d, J = 7.7 Hz, 4H), 7.34 (d, J
= 8.1 Hz, 8H), 7.19 (d, J = 6.5 Hz, 8H), 5.64 (s, 8H). 13C NMR
spectrum (100 MHz, DMSO-d6) δ 167.28 (s), 166.98 (s), 161.95
(s), 153.82 (s), 145.12 (s), 139.72 (s), 132.05 (s), 130.65 (s),
128.88 (s), 128.70 (s), 128.64 (s), 125.70 (s), 61.94 (s).
d.
Yield:
68
mg
(63%).
Anal.
Calcd.
for
C66H46CoN10O12Mn.6H2O: C, 56.90%; H, 4.20%; N, 10.05%;
Found: C, 56.92%; H, 3.87%; N, 9.90%. FTIR spectrum (Zn-Se
ATR, selected peaks): 3062 (CH2; asymm), 2953 (CH2; symm),
1644 (COO), 1594 (C=O) cm-1. Diffused reflectance absorption
spectra (λmax, nm): 699.
[(4)Cd].8H2O (4b). HCP 4b was synthesized by layering a
solution of PFML 4 (100 mg, 0.0666 mmol) in DMSO (4 mL)
over an aqueous solution of Cd(OAc)2.2H2O (38.91 mg, 0.146
mmol) in water (4 mL). Yield: 71 mg (72%). Anal. Calcd. for
C66H46CoN10O12Cd.8H2O: C, 53.32%; H, 4.20%; N, 9.42%;
Found: C, 53.42%; H, 4.55%; N, 9.80%. FTIR spectrum (Zn-Se
ATR, selected peaks): 3045 (CH2; asymm), 2928 (CH2; symm),
1641 (COO), 1620 (C=O) cm-1. Diffused reflectance absorption
spectra (λmax, nm): 679.
Synthesis of Coordination Polymers
[(3)Mn(H2O)2]Br.C2H6SO.25H2O (3a).65 HCP 3a was synthesized
by layering a solution of PFML 3 (100 mg, 0.067 mmol) in
DMSO (4 mL) over an aqueous solution of Mn(OAc)2.4H2O
(35.14 mg, 0.147 mmol) dissolved in water (4 mL). The crystals
were obtained after 8–10 days. Yield: 0.94 g (79%). Anal. Calcd.
for C66H46CoN10O12MnBr(H2O)2.20H2O: C, 45.01%; H, 5.15%;
N, 7.95%; Found: C, 44.74%; H, 4.81%; N, 7.78%. FTIR
spectrum (Zn-Se ATR, selected peaks): 3390 (OH), 3079 (C–H;
asymm), 2936 (CH2; symm), 1625 (COO), 1597 (C=O) cm-1.
Diffused reflectance absorption spectra (λmax, nm): 662.
[(3)Co(H2O)2]Br.24H2O (3b).65 PFML 3 (100 mg, 0.067 mmol)
was treated with Co(OAc)2.4H2O (36.71 mg, 0.147 mmol) in
DMF (6 mL) at room temperature for 2 h under the magnetic
stirring. After 2 h, solvent was removed under the reduced
pressure and the crude product was washed with methanol and
dried under vacuum. This product was dissolved in water and
vapors of acetone were diffused. After a period of one week, dark
red crystals were obtained. Yield 72 mg, (65%). Anal. Calcd. for
C66H46Co2N10O12Br(H2O)2. 14H2O: C, 47.84%; H, 4.74%; N,
8.45; Found: C, 47.53%; H, 4.59%; N, 8.42%. FTIR spectrum
(Zn-Se ATR, selected peaks): 3392 (OH), 3081 (C–H; asymm),
2933 (C–H; symm), 1631 (COO), 1595 (C=O) cm-1. Diffused
reflectance absorption spectra (λmax, nm): 672.
Crystallography
The intensity data were collected at 293 K with an Oxford
XCalibur CCD diffractometer equipped with graphite
monochromatic MoKα radiation (λ = 0.71073 Å).66 Data were
processed with XCalibur S SAINT while the empirical absorption
correction was applied using spherical harmonics implemented in
the SCALE3 ABSPACK scaling algorithm.67 The structures were
solved by the direct methods using SIR-9768 and refined by the
full-matrix least squares refinement techniques on F2 using
program SHELXL-9769 incorporated in WINGX version 2014.1
crystallographic collective package.70 The solvent accessible
voids (SAVs) were calculated using PLATON.71 Additional
refinement details have been included in SI. Details of the
crystallographic data collection and structure solution parameters
are provided in Table 1 whereas Tables S1 and S2 (SI) contain the
selected bonding parameters.
RESULTS AND DISCUSSION
Design Aspects and Synthesis. Post-functionalized metalloligands
(PFMLs) 3 and 4 were synthesized by treating pyridine-appended
metalloligands
bromomethylbenzoic acid in DMSO (Scheme 1). FTIR spectra of
PFMLs and showed characteristic νC=O stretches for
1 or 2
(as the case may be)46 with 4-
[(3)Ni(H2O)2]Br.4H2O (3c).65 HCP 3c was synthesized using an
identical method as discussed for 3b, however, using
Ni(OAc)2.4H2O (36.68 mg, 0.1474 mmol). The crude compound
was dissolved in water and vapor diffusion with acetone for a
period of 6–8 d afforded red colored crystalline product. Yield: 64
mg (65%). Anal. Calcd. for C66H46CoN10O12NiBr(H2O)2.5H2O: C,
53.03%; H, 4.05%; N, 9.37%; Found: C, 53.42%; H, 4.55%; N,
9.80%. FTIR spectrum (Zn-Se ATR, selected peaks): 3384 (OH),
3076 (CH2; asymm.), 2992 (CH2; symm.), 1629 (COO), 1596
3
4
arylcarboxylic acid at 1708 cm-1 and 1707 cm-1, respectively,55
whereas, bands at 3089 and 2927 cm-1 and 3100 and 2929 cm-1 are
assigned to the C–H stretches of methylene group for 3 and 4,
respectively (Figures S1 and S2, Supporting Information).72 1H
NMR spectra of PFMLs 3 and 4 displayed the characteristic
singlet for the methylene group (–CH2–) at 5.85 and 5.64 ppm,
respectively (Figures S3 and S5, SI).73,74 This feature confirmed
ACS Paragon Plus Environment

