Metal-Organic Frameworks with Pyridyl-Based Isophthalic Acid and Their Catalytic Applications in Microwave Assisted Peroxidative Oxidation of Alcohols and Henry Reaction

Article abstract of DOI:10.1021/acs.cgd.5b01178

Reactions of 5-{(pyridin-4-ylmethyl)amino} isophthalic acid (H₂L1) with copper(II), zinc(II), and cadmium(II) were studied, and the obtained metal-organic frameworks (MOFs) [{Cu(L1)(DMF)}·DMF·H₂O]_n (1), [Zn(L1)(H₂

Full text of DOI:10.1021/acs.cgd.5b01178

Subscriber access provided by UCL Library Services
Article
Metal–Organic Frameworks with Pyridyl-Based Isophthalic
Acid and Their Catalytic Applications in Microwave Assisted
Peroxidative Oxidation of Alcohols and Henry Reaction
Anirban Karmakar, Luísa M.D.R.S. Martins, Susanta Hazra,
M. Fátima C. Guedes da Silva, and Armando J. L. Pombeiro
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01178 • Publication Date (Web): 22 Feb 2016
Downloaded from http://pubs.acs.org on February 24, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155
Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 26
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Metal–Organic Frameworks with Pyridyl-Based Isophthalic Acid and
Their Catalytic Applications in Microwave Assisted Peroxidative
Oxidation of Alcohols and Henry Reaction
Anirban Karmakara,* Luísa M.D.R.S. Martinsb,* Susanta Hazraa, M. Fátima C. Guedes da Silvaa and
Armando J. L. Pombeiroa*
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
a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; pombeiro@tecnico.ulisboa.pt
b Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico
de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal. E-mail: lmartins@deq.isel.ipl.pt
Abstract
Reactions of 5-{(pyridin-4-ylmethyl)amino} isophthalic acid (H2L1) with copper(II), zinc(II) and
cadmium(II) were studied and the obtained MOFs [{Cu(L1)(DMF)}.DMF.H2O]n (1), [Zn(L1)(H2O)]n (2)
and [Cd(L1)]n (3) were characterized by elemental analysis, FT-IR spectroscopy and X-ray single-
crystal diffraction. As shown by X-ray crystallography, novel hybrid organic–inorganic coordination-
driven assemblies were obtained which exhibit different two and three dimensional polymeric
architectures. Compounds 1 and 2 have 2D structures whereas compound 3 features a 3D network
type polymer with a dimetallic core act as a secondary building unit. These frameworks act as
heterogeneous polymeric solid catalysts (the most effective one being the copper MOF 1) for
solvent-free microwave assisted peroxidative oxidation of primary and secondary alcohols. They also
effectively catalyze the nitroaldol (Henry) reaction of different aldehydes with nitroalkanes in water.
These MOF-based heterogeneous catalysts are of easy recovery and reused, at least for a few
consecutive cycles, without losing activity.
Keywords: Metal Organic Frameworks, Crystal Structure analysis, Heterogeneous Catalysis, Alcohol
oxidation, Microwave-assisted catalysis, Nitroaldol (Henry) reaction
Introduction
Metal–organic frameworks are compounds consisting of inorganic metal ions and organic linkers,
which have attracted a significant interest recently.1-9 The rapid development in this field is due to
their attractive structures and topologies, as well as to their uses in various areas, e.g., catalysis,10-12
nonlinear optics,13 gas storage and separation,14 and magnetism.15 However, the construction of
multi-dimensional coordination frameworks is still challenging. The reactivity and solubility of the
linkers and the choice of ligands with adequate binding centres play an important role in the suitable
construction of MOFs.16 In recent years a marked improvement in the synthesis of porous MOFs with
multidentate aromatic carboxylate ligands has been accomplished.17-18
Primary and secondary alcohols oxidations are relevant in modern organic chemistry.19-22 Many
different metal catalysts have been reported for this reaction but most of them are homogeneous.23-
24 It is also important to try to develop new catalytic oxidation procedures using green oxidants, such
as O2 or peroxides [H2O2, tert-butylhydroperoxide (TBHP)], namely to overcome the formation of
harmful wastes.25,26
1
ACS Paragon Plus Environment

