Ag-Based Coordination Polymers Based on Metalloligands and Their Catalytic Performance in Multicomponent A3-Coupling Reactions

Article abstract of DOI:10.1021/acs.cgd.8b00833

Two silver(I)-based coordination polymers (CPs), namely, 1-Ag and 2-Ag, have been synthesized by the reaction of Co-based metalloligands offering appended pyridyl groups. X-ray diffraction analyses revealed three-dimensional (3D) architectures for both 1-Ag and 2-Ag due to the coordination of Ag(I) ions to that of appended pyridyl groups. In the case of 1-Ag, transition from a two-dimensional network to the final 3D network was manifested due to the presence of argentophilic interactions. Both CPs illustrated noteworthy structural differences and interesting topologies as a result of coordination of Ag(I) ions to the metalloligands. Both CPs acted as the heterogeneous catalysts for A³-coupling reactions of aldehydes, secondary amines, and alkynes. Recyclability experiments substantiated the stable nature of CPs in promoting the A³-coupling reactions heterogeneously.

Full text of DOI:10.1021/acs.cgd.8b00833

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Article
Ag-based Coordination Polymers Based on Metalloligands and Their
Catalytic Performance in Multi-Component A3#Coupling Reactions
Gulshan Kumar, Saurabh Pandey, and Rajeev Gupta
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00833 • Publication Date (Web): 16 Jul 2018
Downloaded from http://pubs.acs.org on July 19, 2018
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Crystal Growth & Design
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Ag-based Coordination Polymers Based on Metalloligands and Their
Catalytic Performance in Multi-Component A3−Coupling Reactions
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Gulshan Kumar, Saurabh Pandey and Rajeev Gupta*
Department of Chemistry, University of Delhi, Delhiꢀ110007, India
Abstract: Two silver(I) based coordination polymers (CPs) namely, 1-Ag and 2-Ag, have been synthesized by the reaction of Coꢀ
based metalloligands offering appended pyridyl groups. X–ray diffraction analyses revealed 3D architectures for both 1-Ag and 2-
Ag due to the coordination of Ag(I) ions to that of appended pyridyl groups. In case of 1-Ag, transition from 2D network to the
final 3D network was manifested due to the presence of argentophilic interactions. Both CPs illustrated noteworthy structural
differences and interesting topologies as a result of coordination of Ag(I) ions to the metalloligands. Both CPs acted as the
heterogeneous catalysts for A3–coupling reactions of aldehydes, secondary amines and alkynes. Recyclability experiments substanꢀ
tiated the stable nature of CPs in promoting the A3–coupling reactions heterogeneously.
used.56–64 However, there are multiple drawbacks associated
with these metal salts, such as their poor effectiveness, limited
Introduction
Coordination polymers (CPs) have been the subject of imꢀ
stability and water sensitivity, that have restricted their wider
mense interest due to their remarkable structural features often
applications.65,66 Along the similar line, reusability is a major
controlling their interesting physical and chemical properties.1
concern with most of the homogenous catalysts.67–70 Thereꢀ
As a special class of designer porous materials, CPs offer
noteworthy applications in the field of sorption,2–3 separation,4
fore, efforts have been made to immobilize catalytic metals on
catalysis,5–7 sensing,8–9 ionꢀexchange,10–11 transport,12–13 magꢀ
various solid supports, such as zeolite, silica, as well as organꢀ
ic polymers.59,71–74 However, most of such immobilized mateꢀ
netism,14–15 and proton and hydroxide conduction.16–18 One of
rials suffer from cumbersome preparative routes, high temperꢀ
the major challenges being faced in CPs research is to improꢀ
vise the design concepts so as to improve their performance.19–
ature requirement, long reaction time, leaching of catalytic
metals, and poor catalytic performance.62,75–78 In this context,
CPs offer promising heterogeneous catalytic possibilities for
21
In this context, metalloligands have been found to be quite
impressive in controlling the structural aspects so as to move
various organic transformations.79–83 Such an advantageous
towards predictable architectures.1,22 Importantly, metalloligꢀ
situation is primarily due to their ability to retain their strucꢀ
and strategy typically generates stable CPs with minimum
tural architecture during the catalysis, thermal stability and
sensitivity to the structural collapse as a result of the loss of
their reusability.84–87 In this work, two Ag(I) based CPs have
solvates.23–30 More importantly, metalloligands tend to generꢀ
been synthesized using two different Co3+ꢀbased metalloligꢀ
ate nonꢀinterpenetrated networks therefore significantly imꢀ
proving the analyte and/or substrate accessibility.31–34 These
ands offering appended pyridyl groups (Scheme 1). Both CPs
illustrate interesting threeꢀdimensional (3D) architectures inꢀ
structural features have produced some noteworthy catalytic
CPs based on the metalloligands.35,36
cluding argentophillic interactionsꢀled stabilization of 3D netꢀ
work in one case. Both Agꢀbased CPs function as the reusable
Compared to the most of transition metals, silver has a
heterogeneous catalysts for the synthesis of propargylamines
applying one–pot–threeꢀcomponent (A3) coupling.
stronger affinity for Nꢀdonor ligands while supporting variable
coordination numbers and multifaceted geometries, ranging
from linear and Tꢀshaped to all the way to octahedral ones.37–39
Furthermore, Ag(I) ion with a d10 closedꢀshell electronic conꢀ
figuration often displays argentophilic interactions which furꢀ
ther assist in the stabilization of polymetallic architectures.40–44
These structural features have been extensively used in the
construction of assorted architectures.45–50
A3–coupling led synthesis of substituted propargylamines is
significant as such molecules are not only important structural
synthons in natural products and pharmaceuticals but are also
Scheme 1. Preparative route for the synthesis of coordination
polymers, 1-Ag and 2-Ag.