Page 3 of 15
Crystal Growth & Design
that all four pyridyl groups have been functionalized. 13C NMR
signals for –CH2- group were noted at 62.8 and 61.9 for PFML 3
Table 1. Crystallographic data collection and structure refinement parameters for PFMLs 3 and 4 and HCPs 3a, 3d, 4a and 4b.
and 4,
1
2
3
4
3
4
3a
3d
4a
4b
5
6
7
8
Formula
Fw
C66H54Br3CoN10O14 C66H64BrCoN10O23 C68H50BrCoMnN10O40S C132H92Br2Co2N20Zn2O36 C66H66CoMnN10O22 C66H46CdCoN10O20
1509.85
298(2)
1508.1365
298(2)
1873.02
298(2)
2942.68
298(2)
1465.16
298(2)
1470.46
298(2)
T (K)
Crystal
System
9
Monoclinic
Monoclinic
Monoclinic
Orthorhombic
Tetragonal
Tetragonal
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
Space Group
a (Å)
C2/c
P2/c
P21/n
Pna21
19.3548(6)
19.8101(6)
17.6823(7)
90
I 41/a
17.683(4)
17.683(4)
21.469(5)
90
I 41/a
26.6350(10)
14.9763(4)
16.4404(5)
90°
7.6066(9)
15.5949(14)
28.832(2)
90°
15.6220(8)
28.6251(13)
20.8157(9)
90°
17.5602(8)
17.5602(8)
21.6199(14)
90
b (Å)
c (Å)
α (o)
β (o)
102.412(3)°
90°
94.647(9)
90°
107.3150(10)
90°
90
90
90
γ (o)
90
90
90
V (Å3)
Z
6404.7(4)
4
3409.0(6)
2
8886.6(7)
4
6779.8(4)
2
6713(3)
4
6666.7(6)
4
d (Mg/m3)
F (000)
1.566
1.531
1.400
1.441
1.271
2640
1.465
3056
1552
3804
2992
2988
Goodness-of-
fit on F2
R1,wR2
[I>2(I)]
R1,wR2[all
data]
Largest diff.
peak and hole
( e.Å-3)
1.051
1.061
1.059
1.059
1.139
1.034
0.0744, 0.1597
0.1499, 0.1848
0.0823, 0.1120
0.2028, 0.2231
0.0987, 0.2775
0.1699, 0.3122
0.0823, 0.2028
0.1120.2231
0.0859, 0.2382
0.0987, 0.2461
0.1168, 0.3009
0.2353, 0.3732
1.835 and -0.791
1.118 and -1.157
1.473 and -2.215
1.800 and -1.412
0.599 and -0.415
1.584 and -0.429
aR1 = ∑ ∥Fo| − |Fc∥ / ∑ | Fo|; wR2 = {∑ [w(/|Fo|2 − |Fc|2)2] / ∑[w Fo 4]}1/2
.
respectively (Figures S4 and S6, SI).73,74 UV-Visible spectra of
PFMLs 3 and 4 exhibited bathochromically shifted absorption
maxima (ca. 15 nm and 40 nm) when compared to their parent
metalloligands 1 and 2, respectively (Figures S7 and S8, SI).46
This is most probably due to the incorporation of additional π-
electron fragments.75 A close similarity between the XRPD
patterns of as-synthesized PFMLs to that of simulated ones from
their single crystal diffraction data revealed the phase purity of the
bulk samples (Figures S9 and S10, SI). Thermal gravimetric
analysis (TGA) for PFMLs 3 and 4 were performed in the
temperature ranges of 30 – 800 °C. TGA exhibited the loss of
lattice water molecules between 30 – 100 °C whereas both
PFMLs were stable up to 300 °C and decayed beyond this
temperature sequentially. For PFML 3, an observed weight loss
(1.94%) fits with the calculated weight loss of 2.38% for the
release of two water molecules (Figure S11, SI). For PFML 4, a
weight change (obsd./cacld. (%); 5.14/5.21) corresponded to the
loss of four lattice water molecules (Figure S12, SI).
presence of two different metals (%) for the following HCPs as
follows: 3a, Co/Mn (3.94/3.91); 3c, Co/Ni (3.82/3.85); 3d, Co/Zn
(3.61/3.75); and 4a, Co/Mn (3.81/3.75). Importantly, these
analyses establish the presence of two different metals in
approximately 1:1 ratio in all these HCPs.
O
O
O
R
O
R
N
Co
N
N
Co
N
R'
DMSO
R'
N
N
N
N
N
N
N
N
R'
O
R
O
HO
O
R'
R
O
O
Br
N
Br
R =
COOH
COOH
N
3
( )
N
R' =
1
( )
2
( )
N
The two sets of HCPs were synthesized by treating PFMLs 3
and 4 with the appropriate M(OAc)2 salt (Scheme 2). The
crystalline HCPs, once formed, were largely insoluble in most of
the common organic solvents. As the present HCPs contain two
different metals (except 3b) where differentiating between such
metals would be difficult solely based on the difference of their
electron densities from X-ray diffraction studies, ICP-MS
analyses were carried out. Indeed, ICP-MS results revealed the
Br
4
( )
Scheme 1. Synthetic route for the preparation of post-functionalized
metalloligands 3 and 4.
All six HCPs exhibited strong stretches (1625 – 1641 cm-1)
due to the νCOO groups, in their FTIR spectra.50–53 In addition,
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 15
broad features at 3382 – 3416 cm-1 are indica tive of the presence
space groups, respectively (for asymmetric unit, see Figure S31,
1
2
3
4
5
6
7
8
of coordinated and/or lattice water molecules (Figures S13–S18,
SI).53 HCPs 3a–3d, synthesized from PFML 3, displayed λmax in
the range of 662–674 nm in their diffused reflectance absorption
spectra (Figure S19, SI). On the other hand, HCPs 4a and 4b,
originated from PFML 4, showed λmax at 699 and 679 nm,
respectively (Figure S20, SI). In both cases, such features are
tentatively assigned to the d–d transitions based on both primary
(Co3+ ion) and secondary metals (except for Zn2+ and Cd2+
ions).50,52,53
SI). X-ray diffraction analyses revealed that in both cases all four
pyridyl groups were functionalized with 4-(bromomethyl)benzoic
acid and thus are present in the pyridinium form (Figures 1a and
1d). The positive charge on the resultant PFMLs is balanced by
the combinations of bromide ion(s) and anionic arylcarboxylate
group(s). In case of PFML 3, all four pyridyl-N functionalized
arylcarboxylic groups are in their protonated form (i.e., COOH)
whereas the parent metalloligand has 1 charge. Therefore,
overall 3+ charge is balanced by three bromide anions. Notably,
one of the bromide ions lies on bisects of the plane and thereby
contributes two negative charges. In contrast, in PFML 4, out of
four pyridyl-N functionalized arylcarboxylic groups; two each are
present in neutral protonated (i.e., COOH) and anionic
deprotonated (i.e., COO) forms. Therefore an overall mono-
cationic charge is balanced by a bromide ion. However, crystal
structure exhibits two Br- ions with half occupancy and thus both
of them together contribute 1– charge. In PFMLs, geometry of the
central Co(III) ion remained largely unaffected after the post–
functionalization of the pyridyl groups.46 In both cases, avg. Co–
Npyridyl and Co–Namide bond distances were found to be in range of
1.870 – 1.873 Å and 1.970 – 2.010 Å, respectively (Table S1, SI).
These values are quite similar to that of our earlier cobalt-based
metalloligands.46,50-53
9
XRPD patterns of the freshly prepared samples of HCPs 3a-
3d as well as 4a-4b were nearly similar to those simulated from
the single crystal diffraction data indicative of the phase purity of
the bulk samples (Figures S21–S26, SI). To probe thermal profiles
of all six HCPs, TGA studies were performed in the temperature
ranges of 30–800 °C (Figures S27 and S28, SI). For all six HCPs,
a good match was observed for the weight losses between 30 –
120 C corresponding to the lattice and/or coordinated water
molecules, as shown in Table 2. Subsequent to the weight loss for
such water molecules, all HCPs were thermally stable up to 300 –
325 C. Beyond this temperature sequential decomposition of
PFMLs followed by their parent metalloligands took place (ca. 40
– 60 %) which continues up to ca. 600 C and is finally leading to
metal oxides (35 – 50 %). Two representative HCPs, 3a and 4a,
were also investigated for their porosity measurements using
Brunauer–Emmett–Teller (BET) studies (Figures S29 and S30,
SI). HCP 3a and 4a respectively showed surface area of 18.7 m2/g
(average pore size: 134.5 Å) and 22.9 m2/g (average pore size:
339.4 Å).62 These results indicate low surface area as a result of
compact packing of 1D chains in the crystal lattice (cf. crystal
structures).
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
PFML 3 forms H-bonding based assembly via bromide ion,
Br2, which connects two molecules through O6-H group of the
carboxylic acid (O6-H6…Br2: 2.442 Å) (Figure 1b). Such an
interaction generates a 1D chain. Further, such 1D chains interact
with the adjacent ones through other weak interactions and finally
generates a two-dimensional (2D) packing (Figure 1c). In case of
PFML 4, individual molecules are connected to each other via
COOH…OC(OH) H-bonding interactions (O3–H2…O5: 1.723 Å).
Such a bonding produces an overall 2D architecture manifested by
H-bonding interactions and generating square-grid architecture
(Figures 1e and 1f). The topology of the resultant H-bonded
network is sql with {44·62} point symbol (Figure 1g).
N
O
N
O
O
OH2
O
M
O
OH2
O
OH2
N
N
O
M2+
O
O
O
O
O
PFML 3
O
M
N
Co
N
O
O
O
N
O
OH2
N
O
N
O
N
O
Crystal Structures of HCPs 3a–3d.65
where M2+ = Mn ( ), Co ( ), Ni ( ), Zn (
3d
)
3a
3b
3c
Single crystal X-ray diffraction analyses were carried out for all
four HCPs, 3a – 3d (for asymmetric unit, see Figure S32, SI).
Although, all four HCPs presented a very similar 1D polymeric
chain structure; 3d was different by the absence of metal-
coordinated water molecules when compared to the remaining
three HCPs, 3a – 3c. Therefore, crystal structures of 3a (as a
representative case) and 3d are discussed in details.77 HCP 3a
crystallized in monoclinic cell with P21/n space group. The
asymmetric unit contains one PFML 3, one Mn(II)ion, two
coordinated water, one bromide ion, one DMSO and twenty five
lattice water molecules. A 1D polymeric chain is generated via the
coordination of secondary Mn(II) ions to the arylcarboxylate
fragments originating from PFML 3 (Figures 2a–2c). Each Mn(II)
ion exhibits six-coordinated octahedral geometry. Out of six
coordination sites, four are satisfied with Ocaroxylate atoms (O5, O8,
O10 and O12) coming from four different arms of two PFMLs. The
remaining two axial sites are occupied by the water molecules
(O1W and O2W). 1D chains are further connected to the parallel-
running neighboring ones through various H-bonding interactions
involving Ocarboxylate and lattice water molecules as well as C-H…π
interactions to generate a 2D sheet–like architecture (Figure 2d).
PLATON analysis exhibited that only 2.7% solvent accessible
voids (SAVs) per unit cell volume existed due to the compact
packing of 1D chains. From the topological point of view, each
Mn atom is connected to two PFMLs having four arms and thus
can be simplified as a four-connected node while each PFML can
be viewed as a linear linker connecting two Mn centers (Figure
2e). Therefore, the network is constituted of 2,2,2,4 connected 4-
nodal net having Schlafli symbol of {122}{12}10-{22}{2}10.
N
N
O
O
O
O
O
O
N
N
O
O
M2+
O
O
O
O
PFML 4
N
N
Co
M
M
O
N
O
N
O
O
O
O
O
O
N
N
where M2+ = Mn ( ), Cd (
4a
4b
)
Scheme 2. Synthetic route for the preparation of homo- and heterometallic
coordination polymers 3a – 3d and 4a – 4b.
Table 2. Thermal gravimetric analysis data for HCPs 3a – 3d and
4a – 4b.
HCP
Weight loss
(Obsd. %)
Weight loss
(Calcd. %)
Loss of
water
molecules
3a
3b
3c
3d
4a
4b
22.03
17.16
8.01
7.35
9.65
9.97
22.50
17.39
8.43
7.28
10.07
9.68
22
16
7
6
6
8
Crystal Structures
Crystal structures of PFMLs 3 and 4.
Both PFMLs 3 and 4 were crystallographically characterized and
were found to crystallize in monoclinic cells with C2/c and P2/c
ACS Paragon Plus Environment