Crystal Growth & Design
Page 2 of 26
1
2
3
4
5
6
7
8
9
Moreover, the use of solvent-free conditions,27 of ecofriendly and efficient catalysts and green
oxidants, and of microwave (MW) irradiation (with eventual advantages over traditional heating,28,29
e.g., a shorter reaction time and higher product yield and selectivity) is also promising. Efficient
copper(II)30-33 and iron(III)34-35 catalytic systems have been recently achieved by us, for aerobic and
peroxidative (with TBHP) oxidations of various primary and secondary alcohols, namely involving a
solvent-free MW procedure. However, most of our reported catalysts are homogenous, and thus it
would be desirable to spread our work to heterogeneous ones. Moreover, only a few MOFs are
known as heterogeneous catalysts for alcohols oxidation,36 and numerous challenges and
opportunities still remain. Thus, MOF based heterogeneous catalysts with higher stability and
activity, and easier accessible metal centres are worth developing.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The Henry or nitroaldol reaction provides an interesting C–C bond formation method in modern
organic chemistry.37,38 Generally, this reaction is effectively catalyzed by basic catalysts, like alkali
metal hydroxides, alkoxides or amines.39 Recently, some MOFs and discrete complexes were
reported by our group to catalyze this reaction efficiently.40-45 Nevertheless, it is still challenging to
develop new types of heterogeneous catalysts based on MOFs, displaying a high activity under mild
conditions and able to recycling.
In this context, we have chosen 5-{(pyridin-4-ylmethyl)amino}isophthalic acid (H2L1) as an organic
ligand/ linker due to the following features: (a) easy tuning of the extent of deprotonation of the
carboxylic groups by changing the pH of the reaction medium, with expected formation of
multidimensional MOFs; (b) flexibility of the pyridyl arm of H2L1, able to adopt various
conformations, with possible formation of various architectures; (c) introduction of an amine
functionality in H2L1 which can offer additional hydrogen bonding sites, as well as a Lewis-basic
nature to the frameworks (Scheme 1). Recently, various MOFs with interesting architectures and
properties have been synthesized using similar types of ligands.46-50
Therefore, the objectives of this study are the following: (i) design, preparation and characterization
of different multi-dimensional MOFs using H2L1 as a linker; (ii) application of the synthesized
frameworks as heterogeneous catalysts for MW promoted and solvent free oxidation of primary and
secondary alcohols with a peroxide oxidant and for the Henry reaction of aldehydes with
nitroalkanes in a green solvent; (iii) achievement of a catalyst that would be effective in a sequential
catalytic conversion of alcohols to aldehydes followed by the conversion of the latter into
nitroalkanes. In accord, by using H2L1 as a pro-ligand, we report the preparation of
[{Cu(L1)(DMF)}.DMF.H2O]n (1), [Zn(L1)(H2O)]n (2) and [Cd(L1)]n (3) MOFs, their syntheses,
characterization and heterogeneous catalytic activities towards the solvent-free microwave assisted
alcohol (primary and secondary) oxidation and the nitroaldol reaction of aldehydes.
2
ACS Paragon Plus Environment