versatile intermediates in assorted organic reactions.50–55 Altꢀ
hough several methods have been developed for their syntheꢀ
sis but efficient and costꢀeffective protocols are still limꢀ
ited.56,57 The importance of such reactions increases manifold
if reusable catalysts could be used, particularly under heteroꢀ
geneous reaction conditions for the facile product separaꢀ
tion.58,59 For promoting such reactions, several homogeneous
catalysts, such as salts of Zn, Cu, Fe, Ag, and Au have been
Experimental Section
Materials and Reagents
All chemicals and reagents of analytical grades were used
without further purification unless otherwise stated. Standard
literature methods were used for the purification of organic
solvents.88,89 Metalloligands [Co(L4Py)2]− (1) and [Co(L3Py)2]−
(2) (where H2L4Py: 2,6ꢀbis(Nꢀ(4ꢀpyridyl)carbamoyl)pyridine
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Crystal Growth & Design
and H2L3Py: 2,6ꢀbis(Nꢀ(3ꢀpyridyl)carbamoyl)pyridine), as their
Page 2 of 13
data collection and structural solution parameter are provided
1
2
tetraethyl ammonium salt, were synthesized according to our
in Table 1. Topological analysis for 1-Ag and 2-Ag was carꢀ
earlier report.90
ried out by using ToposPro 5.1.0.7 software.96–98
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Syntheses
Table 1. Crystallographic data collection and structure reꢀ
finement parameters for 1-Ag and 2-Ag.
[{(1)Ag2(H2O)2}.2H2O]n (1-Ag). A DMSO solution (3 mL) of
metalloligand 1 (100 mg, 0.1004 mmol) was layered over an
aqueous solution of Ag(CF3COO) (59 mg, 0.3036 mmol) with
an intermediate layer of tertꢀbutanol. Visible light was avoided
during the crystallization. Lightꢀgreen crystalline material was
obtained after 5–7 d which was filtered, washed with diethyl
ether and dried under vacuum. Yield: 208 mg (83 %).
C34H30CoAg2N10O8, (981.34): calcd. C, 41.61; H, 3.08; N,
14.27. Found C, 41.19; H, 3.64; N, 14.79. FTIR spectrum
(Zn–Se ATR, selected peaks): (ν/cm–1) = 3380 (H2O); 1573
(C=O).
1-Ag
2-Ag
Empirical
formula
C34H22Ag2CoN10O8
C72H56Ag3Co2N20O12S2
FW
973.29
1898.95
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T(K)
293(2) K
293(2) K
Crystal
system
Orthorhombic
Orthorhombic
Space
group
Pnna
Pbca
[{(2)2Ag3}·2H2O·2DMSO]n (2-Ag). 2-Ag was synthesized
identically as mentioned for 1-Ag; however, using
metalloligand
C72H60Ag3Co2N20O12S2 (1902.99): calcd. C, 45.44; H, 3.18; N,
14.27; S, 3.37. Found C, 45.19; H, 3.44; N, 14.67. FTIR
spectrum (Zn–Se ATR, selected peaks): (ν/cm–1) = (H2O):
3380; 1593, 1556 (C=O); ν(S=O, DMSO): 1040.
a (Å)
b (Å)
18.302(5)
18.201(5)
14.536(5)
90
15.5552(8)
16.0646(8)
31.4260(12)
90
2.
Yield:
215
mg
(88
%).
c (Å)
α = β = γ (˚)
V (Å)3
4842(3)
4
7853.0(6)
4
Physical Measurements
Z
Elemental analysis data were obtained with an Elementar
Analysen Systeme GmbH Vario ELꢀIII instrument. FTIR
spectra were recorded with a PerkinꢀElmer SpectrumꢀTwo
spectrometer having ZnꢀSe ATR. NMR spectroscopic measꢀ
urements were carried out with a Jeol 400 MHz spectrometer.
Perkin Elmer Clarusꢀ580 and Shimadzu QPꢀ2010 instruments
were respectively used for the gas chromatography (GC) and
GC–MS studies having RTXꢀ5 SILꢀMS column. Thermal
gravimetric analysis (TGA) and differential scanning calorimꢀ
etry (DSC) were performed with Shimadzu DTGꢀ60 and
TADSC Q200 instruments, respectively, under the nitrogen
atmosphere. X–ray powder diffraction (XRPD) studies were
performed either with an X’Pert Pro from PANanalytical or a
Bruker AXS D8 Discover instrument (Cu–Kα radiation, λ =
1.54184 Å). The samples were ground and subjected to 5–35°
θ range at a slow scan rate at room temperature.
d (g cm–3)
µ (mm–1)
F (000)
R (int.)
1.3350
1.189
1.606
1.274
1924
3804
0.1097
0.1328
Final R
R1 = 0.0670
0.1011
indicesa
[I>2σ(I)]
R indices
All data
wR2 = 0.1669
R1 = 0.1443
wR2 = 0.2063
0.928
0.2690
0.1481
0.3116
0.992
GOF on F2
CCDC No.
1846547
1846548
Typical procedure for A3−coupling reaction
Crystallography
In a typical reaction, an aldehyde, an amine, and an alkyne
were allowed to react in 1.0:1.5:1.5 ratio under the solventꢀ
free conditions in presence of 2ꢀmol% of a catalyst (1-Ag or 2-
Ag). The progress of the reaction was monitored by thin layer
chromatography (TLC) and/or gas chromatography (GC)
techniques. After 1 h, ethyl acetate was added that resulted in
the separation of solid catalyst which was filtered off and dried
under vacuum. The recovered catalysts were characterised by
FTIR spectra as well as PXRD studies. The ethyl acetate layer
was washed with water (2x) and dried over anhyd. Na2SO4.