Page 5 of 15
Crystal Growth & Design
Reaction of Co(II) and Ni(II) ions with PFML 3 afforded HCPs
topologies of HCPs 3b and 3c were nearly identical to that of 3a
(Figures S33 and S34, SI).77-79
1
2
3b77,78 and 3c77,79 and both crystallized in triclinic cell with P-1
space group. The crystal structures and packing as well as
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
Figure 1. (a) Stick model diagram with partial numbering scheme for PFML 3; hydrogen atoms, anions, and solvent molecules are omitted
for clarity. (b) Figure showing H-bonding interactions between Br- ion (shown as golden yellow color sphere) and arylcarboxylic acid
fragments. (c) A view of the packing diagram in space fill mode along c axis. (d) Stick model diagram with partial numbering scheme for
PFML 4; hydrogen atoms, anions, and solvent molecules are omitted for clarity. (e) Figure showing H-bonding interactions between
different molecules (shown in assorted colors). (f) A view of packing diagram in space fill mode along c axis. (g) Topological
representation of PFML 4.
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 15
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
Figure 2. (a) Stick model diagram with partial numbering scheme for HCP 3a; hydrogen atoms, bromide anion, and solvent molecules are
omitted for clarity. (b and c) Figures showing H-bonding interactions involving various water molecules (shown as red color spheres). (d)
A view of packing diagram in the space fill mode along c axis. (e) Topological representation of HCP 3a.
HCP 3d, prepared by treating PFML 3 with Zn(II) salt,
crystallized in orthorhombic cell with Pna21 space group. The
asymmetric unit is comprised of one PFML, one Zn(II) ion, one
bromide ion and six lattice water molecules. The Zn(II) ion
acquired tetrahedral geometry where all four coordination sites
are satisfied by Ocarboxyalate groups stemming from two different
PFMLs. In this case as well, 1D polymeric chain was generated
by the coordination of secondary Zn(II) ions to the PFML 3
(Figures 3a-3d). Each 1D chain is further connected to the
adjacent chains via H-bonding between lattice water molecules
and Oamide atoms as well as via C–H…π interactions (O1…O4W:
2.764 Å; O4W…H-C22: 3.055 Å) (Figure 3b). As a result, 1D
chains are stacked to generate a layered structure. The crystal
structure of 3d exhibits 8.4% SAVs per unit cell volume which is
filled with the lattice water molecules. Topological analysis
revealed a similar network topology for 3d as observed in case of
3a – 3c.
ACS Paragon Plus Environment

Page 7 of 15
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
Figure 3. (a) Stick model diagram with partial numbering scheme for HCP 3d; hydrogen atoms, bromide anion, and solvent molecules are
omitted for clarity. (b and d) Figures showing H-bonding interactions involving water molecules (shown as red color sphere). (c) A view of
packing diagram in the space fill mode along c axis. (e) Topological representation of HCP 3d.
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 15
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
Figure 4. (a) Stick model diagram with partial numbering scheme for HCP 4a; hydrogen atoms and solvent molecules are omitted for
clarity. (b) Topological representation of HCP 4a. (c) Stick model diagram with partial numbering scheme for HCP 4b; hydrogen atoms
and solvent molecules are omitted for clarity. (d and f) Figures showing H-bonding interactions involving water molecules (shown as red
color sphere). (e) A view of packing diagram in the space fill mode along c axis. (g) Topological representation of HCP 4b.
Crystal Structures of HCPs 4a and 4b.
M(II) ions generated 1D chains in both cases. In both cases, such
chains are further connected to the neighboring ones through H-
bonding involving lattice water molecules as well as C–H…π
interactions (Figures 4d – 4f). Such interactions generated a 2D
sheet-like packing in both cases. As expected, topological
analyses revealed an identical network topology for both HCPs:
To understand both effect and impact of the position of appended
groups, metalloligand
2 offering para-pyridyl groups was
functionalized. The resultant para-pyridyl-N functionalized
PFML 4, on reaction with Mn(II) and Cd(II) salts, produced HCPs
4a and 4b, respectively. Both HCP 4a and 4b crystallized in
tetragonal cell with I41/a space group. In both cases, asymmetric
unit contained one fourth of PFML 4, one secondary M(II) ion
and two lattice water molecules (for asymmetric unit, see Figure
S35, SI). In both cases, geometry of the secondary metal ion was
nearly square-antiprism wherein all eight coordination sites were
satisfied by the bidentate Ocarboxylate groups (Figures 4a and 4c).
The Mn–O bond distances were found to be in the range of 2.284
– 2.367 Å whereas Cd–O bond lengths were noted between 2.411
– 2.416 Å (Table S1, SI). These bonds are quite longer than that
of other literature examples.50–52 A combination of PFML 4 and
2,2,4-connected nodal net with point symbol of {82}{8}6
–
{22}{2}6. (Figures 4b and 4g).
Application of 3a and 4a in Heterogeneous Catalysis
Heterogeneous catalysis has made significant impact in recent
time.80,81 Such a fact is due to ease in product separation and
recyclability of the catalyst.13,82 In this context, CPs have been
found quite effective as the heterogeneous catalysts due to their
robust architecture, porous nature and crystallinity.50–54 Attempts
have been made to incorporate assorted Lewis acidic as well as
ACS Paragon Plus Environment