Page 3 of 26
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
Scheme 1
Experimental Section
All the chemicals in the current study were purchased from commercial sources and utilized without
further purifications. A Bruker Vertex 70 instrument was used for the IR (4000–400 cm-1)
measurements of samples prepared as KBr pellets; abbreviations: s = strong, m = medium, w = weak,
bs = broad and strong, mb = medium and broad. Elemental analyses of all compounds were
performed at the Microanalytical Service of the Instituto Superior Técnico. Powder X-ray diffraction
(PXRD) was conducted in a D8 Advance Bruker AXS (Bragg Brentano geometry) theta-2theta
diffractometer, with copper radiation (Cu Kα, λ = 1.5406 Å) and a secondary monochromator,
operated at 40 kV and 40 mA. Flat plate configuration was used and the typical data collection range
was between 5˚ and 40˚.
5-{(pyridin-4-ylmethyl)amino}isophthalic acid (H2L1) was synthesized according to the reported
procedure48 in an open atmosphere under air, while the metal organic frameworks were prepared
under hydrothermal conditions.
Synthesis of H3L1+Cl-
To a H2L1 (27.0 mg, 0.10 mmol) solution in methanol (2.0 mL) was added 1 drop of conc. HCl,
whereupon the system was stirred (30 min) and kept for crystallization. After 2 days block shape
colourless crystals were obtained. Anal. Calcd. for C14H13ClN2O4 (M = 308.06): C, 54.47; H, 4.24; N,
9.07; Found: C, 54.60; H, 4.16; N, 9.11. FT-IR (KBr, cm-1): 3315 (bs), 3072 (bs), 1720 (s), 1613 (s),
1506 (s), 1446 (m), 1326 (m), 1262 (m), 1227 (m), 1136 (w), 1032 (m), 921 (m), 824 (s), 761 (s), 678
(s), 469 (m), 437 (m).
Synthesis of 1
A solution of Cu(NO3)2.3H2O (24.0 mg, 0.10 mmol) and H2L1 (27.0 mg, 0.10 mmol) in DMF (2.0 mL)
was stirred at room temperature for 30 min, whereupon 1 mL of 28% aqueous solution of NH4OH
was added into it. The resulting clear dark blue solution was left at room temperature for 3 days
leading to precipitation of block-like deep green crystals. Yield: 77% (based on Cu). Anal. Calcd. for
C20H26CuN4O7 (M = 497.99): C, 48.24; H, 5.26; N, 11.25; Found: C, 48.00; H, 5.07; N, 11.12. FT-IR (KBr,
3
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 26
1
2
3
4
5
cm-1): 3352 (bs), 1616 (s), 1558 (s), 1426 (s), 1405 (s), 1363 (s), 1243 (w), 1065 (w), 1032 (w), 969 (w),
879 (w), 781 (s), 729 (s), 561 (w).
6
7
Synthesis of 2
To an equivalent molar (1:1) solution (5 mL) of H2L1 (27.0 mg, 0.10 mmol) and Zn(NO3)2.6H2O (29.0
mg, 0.10 mmol) in DMF and methanol (1 : 1) was added 0.5 mL of 28% aqueous ammonia. A white
precipitate formed but it was dissolved by further addition of the same amount (0.5 mL) of that
solution. Then, the resulting solution was transferred and sealed in an 8 mL glass vessel and heated
(hydrothermal reactor) at 75 ˚C for 48 h. Subsequent cooling of that solution to room temperature
(0.2 ˚C min-1) afforded plate-like colorless crystals of 2. Yield: 68% (based on Zn). Anal. Calcd. for
C17H19N3O6Zn (M = 426.73): C, 47.85; H, 4.49; N, 9.85; Found: C, 47.63; H, 4.31; N, 9.45. FT-IR (KBr,
cm-1): 3413 (bs), 1619 (s), 1567 (s), 1407 (s), 1384 (s), 1244 (w), 1148 (w), 1065 (w), 1031 (w), 972
(w), 914 (w), 778 (s), 732 (s), 536 (w).
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
Synthesis of 3
A solution of Cd(NO3)2.4H2O (31.0 mg, 0.10 mmol) and H2L1 (27.0 mg, 0.10 mmol) in 5 mL of DMF:
1,4-dioxane: water (2 : 2: 1) mixture was prepared and then transferred and sealed in an 8 mL glass
vessel, and heated (hydrothermal reactor) at 75 ˚C for 48 h. Subsequent cooling of that solution to
room temperature (0.2 ˚C min-1) afforded plate-like colorless crystals of 3. Yield: 71% (based on Cd).
Anal. Calcd. for C19H21CdN3O6 (M = 499.80): C, 45.66; H, 4.24; N, 8.41; Found: C, 45.39; H, 4.15; N,
8.12. FT-IR (KBr, cm-1): 3412 (bs), 1653 (m), 1604 (s), 1556 (s), 1441 (m), 1423 (m), 1382 (s), 1253 (w),
1107 (w), 1061 (w), 1041 (w), 968 (w), 783 (s), 735 (s), 682 (s), 570 (w).
Solvent-Free Microwave-Assisted Peroxidative Oxidation of Alcohols
The alcohol (2.5 mmol), the catalyst (5 μmol) and t-BuOOH (70% aqueous solution, 5 mmol) were
introduced into a cylindrical Pyrex tube which was then sealed and placed into the focused Anton
Paar Monowave 300 microwave reactor. The system was stirred and irradiated (5 W) at 100 ºC for
0.5 h. After the reaction, the system was allowed to cool down to room temperature. The internal
standard (150 μL of benzaldehyde or cyclopentanone, respectively for secondary or primary
alcohols) was added and then acetonitrile (2.5 mL to extract the substrate and the organic products
from the reaction mixture). After stirring the mixture for 10 min, an aliquot (1 μL) from the organic
phase was taken and analyzed by GC. Tests in the absence of catalysts were also undertaken under
the above reaction conditions and no considerable alcohol conversion was detected.
In order to perform the recycling experiment, we have separate the solid catalyst 1 by hot filtration
from the reaction mixture and dried overnight at 50º C. It was then used for next cycle of the
oxidation reaction as described above.
Henry Reaction
To 2 mL water in a glass vessel was added a mixture of aldehyde (1.0 mmol), nitroethane (0.3 mL, 4.0
mmol) and catalyst (2 mol%, 9.9 mg for 1, 8.5 mg of 2 and 10.0 mg of 3) and the capped reaction
system was heated at 75˚C. After the desired time the mixture was centrifuged to remove the solid
catalyst and the separated solution was extracted with CH2Cl2. The extracts were dried over
anhydrous Na2SO4, whereupon evaporation of the solvent gave the crude product which was
4
ACS Paragon Plus Environment