The solvent was evaporated under vacuum to isolate the orꢀ
ganic products. This product was purified using the flash colꢀ
umn chromatography on silica gel with 5% EtOAc/hexanes as
the eluent. The organic products were analyzed and/or quantiꢀ
fied by the GC/GC–MS techniques and proton NMR spectra
(Figures S1 – S16, SI).
Xꢀray diffraction data for 1-Ag and 2-Ag were colected on an
Oxford Xcalibur CCD diffractometer equipped with a graphite
monochromatic MoKα radiation (λ = 0.71073 Å).91 The
frames were collected at 293(2) K. An empirical absorption
correction was applied using spherical harmonics implemented
in SCALE3 ABSPACK scaling algorithm.91 The structures
were solved by the direct methods using SIRꢀ9792 and refined
by the fullꢀmatrix leastꢀsquares refinement techniques on F2
using SHELXLꢀ2016/493 incorporated in WINGX 1.8.05
crystallographic package.94 The hydrogen atoms were fixed at
the calculated positions with isotropic thermal parameters
whereas nonꢀhydrogen atoms were refined anisotropically.
The hydrogen atoms of the coordinated as well as
uncoordinated water molecules could not be located from the
Fourier map; however, their contributions are included in the
empirical formulae. As there was a large amount of diffused
electron density, the model was SQUEEZED for better conꢀ
vergence and to remove any diffused electron density by using
the PLATON SQUEEZE procedure.95 This procedure signifiꢀ
cantly improved the structural convergence both for 1-Ag (R =
0.067) and 2-Ag (R = 0.101). Details of the crystallographic
Characterization data for
a
few representative
A3−coupling products:
1-(1,3-diphenylprop-2-n-1-yl)pyrrolidine. 1H NMR specꢀ
trum (400 MHz, CDCl3) δ 7.62 (d, J = 7.2 Hz, 2H), 7.50 (dd, J
= 6.3, 2.9 Hz, 2H), 7.40–7.34 (m, 2H), 7.34–7.27 (m, 4H),
4.90 (s, 1H), 2.71 (t, J = 6.7 Hz, 4H), 1.81 (t, J = 6.3 Hz, 4H).
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Crystal Growth & Design
13C NMR spectrum (100 MHz, CDCl3) δ 139.39, 131.89,
128.35, 127.7, 87.0, 86.6, 59.2, 50.3, 23.5.
presence of either coordinated or lattice water molecules by
1
displaying weight loss in the temperature range of 60–150 °C
(Figures S19 and S20, SI). For 1-Ag, an observed weight
change of 7.95% fits nicely with the calculated value of 7.33%
corresponding to the loss of one coordinated and one lattice
water molecule. In case of 2-Ag, observed weight loss of
4.70% is in close match with the calculated value of 5.06% for
the loss of one water and one DMSO molecule present in latꢀ
tice. DSC plots for both CPs exhibit broad exothermic features
in the region of 60–150 °C for the loss of solvent molecules
thereby supporting TGA results. Thermal studies further sugꢀ
gest that both CPs are thermally stable up to ca. 350 °C. Difꢀ
fuse–reflectance absorption spectra of both CPs display broad
features at 453ꢀ458 nm and 634ꢀ654 nm (Figure S21, SI). The
lowꢀenergy spectral band has been assigned to be based on
Co3+–based metalloligand.101–103 X–ray powder diffraction
(XRPD) studies were used to confirm the crystalline homogeꢀ
neity and bulk purity of the CPs. The experimental XRPD
patterns closely match the ones simulated from the single crysꢀ
tal diffraction data for both CPs (Figures S22 and S23, SI)
thereby inferring a single crystalline phase.
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1-(1-4-methoxyphenyl)-3-phenylprop-2-yn-1-
yl)pyrrolidine. 1H NMR spectrum (400 MHz, CDCl3) δ 7.52–
7.44 (m, 4H), 7.32–7.28 (m, 3H), 6.90–6.86 (m, 2H), 4.80 (s,
1H), 3.80 (d, J = 3.5 Hz, 3H), 2.66 (t, J = 6.7 Hz, 4H), 1.78 (t,
J = 6.2 Hz, 4H). 13C NMR spectrum (100 MHz, CDCl3) δ
159.0, 131.8, 129.4, 128.3, 128.1, 123.3, 113.6, 87.0, 86.7,
58.6, 55.3, 50.3, 23.5.
1-(1-(4-cholorophenyl)-3-phenylprop-2-yn-1-
yl)pyrrolidine. 1H NMR spectrum (400 MHz, CdCl3) δ 7.55 –
7.42 (m, 4H), 7.34 – 7.28 (m, 3H), 6.92 – 6.82 (m, 2H), 4.80
(s, 1H), 3.80 (s, 3H), 2.66 (t, J = 6.7 Hz, 4H), 1.78 (t, J = 6.2
Hz, 4H). 13C NMR spectrum (100 MHz, CdCl3) δ 138.16,
133.36, 131.87, 129.69, 128.61 – 128.21, 123.02, 87.36,
86.05, 58.45, 50.22, 23.54.