Page 9 of 15
Crystal Growth & Design
redox-active metals in CPs.83 In this direction, our research group
(entry 2). Although, bulkier naphthaldehyde produced nearly
1
2
3
4
5
6
7
8
has successfully developed various heterogeneous catalysts for
noteworthy organic transformations.50–54 The present HCPs
provided a noteworthy opportunity to test their heterogeneous
catalytic applications. This is due to the fact that two sets of HCPs
differ by the presence (3a – 3d) or absence (4a – 4b) of
coordinated water molecules that may have profound effect on the
heterogeneous catalysis. We selected Knoevenagel condensation
reactions (KCRs)84–90 and cyanation reactions (CRs)91,92 to test the
said hypothesis. Both KCRs and CRs are well-established
reactions for the introduction of carbon-carbon bonds via
nucleophilic addition to carbonyl compounds.84–92 Both these
reactions are known to be catalyzed by the Lewis acidic metals.93–
quantitative product with HCP 3a (entry 8); much lower yield was
noted with 2,4,6-trimethoxybenzaldehyde, as a substantially
sterically hindered substrate (entry 8).91,92
Table 3. Optimization experiments for the cyanation reactions.
OH
O
Catalyst
+
Me3SiCN
Ph
CN
Ph
H
9
S. No.a
Catalyst
Solvent
Conversion (%)b
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
96
However, reports are available for the utilization of bases,97–102
1
2
3
4
5
6
3a
3a
3a
3a
3a
4a
MeCN
MeOH
EtOH
Toluene
---
40
35
ionic liquids103 and external stimuli, such as, microwave
irradiation, supersonic waves and grinding for driving such
reactions.104–107
37
For such catalytic reactions, one representative HCP from
each set was selected, 3a and 4a. Both 3a and 4a have Mn(II) ions
as the secondary metals that are coordinated to Ocarboxylate atoms
originating from PFMLs. Importantly, while Mn(II) ion in 3a is
coordinated by two axial water molecules; 4a does not contain
any coordinated solvent molecule. It is a well-known fact that the
coordinated solvent molecules on a catalytic metal are often labile
and thus facilitate their easy replacement and/or exchange by a
suitable solvent and/or a substrate.52,108 Therefore, we investigated
possible replacement and/or exchange of the coordinated water
molecules in 3a. For such a purpose, a vacuum-dried (at 50 C)
54
100
68
---
aReaction Conditions: catalyst: 1-mol%; reaction time: 2h;
temperature: 25 °C. bProducts were quantified by using gas
chromatograph.
sample of 3a was sealed in an atmosphere of D2O.52
A
comparison of the FTIR spectra of as-synthesized 3a and the one
after D2O exchange experiment exhibited that the most of the
water molecules (potentially both coordinated as well as lattice) in
3a were replaced by D2O and such a sample exhibited O-D
stretches at ca. 2500 cm-1 (Figure S36, SI). This simple
experiment infers that the coordinated water molecules in 3a are
labile and a suitable solvent can potentially replace them.52
Table 4. Cyanation reaction of assorted aldehydes with
(CH3)3SiCN in presence of catalysts 3a and 4a under the solvent
free condition.
OH
O
Catalyst
Me3SiCN
R
CN
R
H
Conversion (%)b
S. No.a
R
To further explore possible replacement of the labile water
molecules by a potential substrate, benzaldehyde was selected
along with HCP 3a, as a representative case. For such an
experiment, vacuum-dried (at 50 C) sample of 3a was dipped in
a CH2Cl2 solution of benzaldehyde. This impregnated sample was
then investigated by FTIR spectrum that showed red-shifted
stretches for the aldehyde group (1696 cm-1) compared to neat
benzaldehyde (1707 cm-1). This experiment strongly suggests that
benzaldehyde has potentially substituted the coordinated water
molecule in HCP 3a (Figure S37, SI).52
We started with CRs91,92 of benzaldehyde for exploring the
catalytic efficiencies of the present HCPs. For optimizing the
reaction conditions, 3a was used as a representative catalyst along
with benzaldehyde as a model substrate and trimethylsilyl cyanide
as the cyanide source (Table 3). Such reactions were performed at
25 C using only 1-mol% of a catalyst and were completed within
2 h. As can be seen, quantitative product was noted under the
solvent-free conditions (entry 5) when compared to the use of
various solvents (35 – 54 %; entries 1–4). Under the identical
reaction conditions, HCP 4a resulted in 68% product formation
(entry 6).
3a
4a
1
2
3
4
5
6
7
-C6H5
100
74
96
95
94
93
98
68
35
77
65
56
78
70
2-NO2C6H4
4-NO2C6H4
4-ClC6H4
4-OMeC6H4
3-OMeC6H4
1-Naphthyl
2,4,6-
OMeC6H2
8
63
42
aReaction Conditions: catalyst: 1-mol%; reaction time: 2h;
temperature: 25 °C. bProducts were quantified by using gas
chromatograph.
With these optimized reaction conditions, catalytic scope was
investigated. To understand the effect of an electronic group
present on the benzaldehyde; assorted substituted aldehydes were
used (Table 4).92,96 Notably, CRs were quite effective both with
electron-rich and electron-deficient benzaldehydes when
compared to benzaldehyde (entries 1-6). However, electronic
group effect was much more pronounced with 2-nitro-
benzaldehyde due to the anticipated –R effect of the nitro group
Subsequently, HCPs 3a and 4a were used as the
heterogeneous catalysts for KCRs (Tables 5 and 6).99 In these
reactions, an aldehyde substrate was treated with malononitrile at
40 C in presence of only 1-mol% of HCPs as the catalyst. A
screening of various solvents suggested that the quantitative
results are obtained under the solvent-free conditions (entry 5;
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 15
Table 5); however, use of MeCN (entry 1) and toluene (entry 4)
in 3a is coordinated by two axial water molecules; 4a does not
1
2
3
4
5
6
7
8
also produced the corresponding product in high yield. To explore
the scope of catalysis, different aldehydes containing electron-
withdrawing and electron-donating groups were used (Table
6).47,48,55,84–90 As anticipated, former substrates resulted in
increased product formation (entries 2 – 4) when compared to
para-methoxy benzaldehyde (entry 5).48 Use of 1-naphthaldehyde
produced the respective product in good yield (entry 6) with HCP
3a when compared to sterically demanding substrate, 2,4,6-
trimethoxybenzaldehyde (entry 7) 48
contain any coordinated solvent molecule. In addition, Mn(II) ion
in 4a exhibits an eight-coordinated geometry wherein a metal is
symmetrically surrounded by eight Ocarboxylate groups and not
having any open and/or vacant site. These facts strongly suggest
that while a substrate may not have difficulty in accessing the
Lewis acidic metal ions in 3a; in contrast, 4a does not provide
substrate accessibility. Furthermore, D2O and benzaldehyde
exchange experiments asserted the labile nature of coordinated
water molecules in 3a. Further evidence came from the time-
dependent reaction profile between benzaldehyde and
(CH3)3SiCN using HCPs 3a (blue trace) and 4a (red trace) as the
catalysts under the solvent-free conditions (Figure 5). This
experiment explicitly distinguishes between HCPs 3a and 4a and
proves the better catalytic efficiency of 3a when compared to 4a,
justifying the aforementioned points.
9
Table 5. Optimization experiments for the Knoevenagel
condensation reactions.
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
O
Catalyst
CN
CH2(CN)2
R
40 oC, 4h
Ph
H
CN
S. No.a
Catalyst
Solvent
Conversion (%)b
110
100
1
2
3
4
5
6
3a
3a
3a
3a
3a
4a
MeCN
MeOH
EtOH
Toluene
---
97
92



90
80
70
60
50
40
30
20
10


94

95



100
72

---
aReaction Conditions: catalyst: 1-mol%; reaction time: 4h;
temperature: 40 °C. bProducts were quantified by using gas
chromatograph.
0

0
1
2
3
4
5
6
Time (Hours)
Figure 5. Cyanation reaction between benzaldehyde and
(CH3)3SiCN using HCPs 3a (blue trace) and 4a (red trace) as the
catalysts under the solvent-free condition as a function of time.
Table 6. Knoevenagel condensation reaction of assorted
aldehydes with malononitrile in presence of catalyst 3a and 4a
under the solvent free condition.
Heterogeneous Nature of Catalysis and Reusability
O
Catalyst
It is desirable for a heterogeneous catalyst to exhibit both
recyclability and reusability.109 For such a purpose, HCP 3a was
selected as a representative catalyst for performing filtration test
during the KCR between benzaldehyde and malononitrile.53,110 As
can be seen from Figure 6, the catalytic reaction is nearly ceased
when HCP 3a was removed by filtration at 2 h from the reaction
mixture. The re-addition of 3a at 3 h resulted in the immediate
commencement of the catalysis. These observations potentially
suggest that the actual catalytic metal sites have not leached out
from HCPs during the catalysis.53,110 Additional evidences came
from the recyclability studies in which HCP 3a was filtered from
the reaction mixture and was reused for five consecutive cycles
for a reaction between benzaldehyde and malononitrile (inset;
Figure 6). While drop in the product yield was negligible for the
first three cycles; 5-6 % decrease in the product yield was noted at
the 4th and 5th cycle.53,110
CN
CH2(CN)2
R
40 oC, 4h
R
H
CN
Conversion (%)b
S. No.a
R
3a
4a
1
2
3
4
5
6
7
-C6H5
100
79
87
98
60
87
44
72
46
64
72
48
62
31
2-NO2C6H4
4-NO2C6H4
4-ClC6H4
4-OMeC6H4
1-Naphthyl
2,4,6-
OMeC6H2
aReaction conditions: catalyst: 1-mol%; temperature: 40 °C;
reaction time: 4h. bProducts were quantified by using gas
chromatograph.
A comparison of catalytic results both for CRs and KCRs
illustrate that HCP 3a is a much efficient catalyst when compared
to 4a. The crystal structures have confirmed that while Mn(II) ion
ACS Paragon Plus Environment

Page 11 of 15
Crystal Growth & Design
Corresponding Author
1
2
E-mail: rgupta@chemistry.du.ac.in;
Web: http://people.du.ac.in/~rgupta.
3
4
ORCID
5
6
7
8
Rajeev Gupta: 0000-0003-2454-6705
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
9
10
11
12
13
RG acknowledges Science and Engineering Research Board
(SERB; EMR/2016/000888), New Delhi for the financial support.
SP thanks CSIR, New Delhi for the SRF fellowship. Authors
thank CIF-USIC of this university for the instrumentation facility
including X-ray data collection.
Figure 6. (a) Knoevenagel condensation reaction between
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
benzaldehyde and malononitrile in presence of catalyst 3a. (b)
Catalyst 3a was filtered off after 2 h resulting in the termination
of the catalysis. (c) Re-addition of 3a at 3 h resulted in
commencement of catalysis leading to completeness. Inset
displays recyclability of HCP 3a for five consecutive catalytic
cycles.
REFERENCES
1.
Zhou, H.-C.; Kitagawa, S. Metal–Organic Frameworks
(MOFs). Chem. Soc. Rev. 2014, 43, 5415–5418.
Kumar, G.; Gupta, R. Molecularly designed architectures –
the metalloligand way. Chem. Soc. Rev. 2013, 42, 9403–
9453.
2.
Taking advantage of the heterogeneous nature of catalysis,
both HCPs 3a and 4a were recovered from the reaction mixture of
a KCR of benzaldehyde with malononitrile and characterized. The
sample homogeneity of 3a and 4a was confirmed by the XRPD
studies.50–55 XRPD patterns, both for 3a and 4a, exhibited a nearly
identical match to that of as-synthesized samples suggesting that
the crystallinity of the HCPs is maintained during the catalysis
(Figures S38 and S39, SI). Similarly, FTIR spectra of the
recovered HCPs 3a and 4a after the catalysis overlapped nicely to
that of pristine HCPs thus further confirming structural stability
during the catalysis (Figures S40 and S41, SI).
3.
Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J.
Supramolecular Coordination: Self-Assembly of Finite
Two-and Three-Dimensional Ensembles. Chem. Rev. 2011,
111, 6810–6918.
4.
5.
Chen, B.; Xiang, S.; Qian, G. Metal–Organic Frameworks
with Functional Pores for Recognition of Small Molecules.
Acc. Chem. Res. 2010, 43, 1115–1124.
Cook, T. R.; Stang, P. J. Recent Developments in the
Preparation and Chemistry of Metallacycles and
Metallacages via Coordination. Chem. Rev. 2015, 115,
7001–7045.
6.
7.
Sessoli, R.; Powell, A. K. Strategies towards single
molecule magnets based on lanthanide ions. Coord. Chem.
Rev. 2009, 253, 2328–2341.
Mishra, A.; Gupta, R. Supramolecular architecture with
pyridine-amide based ligands: discrete molecular
assemblies and their applications. Dalton Trans. 2014, 43,
7668–7682.
CONCLUSIONS
In this work, two different post–functionalized metalloligands
(PFMLs 3 and 4) have been utilized for the synthesis of 1D HCPs,
3a – 3d and 4a – 4b. These chain-like HCPs illustrated intriguing
catenated architectures and differed by the presence (3a – 3d) or
absence (4a – 4b) of coordinated water molecules. The secondary
metals of HCPs derived from PFML 3 displayed six-coordinated
geometry with two axially coordinated water molecules. In
8.
Srivastava, S.; Gupta, R. Metalloligands to material: design
strategies and network topologies. Cryst.Eng. Comm. 2016,
18, 9185–9208.
9.
Farha, O. K.; Hupp, J. T. Rational Design, Synthesis,
Purification, and Activation of Metal–Organic Framework
Materials. Acc. Chem. Res. 2010, 43, 1166–1175.
Das, M. C.; Xiang, S.; Zhang, Z.; Chen, B. Functional
Mixed Metal–Organic Framework with Metalloligands.
Angew. Chem. Int. Ed. 2011, 50, 10510–10520.
Liu; Chen, L.; Cui, H.; Zhang, J.; Zhang, L.; Su, C.-Y.
contrast, PFML
4 derived HCPs showed saturated eight-
coordinated geometry of the secondary metals with no ligated
solvent molecule. Representative HCPs 3a and 4a were utilized as
the heterogeneous catalysts for carrying out cyanation reactions
and Knoevenagel condensation reactions and illustrated profound
effect of the presence of labile water molecules on the secondary
metals on catalysis. These catalytic results are noteworthy and
will help in designing better heterogeneous catalysts. The present
design strategy has provided a noteworthy alternate procedure to
synthesize post-functionalized metalloligands having extended
functional groups. It is believed that such a design strategy will
help in preparing desirable architectures offering open-structures
for various porosity related applications.
10.
11.
Applications
of
metal–organic
frameworks
in
heterogeneous supramolecular catalysis. Chem. Soc. Rev.
2014, 43, 6011–6061.
12.
Dhakshinamoorthy, A.; Garcia, H. Metal–organic
frameworks as solid catalysts for the synthesis of nitrogen
containing heterocycles. Chem. Soc. Rev. 2014, 43, 5750–
5765.
13.
14.
Corma, A.; Garcia, H.; Xamena, F. X. L. I. Engineering
Metal–Organic Frameworks for Heterogeneous Catalysis.
Chem. Rev. 2010, 110, 4606–4655.
Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.;
Nguyen, S. B.T.; Hupp, J. T. Metal–organic framework
materials as catalysts. Chem. Soc. Rev. 2009, 38, 1450–
1459.
ASSOCIATED CONTENT
Supporting Information. Figures for FTIR, NMR and absorption
spectra; TGA; PXRD patterns; BET isotherms; and crystal
structures; and tables for the crystallographic bonding parameters.
AUTHOR INFORMATION
15.
Ma, L.; Abney, C.; Lin, W. Enantioselective catalysis with
ACS Paragon Plus Environment