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1-(3-(4-(tert-butyl)phenyl)-1-phenylprop-2-yn-1-
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yl)pyrrolidine. H NMR spectrum (400 MHz, CDCl3) δ 7.59
(d, J = 7.3 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.34 (t, J = 7.5
Hz, 4H), 7.28 (d, J = 7.1 Hz, 1H), 4.87 (s, 1H), 2.66 (d, J = 6.4
Hz, 4H), 1.78 (t, J = 6.0 Hz, 4H), 1.30 (s, 9H). 13C NMR specꢀ
trum (100 MHz, CDCl3) δ 151.4, 139.7, 131.5, 128.3, 127.5,
125.3, 120.2, 87.0, 85.9, 59.1, 50.2, 34.8, 31.2, 23.5.
1-(3-(4-(tert-butyl)phenyl)-1-(4-cholorophenyl)prop-2-yn-1-
1
yl)pyrrolidine. H NMR spectrum (400 MHz, CDCl3) δ 7.54
(d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 7.35–7.28 (m,
4H), 4.85 (s, 1H), 2.65 (dd, J = 10.4, 5.9 Hz, 4H), 1.77 (t, J =
6.1 Hz, 4H), 1.30 (s, 9H). 13C NMR spectrum (100 MHz,
CDCl3) δ 151.6, 138.3, 133.2, 131.5, 129.6, 128.4, 125.4,
120.0, 85.3, 58.4, 50.1, 34.8, 31.2, 23.5.
1-(3-(4-fluorophenyl)-1-(4-meyhoxyphenyl)prop-2-yn-
1yl)pyrrolidine. 1H NMR spectrum (400 MHz, CDCl3) δ 7.50
(d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.3
Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 4.80 (s, 1H), 3.80 (s, 3H),
2.65 (s, 4H), 1.77 (t, J = 5.6 Hz, 4H), 1.30 (s, 9H). 13C NMR
spectrum (100 MHz, CDCl3) δ 159.0, 151.3, 131.9, 131.5,
129.4, 125.3, 120.3, 113.6, 86.7, 86.3, 58.5, 55.3, 50.2, 34.8,
31.2, 23.5.
1-(3-(4-fluorophenyl)-1-phenylprop-2-yn-1-yl)pyrrolidine.
1H NMR spectrum (400 MHz, CDCl3) δ 7.57 (d, J = 7.3 Hz,
2H), 7.45 (dd, J = 8.5, 5.4 Hz, 2H), 7.35 (t, J = 7.3 Hz, 2H),
7.29 (d, J = 7.1 Hz, 1H), 7.00 (dd, J = 14.2, 5.5 Hz, 2H), 4.84
(s, 1H), 2.67 (s, 4H), 1.80 (d, J = 5.9 Hz, 4H). 13C NMR specꢀ
trum (100 MHz, CDCl3) δ 133.7, 128.3, 127.7, 115.7, 115.4,
92.5, 84.4, 59.2, 50.4, 23.5.
1-(1-(4-chlorophenyl)-3-(4-fluorophenyl)prop-2-yn-1
1
yl)pyrrolidine. H NMR spectrum (400 MHz, CDCl3) δ 7.52
(d, J = 8.4 Hz, 2H), 7.44 (dd, J = 8.6, 5.5 Hz, 2H), 7.36–7.28
(m, 2H), 7.00 (dd, J = 12.2, 5.1 Hz, 2H), 4.82 (s, 1H), 2.63 (s,
4H), 1.79 (d, J = 5.9 Hz, 4H). 13C NMR spectrum (100 MHz,
CDCl3) δ 138.1, 133.7, 133.4, 129.6, 128.5, 115.7, 115.5, 86.2,
85.8, 58.4, 50.3, 23.5.
Results and Discussion
Pale green–coloured crystalline 1-Ag and 2-Ag were respecꢀ
tively synthesized from metalloligands 1 and 2. Both CPs
show broad νOꢀH stretches in the range of 3360–3410 cm–1 due
to the presence of coordinated water in 1-Ag and lattice water
molecules in 2-Ag (Figures S17 and S18, SI).99,100 Strong
bands in the region of 1545–1565 cm–1 corresponds to the
amidic νC=O stretches.99,100 For both CPs, TGA supports the
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Figure. 1 (a) Asymmetric unit of 1-Ag, a lattice water molecule and hydrogen atoms are omitted for clarity. Selected bond distances (Å):
Co1–N(1), 1.954(5); Co1–N(2), 1.869(5); Co1–N(3), 1.984(5); Ag1–N(4), 2.148(6); Ag1–O2W, 2.093(6); Selected bond angles (°): N(1)–
Co1–N(2), 81.2(2); N(1)–Co1–N(3), 162.1(2); N(2)–Co1–N(3), 80.9. (b) Partial crystal structure of 1-Ag illustrating the coordination of
pyridyl fragments to the secondary Ag(I) ions. (c) A combination of metalloligands (shown in different colors) to that of silver atoms
generates a 2D network. (d) Weak argentophilic interactions between adjacent Ag(I) ions from two different layers (shown in red and
green colors, respectively) connect two parallel 2D layers together. (e) Topological representation of 1-Ag where yellow and green nodes
respectively represent silver atoms and metalloligands.
Crystal Structures
(shown by red and green colors in Figure 1d) are further conꢀ
nected to each other and generate a threeꢀdimensional (3D)
architecture. Thus, argentophilic interactions play a critical
role in controlling the overall 3D structure of 1-Ag. The 3D
nature of 1-Ag as a result of argentophilic interactions is clearꢀ
ly visible in the resultant topology (Figure 1e).108 Herein, a
SBU is composed of a silver atom coordinated by two pyridyl
rings (shown in yellow color) whereas two parallel sheets are
further connected as a result of argentophilic interactions.
Such SBUs are connected to the Co3+–based building blocks
acting as tetratopic nodes (shown in green color) while parallel
sheets are held together due to argentophilic interactions,
therefore generating a 3D network. Topologically, 1-Ag illusꢀ
trates a 3D network with two nodal net and point symbol
{82.12} (Figure 1e).96ꢀ98
Both CPs, 1-Ag and 2-Ag, were crystallographically charꢀ
acterized and their structures are shown in Figures 1 and 2,
respectively. CP 1-Ag was crystallized in orthorhombic cell
with Pnna space group. The asymmetric unit of 1-Ag is conꢀ
sisted of half Coꢀbased metalloligand, one silver atom, one
coordinated water molecule, and a lattice water molecule
(Figure 1a). Every metalloligand provides one negative charge
which is balanced by one Ag+ ion. A metalloligand illustrates
two tridentate ligands arranged meridionally around the Co3+
ion maintaining a compressed octahedral geometry (Figure
1b). The Co3+ ion is coordinated by four Namide atoms in a disꢀ
torted basal plane whereas two Npyridine atoms occupy the axial
positions.104–107 The Co−Namide (avg. 1.952 Å) bond distances
were longer than that of Co−Npyridine distances (avg. 1.860
Å).104–107 The Ag(I) ion exhibits T–shaped geometry where
two coordinations come from two pyridyl groups from two
different metalloligands whereas the remaining one site is
ligated by a water molecule (Figures 1b and 1c).
A metalloligand offers four appended pyridyl groups that
coordinate to four different Ag(I) ions in different directions
therefore generating a twoꢀdimensional (2D) sheetꢀlike archiꢀ
tecture. Importantly, crystal structure of 1-Ag exhibits promiꢀ
nent argentophilic interactions with dAg····Ag of 3.375 Å. These
Ag…Ag interactions are present between two silver atoms
from two parallel sheets (Fig. 1d). As a result, two 2D sheets
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Crystal Growth & Design
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Figure. 2 (a) Asymmetric unit of 2-Ag, one lattice water, a DMSO molecules and hydrogen atoms are omitted for clarity. Selected bond
distances (Å): Co1–N(1), 1.957(8); Co1–N(2), 1.852(8); Co1–N(3), 1.953(9); Co1–N(4), 1.979(8); Co1–N(5), 1.876(8); Co1–N(6),
1.969(9); Ag1–N(10), 2.228(9); Ag2–N(8), 2.192(12); Selected bond angles (°): N(2)–Co1–N(5), 177.9(4); N(2)–Co1–N(3), 81.29(5);
N(5)–Co1–N(3), 96.7(4); N(10)–Ag1–N9, 110.9(4); N(10)–Ag1–N(7), 145.1(3); N(8)–Ag1–N(8), 180.0. (b) Partial crystal structure of 2-
Ag illustrating the coordination of pyridyl fragments to the secondary silver metals. (c) Coordination environment around the Ag1 and Ag2
atoms and its bonding to Npyridyl groups from different metalloligands. (d) A combination of metalloligands (shown in different colors) and
silver atoms give rise to a network which is actually composed of two individual parts shown on left and right sides; see text for details. (e)
Topological representation (view along 001) of 2-Ag where yellow and green nodes respectively represent silver atoms and metalloligands.
(f) A different orientation of topological representation illustrating a layerꢀbased structure.
Notably, Ag…Ag distance in silver metal is 2.88 Å whereꢀ
as sum of van der Waals radii for two Ag atoms is 3.44 Å.109
Strong argentophilic interactions are typically ˂3.0Å whereas
distances >3.3Å are considered to be weak argentophilic interꢀ
actions.110 A comparison suggests that 1-Ag illustrates weak
argentophilic interactions.110ꢀ112
Importantly, 1-Ag exhibits the presence of pores in the reꢀ
sultant 3D network with dimensions of 13.62 x 8.21 Å2. Such
pores are arranged into channels throughout the network and
accommodate lattice water molecules. Such a unique structural
feature is expected to enhance substrate accessibility during
the catalytic applications.
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Single crystal X–ray diffraction of 2-Ag revealed that it network in accommodating and releasing molecular iodine
1
crystallized in orthorhombic cell with Pbca space group. The
asymmetric unit of 2-Ag contains one metalloligand, two half
occupancy silver atoms, one water and a DMSO molecule in
the crystal lattice (Figure 2a). Every metalloligand generates
one negative charge which is balanced by two half occupancy
Ag(I) ions. As seen in 1-Ag, Co3+ ion displays a compressed
octahedral geometry coordinated by two meridional tridentate
ligands (Figure 2b).104ꢀ107 Interestingly, in 2-Ag, silver exhibits
two different coordination geometries; threeꢀcoordinated disꢀ
torted triangular planar geometry and twoꢀcoordinated linear
geometry (Figure 2c). Importantly, in both cases, all coordinaꢀ
tion sites are satisfied by Npyridyl groups. The overall 3D netꢀ
work is composed of two parts. Initially, a 2D sheetꢀlike strucꢀ
ture is created by the involvement of threeꢀcoordinated Ag(I)
ions (right side of Figure 2d). Subsequently, such 2D sheets
are perpendicularly connected via twoꢀcoordinated Ag(I) ions
(left side of Figure 2d) therefore producing a 3D network.
Such a packing between metalloligands and Ag(I) ions proꢀ
duces a densely packed 3D structure (Figure 2d). Topology of
2-Ag (Figure 2e) clearly exhibits both twoꢀcoordinated (as 2ꢀ
connected node) as well as threeꢀcoordinated (as 3ꢀconnected
nodes) Ag atoms. Such nodes act as the SBUs in the resultant
network whereas metalloligands function as the tetraꢀtopic
nodes. A combination of two provides five nodal net and point
symbol {10.16.18}2{103}4{10}2{16} (Fig. 1e).96ꢀ98
from its pores and channels.