Crystal Growth & Design
Page 12 of 15
homochiral metal–organic frameworks. Chem. Soc. Rev.
34.
Shin, J. W.; Bae, J. M.; Kim, C.; Min, K. S. Three-
2009, 38, 1248–1256.
Dimensional Zinc (II) and Cadmium Coordination
Frameworks with N, N, N’, N’-Tetrakis(pyridine-4-
yl)methanediamine: Structure, Photoluminescence, and
Catalysis. Inorg. Chem. 2013, 52, 2265–2267.
Mukherjee, S.; Samanta, D.; Mukherjee, P. S. New
Structural Topologies in a Series of 3d Metal Complexes
with Isomeric Phenylenediacetates and 1,3,5-Tris(1-
imidazolyl)benzene Ligand: Syntheses, Structures, and
Magnetic and Luminescence Properties. Cryst. Growth
Des. 2013, 13 5335–5343.
Chae, H. K.; Kim, J.; Friedrichs, O. D.; O’Keefe, M.;
Yaghi, O. M. Design of Framework with mixed triangular
and octahedral building blocks exemplified by the structure
of [Zn4O(TCA)2] having the pyrite topology. Angew Chem.
Int. Ed. 2003, 42, 3907–3909.
Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M.
The Chemistry and Applications of Metal-Organic
Framework. Science. 2013, 341, 1230444–1230455.
Burrows, A. D.; Mahon, M. F.; Renouf, C. L.; Richardson,
C.; Warrena, J.; Warrenc, J. E. Dipyridyl β-diketonate
complexes and their use as metalloligands in the formation
of mixed-metal coordination networks. Dalton Trans. 2012,
46, 4153–4163.
1
2
3
4
5
6
7
8
16.
17.
Zhu, Li.; Liu, X. –Q.; Jiang, H.-L.; Sun, L.-B. Metal–
Organic Frameworks for Basic Heterogeneous Catalysis.
Chem. Rev. 2017, 117, 8129–8176.
Wu, C.-D.; Zhao, M. Incorporation of Molecular Catalysis
in Metal–Organic Frameworks for Highly Efficient
Heterogeneous Catalysis. Adv. Mater. 2017, 29, 1605446–
1605466.
Marques, -G. M.; Galve, C. N.; Palomino, M.; Valencia, S.;
Rey, Fernando.; Sastre, G.; Yrezabal, V. J. I.; Ruiz, -J. M.;
Velamazan, R. A.; Gonzalez, M. A.; Jorda, J. L.; Coronado,
E.; Espallargas, G. M. Gas confinement in
compartmentalized coordination polymers for highly
selective sorption. Chem. Sci. 2017, 8, 3109–3120.
He, Y.; Zhou, W.; Qian, G.; Chen, B. Methane storage in
metal–organic frameworks Chem. Soc. Rev. 2014, 43,
5657–5678.
Yang, X.; Xu, Q. Bimetallic Metal–Organic Frameworks
for Gas Storage and Separation. Cryst. Growth Des. 2017,
17, 1450–1455.
Barea, E.; Montoro, C.; Navarro. Toxic gas removal–
metal–organic frameworks for the capture and degradation
of toxic gases and vapours. Chem. Soc. Rev. 2014, 43,
5419–5430.
Kumar, K. V.; Preuss, K.; Titrici, M.-M.; Rodriguez-
Reinoso, F. Nanoporous Materials for the Onboard Storage
of the Natural Gas. Chem. Rev. 2017, 117, 1796–1825.
Hu, Z.; Deibert, B. J.; Li, J. Luminescent metal–organic
frameworks for chemical sensing and explosive detection.
Chem. Soc. Rev. 2014, 43, 5815–5840.
Stavila, V.; Talin, A. A.; Allendorf, M. D. MOF-based
electronic and opto-electronic devices. Chem. Soc. Rev.
2014, 43, 5994–6010.
Wang, C.; Zhang, T.; Lin, W. Rational Synthesis of
Noncetrosymmetric Metal–Organic Frameworks for
Second-Order Nonlinear Optics. Chem. Rev. 2012, 112,
1084–1104.
Kurmoo, M. Magnetic metal–organic frameworks. Chem.
Soc. Rev. 2009, 38, 1353–1379.
Cheng, X. N.; Zhang, W. X.; Lin, Y. Y.; Chen, X. M. A
Dynamic Porous Magnet Exhibiting Reversible Guest-
Induced Magnetic Behavior Modulation. Adv. Mater. 2007,
19, 1494–1498.
Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa,
S. Structuring of metal–organic frameworks at the
mesoscopic and macroscopic scale. Chem. Soc. Rev. 2014,
43, 5700–5734.
35.
18.
9
36.
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
19.
20.
21.
37.
38.
39.
Zhang, Y.; Chen, B.; Fronczek F. R.; Maverick, A. W. A
Nanoporous Ag-Fe Mixed-Metal Organic Framework
22.
23.
24.
25.
Exhibiting
Single-crystal-to-Single-Crystal
Transformations upon Guest Exchange. Inorg. Chem.
2008, 47, 4433–4435.
40.
41.
Halper, S. R.; Do, L.; Stork, J. R.; Cohen, S. M.
Topological Control in Heterometallic Metal-Organic
Frameworks by Anion Templating and Metalloligand
Design. J. Am. Chem. Soc. 2006, 128, 15255–15268.
Mishra, A.; Ali, A.; Upreti, S.; Whittingham, M. S.; Gupta,
R. Cobalt complex as building blocks: synthesis,
characterization, and catalytic applications of {Cd2+-Co3+-
Cd2+} and {Hg2+-Co3+-Hg2+}heterobimetallic complexes.
Inorg. Chem. 2009, 48, 5234–5243.
Mishra, A.; Ali, A.; Upreti, S.; Gupta, R. Cobalt
Coordination Induced Functionalized Molecular Clefts:
Isolation of {CoIII-ZnII} Heterometallic Complexes and
Their Applications in Beckmann Rearrangement Reactions.
Inorg. Chem. 2008, 47, 154–161.
Ali, A.; Singh, A. P.; Gupta, R. Lewis acidic metal
catalyzed organic transformations by designed multi-
component structures and assemblies. J. Chem. Sci. 2010,
122, 311–320.
Singh, A.; Gupta, R. Copper(I) in the cleft: Syntheses,
structures and catalytic properties of {Cu+-Co3+-Cu+} and
{Cu+-Fe3+-Cu+}. Eur. J. Inorg. Chem. 2010, 4546–4554.
Kumar, G.; Singh, A. P.; Gupta, R. Synthesis, structures,
and heterogeneous catalytic applications of {Co3+-Eu3+}
and {Co3+-Tb3+} heterodimetallic coordination polymers.
Eur. J. Inorg. Chem. 2010, 5103–5112.
Singh, A. P.; Ali, A.; Gupta, R. Cobalt complexes as the
building blocks: {Co3+-Zn2+} heterobimetallic networks
and their properties. Dalton Trans. 2010, 39, 8135–8138.
Srivastava, S.; Ali, A.; Tyagi, A.; Gupta, R. {Cu2+-Co3+-
Cu2+} and {Cu2+-Fe3+-Cu2+} Heterobimetallic Complexes
and Their Catalytic Properties. Eur. J. Inorg. Chem. 2014,
2113–2123.
Bansal, D.; Pandey, S.; Hundal, G.; Gupta, R.
Heterometallic coordination polymers: syntheses, structures
and heterogeneous catalytic applications. New J. Chem.
2015, 39, 9772—9781.
Srivastava, S.; Dagur, M. S.; Ali, A.; Gupta, R. Trinuclear
{Co2+–M3+–Co2+} complexes catalyze reduction of nitro
compounds. Dalton Trans. 2015, 44, 17453–17461.
Kumar, G.; Gupta, R. Cobalt Complexes Appended with p-
and m-Carboxylates: Two Unique {Co3+–Cd2+} Networks
26.
27.
42.
43.
28.
44.
45.
29.
30.
Zhu, Q.-L.; Xu, Q. Metal–organic framework composites.
Chem. Soc. Rev. 2014, 43, 5468–5512.
Yang, Q. Y.; Li, K.; Luo, J.; Pan, M.; Su, C.Y. A simple
topological identification method for highly (3,12)-
connected 3D MOFs showing anion exchange and
luminescent properties. Chem. Commun. 2011, 47, 4234–
4236.
Zhang, Y. –B.; Furukawa, H.; Ko, N.; Nie, W.; Park, H. J.;
Okajima, Cordova, K. E.; Deng, H.; Kim, J.; Yaghi, O. M.
Introduction of Functionality and Selection of Topology,
and Enhancement of Gas Adsorption in Multivariate
Metal–Organic Framework. J. Am. Chem. Soc. 2015, 137,
2641–2650.
Kim, J.; Chen, B.; Reineke, T. M.; Li, H.; Eddaoudi, M.;
Moler, D. B.; O’Keeffe, M.; Yaghi, O. M. Assembly of
Metal–Organic Frameworks from Large Organic and
Inorganic Secondary Building Units: New Examples and
simplifying Principles for Complex Structures. J. Am.
Chem. Soc. 2001, 123, 8239–8247.
Tranchemontagne, D. J.; Mendoza-Corte, J. L.; O’Keefe,
M.; Yaghi, O. M. Secondary building units, nets and
bonding in the chemistry of metal–organic frameworks.
Chem. Soc. Rev. 2009, 38, 1257–1283.
46.
47.
31.
32.
33.
48.
49.
50.
ACS Paragon Plus Environment