2
3
4
5
6
7
8
9
We also investigated inclusion of benzaldehyde (subseꢀ
quently used in A3ꢀcoupling) both with 1-Ag and 2-Ag. For
such studies, deꢀsolvated samples were impregnated by dipꢀ
ping crystals in a CH2Cl2 solution of benzaldehyde. Such imꢀ
pregnated samples were investigated by FTIR spectra, XRPD
patterns as well as SEM and optical images. The FTIR spectra
suggested the inclusion of benzaldehyde within the crystal
lattice as noted by the redꢀshifted νC=O stretches of benzaldeꢀ
hyde (Figures S27 and S28, SI). Interestingly, inclusion of
benzaldehyde resulted in a visible color change of the crystals
from green to black (Figures S29 and S30, SI). However, SEM
images did not show noticeable morphological changes to the
crystal surface (Figures S31 and S32, SI) suggesting that the
inclusion has not significantly affected the crystallinity. The
convincing proof about the stability of the crystalline samples
was obtained from the XRPD studies that did not show measꢀ
urable changes to that of pristine samples (Figures S33 and
S34, SI). Collectively, these studies strongly suggest the incluꢀ
sion of benzaldehyde within the crystal lattice without comꢀ
promising the crystallinity.
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Catalytic A3−Coupling Reactions
The presence of lowꢀcoordinated Ag(I) ions both in 1-Ag and
2-Ag suggest that a suitable substrate and/or reagent could
potentially approach such metals whereas exchange and sorpꢀ
tion studies with 1-Ag indeed proves such a point. On the othꢀ
er hand, 3D polymeric nature of two CPs suggests their potenꢀ
tial utilization as the heterogeneous catalysts. Therefore, both
1-Ag and 2-Ag were screened as the heterogeneous catalysts
for the synthesis of propargylamines via A3ꢀcoupling of aldeꢀ
hydes, amines and alkynes.
There are several notable structural differences between the
two CPs. In 1-Ag, all silver atoms offered identical coordinaꢀ
tion environment where two coordinations come from the
metalloligands while the third one was satisfied by a water
molecule. The presence of a water molecule may assist in its
facile removal and/or exchange and such a situation is likely to
assist in catalysis (vide infra). In contrast, silver atoms in 2-Ag
displayed two types of coordination environments that resulted
in densely packed molecular components when compared to 1-
Ag. We anticipate that such a difference between two CPs
may result in considerable difference in their catalytic perforꢀ
mance (vide infra).
Initially, reaction conditions were optimized to achieve
maximum product formation using benzaldehyde, phenyl
acetylene and pyrrolidine as the model coupling reagents
utilizing only 1 mol% of 1-Ag as a representative catalyst
(Table 2). Various solvents such as ethanol, water, THF, and
toluene were screened to find out the best solvent (entries 1 –
4); however, maximum product formation was observed
without the use of any solvent (92%; entry 7). Temperature
screening revealed that elevated temperature enhanced the
product formation (entries 5 – 8). Although best results were
obtained at 100 °C; subsequent reactions were only performed
at 80 °C. The effect of assorted secondary amines as the
nucleophile (pyrrolidine, piperidine, piperazine and
morpholine) was also evaluated (entry 7–11) and the best
product yield was noted with pyrrolidine when compared to
other amines. The use of Ag(CF3COO), Ag(OTf) and AgCl as
the catalyst resulted in quite low product formation (entry 12–
14). Such a fact suggests the significance of 1-Ag in
promoting A3ꢀcoupling reactions. Finally, an identical reaction
was carried out without the use of any catalyst that produced
the respective product in only 12% yield (entry 15). Similarly,
use of metalloligands 1 and 2 as the catalysts only produced
desired product in 10 – 15% yield (entries 16–17). These
Exchange, Adsorption and Inclusion Studies
As 1-Ag displayed a coordinated water molecules to the Ag(I)
center, solvent–exchange studies were carried out to evaluate
its possible exchange or replacement with potential substrate
and/or reagents.113,114 For such a study, 1-Ag was heated up to
80 °C under vacuum for 6 h to remove both coordinated and
lattice water molecules. Subsequently, desolvated 1-Ag was
allowed to equilibrate in a sealed environment of D2O vaꢀ
pours. Such a sample exhibited νOꢀD stretches at ca. 2500 cm–1
(ꢀ = 900 cm–1) and potentially suggest the exchange of ligated
H2O with D2O (Figure S24, SI).115–117 A similar exchange usꢀ
ing CH3OH vapours displayed νC–O stretch for the ligated
CH3OH at 1020 cm–1 (Figure S25, SI).
The desolvated sample of 1-Ag was further used to invesꢀ
tigate possible inclusion of molecular iodine within its pores
and channels. Notably, a 20 mg sample of 1-Ag was able to
adsorb nearly 2 mg of I2 which corresponded to ca. 10.0%
weight change. Such an adsorption resulted in a distinct colour
change from green (1-Ag) to dark brown (1-Ag+I2) (Figure
S26, SI).118,119 Importantly, iodine adsorption process was reꢀ
versible as the green coloured 1-Ag was regenerated after
evacuating the dark brown solid indicating the stable nature of
reactions confirmed the importance of 1-Ag as
a
heterogeneous catalyst and rule out the leaching of Ag(I) ion
from the CPs (vide infra).
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Crystal Growth & Design
Table 2. Optimisation of the reaction conditions for the A3–
coupling reactions.
1
2
ꢀH
ꢀCl
ꢀH
ꢀH
ꢀH
ꢀH
92
93
92
98
94
96
91
99
83
84
81
91
86
77
79
91
84
84
87
88
79
79
77
87
1
2
3
4
5
6
7
8
3
ꢀOMe
ꢀNO2
ꢀH
4
t
5
ꢀ Bu
T
(o C)
t
S.
Yield
(%)
6
ꢀCl
ꢀ Bu
Catalyst
No
Amine
Solvent
t
7
ꢀOMe
ꢀNO2
ꢀH
ꢀ Bu
1
2
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Piperidine
Piperazine
Morpholine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
80
80
80
80
40
60
80
100
80
80
80
80
80
80
80
80
80
EtOH
66
71
59
54
36
74
92
93
76
58
30
30
23
26
12
11
15
1-Ag
1-Ag
t
8
ꢀ Bu
H2O
9
9
ꢀF
ꢀF
ꢀF
ꢀF
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
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59
60
3
1-Ag
THF
10
11
12
ꢀCl
4
Toluene
1-Ag
ꢀOMe
ꢀNO2
5
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
1-Ag
6
1-Ag
Conditions: Catalyst: 1ꢀmol%; Temperature: 80 °C; Time: 60 min.
7
1-Ag
We further extended A3ꢀcoupling reactions to a few chalꢀ
lenging aldehydes of biological importance along with pyrrolꢀ
idine and phenyl acetylene (Table 4). Importantly, both CPs,
1-Ag and 2-Ag, promoted such reactions smoothly to afford
the respective propargylamines in yields ranging from 70 to 88
%.
8
1-Ag
9
1-Ag
10
11
12
13
14
15
16
17
1-Ag
1-Ag
AgCOOCF3
AgOTf
AgCl
No catalyst
1
Table 4. A3–coupling reaction of some biologically relevant
aldehydes using 1-Ag and 2-Ag as the catalysts.
Yield (%)
Aldehyde
Product
1-Ag
2-Ag
2
Conditions: Catalyst: 1ꢀmol%; Time: 60 min.
88
82
These control experiments paved the foundation to evaluate
the scope as well as the versatility of both CPs as the heteroꢀ
geneous catalysts in promoting multiꢀcomponent coupling
reactions using different coupling partners bearing electronic
substituents (Table 3). To evaluate the effect of electronic
subsituents (e–ꢀdonating or e–ꢀwithdrawing) on product yield,
several para–substituted benzaldehydes as well as para–
substituted alkynes were used. It was observed that both
electron rich as well as electron poor aldehydes were
somewhat equally effective with both the catalysts. Although,
presence of eꢀꢀwithdrawing substituent at the para–position of
benzaldehyde did increase the product yield (entry 4); eꢀꢀ
donating group at paraꢀposition did not show much effect
(entry 3) when compared to only benzaldehyde. Notably, an eꢀ
ꢀdonating group at the paraꢀposition of ethynylbenzene
increased the product conversion due to the enhanced
nucleophilicity (entries 5–8). In contrast, when 1ꢀethynylꢀ4ꢀ
fluorobenzene was used in place of ethynylbenzene, product
yield was reduced due to the lower nucleophilicity of alkyne
(entries 9–12). In fact, nearly quantitative A3ꢀcoupling product
was obtained using 1-Ag as a catalyst when –tBu and –NO2
groups were respectively placed on the para position of
ethynylbenzene and benzaldehyde (entry 8).
86
83
80
76
78
75
74
70
Conditions: Catalyst: 1ꢀmol%; Temperature: 80 °C; Time: 60 min.
Although both 1-Ag and 2-Ag efficiently carried out A3ꢀ
coupling of substituted benzaldehydes, substituted alkynes and
pyrrolidine but it can precisely be noticed that 1-Ag is a better
catalyst than 2-Ag. We believe that such a difference in catalꢀ
ysis is related to the structures of two CPs. 1-Ag offers open
structure as a result of well–defined pores and channels
throughout its 3D architecture that allows facile diffusion of
substrates and reagents as was also illustrated by the exchange
and adsorption studies. In contrast, 2-Ag presents somewhat
Table 3. A3–coupling reactions using 1-Ag and 2-Ag as the
catalysts.
Yield (%)
Entry
R1
R2
1-Ag
2-Ag
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Figure 3. Reusability of 1-Ag as a catalyst for five consecutive
densely packed structure that may not have effectively supꢀ
ported the substrate and reagents’ diffusion that has resulted in
comparatively poor product yield.
1
2
runs for the A3ꢀcoupling reaction between benzaldehyde, pyrroliꢀ
dine and phenyl acetylene.
3
4
Recyclability Studies
100
90
80
70
60
As catalytic reactions were carried out heterogeneously, both
CPs can be conveniently recovered after the reactions. Such a
fact provided the opportunity to test their reusability as well as
stability before and after the catalytic reactions. Subsequently,
1-Ag, as a representative example, was recovered from a reacꢀ
tion between benzaldehyde, pyrrolidine and phenyl acetylene
in nearly quantitative yield and was reused five times without
apparent loss in its catalytic performance (Figure 3).
5
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60
50
a
b
c
d
40
30
20
10
0
A major disadvantage of heterogeneous catalysis is the poꢀ
tential leaching of the catalytically active species from a solid
catalyst.120–122 Often, such a leached but a catalytically active
120–122
species actually carries out a reaction.