Page 13 of 15
1
Crystal Growth & Design
and Their Regioselective and Size-Selective Heterogeneous
68.
69.
70.
Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi,
A. J. Appl. Crystallogr. 1993, 26, 343.
Sheldrick, G. M. Acta Crystallogr., Sect. A: Found.
Crystallogr. 2008, 64, 112.
Catalysis. Inorg. Chem. 2012, 51, 5497–5499.
51.
Kumar, G.; Gupta, R. Three-Dimensional {Co3+– Zn2+} and
{Co3+– Cd2+} Networks Originated from Carboxylate-rich
Building Blocks: Syntheses, Structures, and Heterogeneous
Catalysis. Inorg. Chem. 2013, 52, 10773–87.
Kumar, G.; Kumar, G.; Gupta, R. Manganese- and Cobalt-
Based Coordination Networks as Promising Heterogeneous
Catalysts for Olefin Epoxidation Reactions. Inorg. Chem.
2015, 54, 2603–2615.
Kumar, G.; Hussain, F.; Gupta, R. Carbon-sulphur cross
coupling reactions catalyzed by nickel-based coordination
polymers based on metalloligands. Dalton Trans. 2017, 46,
15023–15031.
2
3
4
5
6
7
8
9
Farrugia, L. J. WinGX v 1.70, An Integrated System of
Windows Programs for the Solution, Refinement and
Analysis of Single-Crystal X-ray Diffraction Data;
Department of Chemistry, University of Glasgow, 2003.
Spek, A. L. PLATON, A Multipurpose Crystallographic
Tool; Utrecht University, The Netherlands, 2002.
Silverstein, R. M.; Webster, F. X.; Kiemle, D. J.
Spectrometric Identification of Organic Compounds. John
Wiley & Sons. 2005.
Emmanuel, K.; Cheng, C.; Mondal, Erigene, B.; Hossain,
M. M.; Afsar, N. U.; Khan, M. I.; Wu, L.; Xu, T.
Covalently Cross-Linked Pyridinium Based AEMs with
Aromatic Pendant Groups for Acid Recovery via Diffusion
Dialysis. Separ. Purific. Techn. 2016, 164, 125–131.
Jasmani, L.; Eyley, S.; Wallbridge, R.; Thielemans, W. A
Facile One pot Route to Cationic Cellulose Nanocrystals.
Nanoscale, 2013, 5, 10207–10211.
52.
53.
54.
55.
71.
72.
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
73.
Kumar, G.; Kumar, G.; Gupta, R. Lanthanide-based
coordination polymers as promising heterogeneous
catalysts for ring-opening reactions. RSC Adv. 2016, 6,
21352–21361.
Srivastava, S.; Kumar, V.; Gupta, R. A Carboxylate-Rich
Metalloligands and Its Heterometallic Coordination
Polymers: Syntheses, Structures, Topologies, and
Heterogeneous Catalysis. Cryst. Growth Des. 2016, 16,
2874–2886.
74.
75.
76.
Hanson, K.; Roskop, L.; Djurovich, P. I.; Zahariev, F.;
Gordon, M. S.; Thompson, M. E. J. Am. Chem. Soc. 2010,
131, 16247–16255.
Shmilovits, M.; Vinodu, M.; Goldberg, I. Coordination
Polymers of Tetra(4-carboxyphenyl)porphyrins Sustained
by Tetrahedral Zinc Ion Linkers. Cryst. Growth Des.
2016, 4, 633–638.
HCPs 3b and 3c always produced poorly diffracting thin
fibrous crystals despite multiple attempts of growing
crystals using different solvents and conditions as well as
data collection. Using such data, with large RInt. values,
only partial structure solution was possible.
56.
57.
58.
59.
Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S.B.;
Choi, E.; Choi, E.; Yazaydin, A. Q.; Snurr, R. Q.;
O’Keeffe, M.; Kim, J.; Yaghi, O. M. Ultra-High Porosity in
Metal–Organic Frameworks. Science. 2010, 239, 424–428.
Song, K.S.; Kim, D. Polychronopoulou, Coskun, A.
Synthesis of Highly Porous Coordination Polymers with
Open Metal Sites for Enhanced Gas Uptake and Separation.
ACS Appl. Mater. Interfaces. 2016, 8, 26860–26867.
Chae, H. K.; Siberio Pe’rez, D. Y.; Kim, J.; Go, Y.;
Eddaoudi, M.; Matzger, A. J.; O’Keeffe, M. A route to high
surface area, porosity and inclusion of large molecules in
crystals. Nature. 2004, 427, 523–527.
Chae, H. K.; Eddaoudi, M.; Kim, J.; Hauck, S. I.; Hartwig,
J. F.; O’Keeffe, J.; Yaghi, O. M. Tertiary Building Units:
Synthesis, Structure, and Porosity, of a Metal-Organic
Framework Dendrimer Framework (MODF-1). J. Am.
Chem. Soc. 2001, 123, 11482–11483.
Kitagawa, S.; Kitaura, R.; Noro, S. –I. Functional Porous
Coordination Polymers. Angew. Chem. Int. Ed. 2004, 43,
2334–2375.
Kitagawa, S.; Matsuda, R. Chemistry of space of porous
coordination polymers. Coord. Chem. Rev. 2007, 251,
2490–2509.
Hmadeh, M.; Lu, Z.; Liu, Z.; Gandara, F.; Furukawa, H.;
Wan, S.; Augustyn, V.; Chang, R.; Liao, L.; Zhou, F.;
Perre, E.; Ozolins, V.; Suenaga, K.; Duan, X.; Dunn, B.;
Yamamto, Y.; Terasaki, O.; Yaghi, O. M. New Porous
Crystals of Extended Metal–Catecholates. Chem. Mater.
2012, 24, 3511–3513.
Lorion, M. M.; Matt, B.; Alves, S.; Proust, A.; Poli, G.;
Oble, Julie.; Izzet, G. Versatile Post-functionalization of
Polyoxometalate Platforms By Using An Unprecedented
Range of Palladium-Catalyzed Coupling Reactions. Chem.
Eur. J. 2013, 19, 12607–12612.
77.
78.
Crystal data of 3b: cell = Triclinic; space group = P-1; a =
12.8413(6);
b = 15.3364(7); c = 21.9533(10); α =
90.5190(10); β = 98.0160(10); γ = 111.4980(10); V =
3974.9(3); Z = 2.
79.
80.
81.
82.
Crystal data of 3c: cell = Triclinic; space group = P-1; a =
13.045(3); b = 15.4065(17); c = 22.128(2); α = 89.370(8); β
= 82.555(11); γ = 67.901(14); V =4082.4(10); Z = 2.
Dhakshinamoorthy, A.; Li, Z.; Garcia, H. Catalysis and
Photocatalysis by Metal Organic Frameworks. Chem. Soc.
Rev. 2018, 47, 8134–8172.
Liu, L.; Corma, A. Metal Catalysts for Heterogeneous
Catalysis: From Single Atoms to Nanoclusters and
Nanoparticles. Chem. Rev. 2018, 118, 4981–5079.
Wang, X.; Liu, M.; Wang, Y.; Fan, H.; Wu, J.; Huang, C.;
Hou, H. Cu(I) Coordination Polymers as Green
Heterogeneous Catalysts for Direct C-H Bonds Activations
of Arylalkanes to Ketones in Water with Spatial
Confinement Effect. Inorg. Chem. 2017, 56, 13329–13336.
Tan, B.; Chen, C.; Cai, L.-X.; Zhang, Y.-J.; Huang, X. –Y.;
Zhang, J. Introduction of Lewis Acidic and Redox Active
Sites into a Porous Framework for Ammonia Capture with
Visual Color Response. Inorg. Chem. 2015, 54, 3456–
3461.
60.
61.
62.
83.
63.
84.
85.
86.
Freeman,
F.
Properties
and
Reactions
of
64.
65.
Stengel, I.; Strassert, C. A.; Plummer, E. A.; Chien, C,-H.;
Cola, L. D.; Bauerle, P. Postfunctionalization of
Luminescent Bipyridine PtII Bisacetylides by Click
Chemistry. Eur. J. Inorg. Chem. 2012, 1795–1809.
The empirical formulae as well as crystal structures of
HCPs 3a – 3d displayed the presence of one bromide ion;
however, corresponding proton to balance the charge could
not be identified. We believe that one of the lattice water
molecules exists in the form of hydronium ion to balance
the mono-anionic charge.
Ylidenemalononitriles. Chem. Rev. 1980, 80, 329–350.
Tietze, L. F. Domino Reactions in Organic Synthesis.
Chem. Rev. 1996, 96, 115–136.
Lee, A.; Michrowska, A.; Sulzer-Mosse, S.; List, B. The
Catalytic Asymmetric Knoevenagel Condensation. Angew.
Chem. Int. Ed. 2011, 50, 1707.
Ma, L.; Wu, H.; Yang, J.; Liu, Y.-Y. Ma, J. –F. Synthesis,
crystal structures and Knoevenagel condensation reactions
of three coordination polymers assembled with Lewis basic
ligand. Polyhedron. 2018, 144, 6–10.
87.
88.
66.
67.
CrysAlisPro, v 1.171.33.49b; Oxford Diffraction Ltd.,
2009.
SAINT, Version 6.02; Bruker AXS: Madison, WI, 1999.
Karmakar, A.; Rubio, G. M. D. M.; Guedes da Silva, M. F.
C.; Hazra, S. Pombeiro, A. J. L. Solvent-Dependent
Structural Variation of Zinc(II) Coordination Polymers and
ACS Paragon Plus Environment