To test such a
hypothesis, hot filtration test, in which solid catalyst is filtered
off during the reaction while the filtrate is monitored for
continued activity, was performed.102 A reaction involving
benzaldehyde, pyrrolidine and phenylacetylene was taken as a
model reaction for the hot filtration test in presence of 1-Ag as
a representative catalyst (Figure 4). The reaction was allowed
to coninue for 30 min and thereafter solid 1-Ag was removed
via filtration while the reaction was further continued. As
clearly visible, negligible product formation took place after
the removal of 1-Ag. However, once 1-Ag was readded to the
same reaction mixture at 60 min, the catalysis resumed
producing the product in high yield. This simple test confirm
the true heterogeneous nature of catalysis and rules out the
leaching of any catalytically active species. Figure 4 also disꢀ
plays disappearance of benzaldehyde as a function of time (red
dots) that correlates nicely with the formation of propargylaꢀ
mine, as the desired product (black squares). Such a fact rules
out other undesirable reactions parallely taking place within
the reaction mixture.
0
10
20
30
40
50
60
70
80
90
Time (Minutes)
Figure 4. (a) A3–coupling reaction of benzaldehyde, pyrrolidine
and phenylacetylene in presence of 1-Ag as a catalyst. (b) Disapꢀ
pearance of benzaldehyde as a function of time. (c) Catalyst 1-Ag
was filtered off after 30 min. leading to nearly termination of the
catalytic reaction. (d) Catalyst 1-Ag was reꢀadded at 60 min. causꢀ
ing commencement of the reaction.
Mechanistically, A3–coupling reactions proceed via the iniꢀ
tial coupling between an aldehyde and an amine producing the
corresponding iminium ion as the intermediate. Subsequently,
phenyl acetylene attacks the iminium ion to form the proparꢀ
gylamine. In this context, nucleophilicity of phenyl acetylene
becomes a decisive factor and eꢀꢀdonating groups on
ethynylbenzene are likely to enhance product formation as was
also noted in the present case (cf. Table 3).
Conclusions
The recovered 1-Ag was characterized and compared to
that of pristine sample. FTIR spectrum of recovered 1-Ag exꢀ
hibited nearly identical resonances to that of asꢀsynthesized 1-
Ag (Figure S35, SI). Furthermore, a comparison between the
XRPD patterns of as synthesized 1-Ag to that of recovered 1-
Ag after 2nd cycle revealed that both crystallinity as well as the
structural integrity of the sample is preserved during the cataꢀ
lytic cycles (Figure S36, SI). Collectively, these experiments
convincingly point towards the stable and reusable nature of
the present CPs in carrying out the A3–coupling reactions.
This work has shown synthesis and characterization of two
Agꢀbased CPs (1-Ag and 2-Ag) constructed by using two Coꢀ
based metalloligands decorated with appended pyridyl rings.
Crystal structures of 1-Ag and 2-Ag displayed 3D
architectures due to the coordination of Ag(I) ions by the
appended pyridyl groups. In case of 1-Ag, transition from 2D
sheets to a 3D network was manifested due to the presence of
argentophilic interactions. Two CPs illustrated noteworthy
structural differences and interesting topologies as a result of
coordination of Ag(I) ions to the metalloligands. Both CPs
acted as the heterogeneous catalysts for the A3–coupling
reactions of aldehydes, secondary amines and alkynes. Recyꢀ
clability experiments substantiated the stable nature of CPs in
promoting the A3–coupling reactions. This work has illustrated
that the relative position of substituted pyridyl ring not only
influenced the structural outcome but also the catalysis results.
ASSOCIATED CONTENT
Supporting Information. Figures for FTIR and NMR spectra;
TGA; PXRD patterns; SEM and optical images. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
Email: rgupta@chemistry.du.ac.in
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Webpage: http://people.du.ac.in/~rgupta/
Crystal Growth & Design
Framework Incorporating Zn8O Clusters with Aligned Imꢀ
idazolium Groups Decorating the Channels J. Am. Chem.
Soc., 2012, 134, 19432ꢀ19437.
1
2
3
Author Contributions
17. Sadakiyo, M.; Yamada, T.; Kitagawa, H. Proton conductivꢀ
ity control by ion substitution in a highly protonꢀconductive
metal–organic framework. J. Am. Chem. Soc., 2014, 136,
13166–13169.
18. Sadakiyo, M.; Yamada, T.; Kitagawa, H. Rational designs
for highly protonꢀconductive metal–organic frameworks. J.
Am. Chem. Soc., 2009, 131, 9906–9907.
19. Hendon, C. H.; Reith, A. J.; Korzynski, M. D.; Dinca, M.
Grand challenges and future opportunities for metal–
organic frameworks. ACS Cent. Sci., 2017, 3, 554–563.
20. Wang, W.; Xiaomin, X.; Zhou, W.; Shao, Z. Recent proꢀ
gress in metalꢀorganic frameworks for applications in elecꢀ
trocatalytic and photocatalytic water splitting. Adv.Sci.
2017, 4, 1600371DOI: 10.1002/advs.201600371.
The manuscript was written through contributions of all authors.
4
Notes
5
6
The authors declare no competing financial interest.
7
ACKNOWLEDGMENT
8
9
RG acknowledges Science and Engineering Research Board
(EMR/2016/000888), New Delhi for the financial support. SP
thanks CSIR, New Delhi for the SRF fellowship. Authors thank
CIFꢀUSIC of this university for the instrumental facilities includꢀ
ing Xꢀray data collection.
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Crystal Growth & Design
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For Table of Contents Use Only
Manuscript Title: Agꢀbased Coordination Polymers Based on Metalloligands and Their Catalytic Perꢀ
formance in MultiꢀComponent A3−Coupling Reactions
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Author List: Gulshan Kumar, Saurabh Pandey and Rajeev Gupta*
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TOC Graphic
Synopsis: Two Ag(I)ꢀbased 3D coordination polymers have been synthesized and utilized as the
heterogeneous catalysts for A3–coupling reactions of assorted aldehydes, secondary amines and
substituted alkynes.
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