Crystal Growth & Design
Page 14 of 15
Their Catalytic Activity in the Knoevenagel Condensation
different aromatic aldehydes and malononitrile and their
Reaction. Cryst. Growth Des. 2015, 15, 4185–4197.
Ugale, B.; Dhankar, S. S. Nagaraja, C. M. Construction of
3D homochiral metal–organic frameworks (MOFs) of
Cd(II): selective CO2 adsorption and catalytic properties
for Knoevenagel and Henry reaction. Inorg. Chem. Front.
2017, 4, 348–359.
Chadar, D.; Rao, S. S.; Gejji, S. P.; Ugale, B.; Nagaraja, C.
M.; Nikalje, M.; Salunke-Gawali, S. Regioselective
synthesis of a vitamin K3 based dihydrobenzophenazine
derivative: its novel crystal structure and DFT studies. RSC
Adv. 2015, 5, 76419–76423.
Gregory, R. J. H. Cyanohydrins in Nature and the
Laboratory: Biology, Preparations, and Synthetic
Applications. Chem. Rev. 1999, 99, 3649–3682.
Brunel, J. M.; Holmes, I. P. Chemically Catalyzed
Asymmetric Cyanohydrin Syntheses. Angew. Chem., Int.
Ed. 2004, 43, 2752–2778.
Brooks, A. C.; France, L.; Gayot, C.; Li, J.; Pui, H.; Sault,
R.; Stafford, A.; Wallis, J. D.; Stockenhuber, M. A
designed organic–zeolite hybrid acid-base catalyst. J.
Catal. 2012, 285, 10–18.
Peng, Y.; Wang, J.Y.; Long, J.; Liu, G. H. Controllable
acid-base bifunctionalized mesoporous silica: Highly
efficient catalyst solvent-free Knoevenagel condensation
reaction. Catal. Commun. 2011, 15, 10–14.
Postole, G.; Chowdhury, B.; Karmakar, B.; Pinki, K.;
Banerji, J.; Auroux, A. Knoevenagel condensation reaction
over acid-base bifunctional nanocrystalline CexZr1-XO2
solid solutions. J. Catal. 2010, 269, 110–121.
Merino, E.; Verde-Sesto, E.; Maya, E. M.; Igesias, M.;
Sanchez, F.; Corma, A. Synthesis of Structured Porous
Polymers with Acid and Basic Sites and Their Catalytic
Applications in Cascade-Type Reactions. Chem. Mater.
2013, 25, 981–988.
Li, G. W.; Xiao, J.; Zhang, W. Q. Efficient and reusable
amine-functionalized polyacrylonitrile fiber catalysts for
Knoevenagel condensation in water. Green Chem. 2012,
14, 2234–2242.
subsequent non-catalytic Diels-Alder reactions. J. Mol.
Catal. A. 2011, 335, 236–241.
Xu, D. Z.; Shi, S.; Wang, Y. Polystyrene immobilized
DABCO as highly efficient and recyclable organocatalyst
for the Knoevenagel condensation reaction. RSC Adv.
2013, 3, 23075–23079.
Luo, J.; Xin, T.; Wang, Y. A PEG bridged tertiary amine
functionalized ionic liquid exhibiting thermoregulated
reversible biphasic behavior with cyclohexane/isopropanol:
synthesis and application in Knoevenagel condensation
reaction. New J. Chem. 2013, 37, 269–273.
1
2
3
4
5
6
7
8
89.
90.
102.
103.
9
91.
92.
93.
104.
105.
106.
Parvin, M. N.; Jin, H.; Ansari, M. B.; Oh, S. M.; Park, S. E.
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
Imidazolium Chloride Immobilized SBA-15 as
a
Heterozenized Organocatalyst for Solvent free
Knoevenagel Condensation using Microwave. Appl. Catal.
A. 2012, 205, 413–414.
Mallouk, S.; Bougrin, K.; Laghzizil, A.; Benhida, R.
Microwave-Assisted
and
Efficient
Solvent-free
Knoevenagel Condensation. A sustainable Protocol using
Porous Calcium Hydroxyapatite as Catalyst. Molecules,
2010, 15, 813–823.
Martin-Aranda, R. M.; Ortega-Cantero, E.; Rojas-
Cervantes, M. L.; Vincete-Rodriguez, M. A.; Banares-
Munoz, M. A. Technical Note Ultasound-activated
Knoevenagel condensation of malononitrile with
carbonylic compounds catalyzed by alkaline-doped
saponites. J. Chem. Technol. Biotechnol. 2005, 80, 234–
238.
McCluskey, A.; Robinson, P. J.; Hill, T.; Scott, J. L.;
Edwards, J. K. Green Chemistry Approaches to the
Knoevenagel Condensation: Comparison of Ethanol, Water
and Solvent Free (Dry Grind) Approaches. Tetrahedron
Lett. 2002, 43, 3117–3120.
Zhang, W. –Q.; Zhang, W. –Y.; Wang, R. –D.; Ren, C. –
Y.; Li, Q. –Q.; Fan, Y. –P.; Liu, B.; Liu, P.; Wang, Y. –Y.
Effect of Coordinated Solvent Molecules on Metal
94.
95.
96.
107.
108.
97.
Coordination
Sphere
and
Solvent-
Induced
Transformations. Cryst. Growth Des. 2017, 17, 517–526.
Cai, Q.; Liang, G.; Xu, Y.; Qian, X.; Zhu, W. A Reusable
Heterogeneous Catalyst without Leaking Palladium for
Highly-Efficient Suzuki-Miyaura Reaction in Pure Water
under Air. RSC Adv. 2016, 6, 60996–61000
98.
99.
Robichaud,
B.
A.;
Liu,
K.
G.
Titanium
109.
110.
isopropoxide/pyridine mediated Knoevenagel reactions.
Tetrahedron Lett. 2011, 52, 6935–6938.
Wei, Y. D.; Zhang, S. G.; Yin, S. F.; Zhao, C.; Luo, S. L.;
Au, C. T. Solid superbase derived from lanthanum–
magnesium composite and its catalytic performance in the
Knoevenagel condensation under solvent-free condition.
Catal. Commun. 2011, 12, 1333–1338.
Ikeue, K.; Miyoshi, N.; Tanaka, T.; Machida, M. Ca-
Containing Mesoporous Silica as a Solid Base Catalyst for
the Knoevenagel Condensation Reaction Catal. Lett. 2011,
141, 877–881.
Pandey, S.; Bansal, D.; Gupta, R.
A Metalloligand
Appended with Benzimidazole Rings: Tetranuclear
[CoZn3] and [CoCd3] Complexes and Their Catalytic
Applications. New J. Chem. 2018, 42, 9847–9856.
100.
101.
Mondal, J.; Modak, A.; Bhaumik, A. Highly efficient
mesoporous base catalyzed Knoevenagel condensation of
ACS Paragon Plus Environment

Page 15 of 15
Crystal Growth & Design
1
2
3
4
5
6
For Table of Contents Use Only
7
8
9
Manuscript Title: Post-functionalized Metalloligands Based Catenated Coordination Polymers:
Syntheses, Structures and Effect of Labile Sites on Catalysis
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
Authors: Saurabh Pandey, Girijesh Kumar and Rajeev Gupta*
TOC Graphic:
Synopsis: This work illustrates the use of two post-functionalized metalloligands for the synthesis of
several homo- and hetero-metallic coordination polymers (HCPs) displaying intriguing one-dimensional
catenated architectures. Two sets of HCPs, differing by the presence or absence of coordinated water
molecules, demonstrate profound effect on the heterogeneous catalysis of Knoevenagel condensation
and cyanation reactions.
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
15
ACS Paragon Plus Environment