Page 5 of 26
Crystal Growth & Design
1
2
3
4
5
6
7
8
1
analyzed by H NMR after dissolving in DMSO-d6. The β-nitroalkanol yield and the corresponding
syn/anti selectivity were estimated following our published procedure.44 The product isomers were
1
identified by H NMR (Figure S3, supporting information). The values of vicinal coupling constants
between the α-N–C–H and the α-O–C–H protons characteristic of the isomers are as follows: J = 7–9
or 3.2–4 Hz for the syn or anti isomers, respectively.51
9
The recycling experiments were performed after washing and drying the used catalyst at room
temperature. The rest of the procedure was followed as indicated above.
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
Crystal Structure Determinations
X-ray quality single crystals of the compounds were mounted in a nylon loop and their intensity data
were collected using a Bruker AXS-KAPPA APEX II or a Bruker APEX-II PHOTON 100 diffractometer
with graphite monochromated Mo-Kα (λ 0.71069) radiation at 150 K (2) or at room temperature (1,
3 and H3L1+Cl-). Cell parameters were retrieved and refined using Bruker SMART52-54 and Bruker
SAINT52 softwares, respectively. Absorption corrections were made using SADABS.52 Structures were
solved and refined using the SHELXS-9753 with SHELXL-9753 packages, respectively. Calculations were
performed using the WinGX System–Version 1.80.03.54 The hydrogen atoms attached to carbon
atoms and to the nitrogen atoms were inserted at geometrically calculated positions and included in
the refinement using the riding-model approximation; Uiso(H) were defined as 1.2Ueq of the parent
nitrogen atoms or the carbon atoms for phenyl and methylene residues, and 1.5Ueq of the parent
carbon atoms for the methyl groups. The hydrogen atoms of coordinated water molecules were
located from the final difference Fourier map and the isotropic thermal parameters were set at 1.5
times the average thermal parameters of the belonging oxygen atoms. Least square refinements
with anisotropic thermal motion parameters for all the non-hydrogen atoms and isotropic ones for
the remaining atoms were employed. PLATON/SQUEEZE55 was used to correct the data and in
framework 3 the potential volume of 1872 Å3 was found with 494 electrons per unit cell worth of
scattering. The electron count suggests the presence of ca. one dimethylformamide and two water
molecules per asymmetric unit. The elemental analysis also supports these results. Crystallographic
data are summarized in Table S1 (Supplementary Information file) and selected bond distances and
angles are presented in Table S2. CCDC 1419063-1419066 for 1-3 and H3L1+Cl-, contain the
supplementary crystallographic data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Results and Discussion
Syntheses and Characterization
The dicarboxylic acid ligand 5-{(pyridin-4-ylmethyl)amino}isophthalic acid (H2L1) was synthesized
according to the procedure reported earlier.48
We have used solvothermal reaction procedures for the syntheses of the frameworks 2 and 3, but
room temperature synthesis for 1. The reaction of copper(II) nitrate with H2L1 in the presence of
dimethyl formamide (DMF) and NH4OH leads to the formation of [{Cu(L1)(DMF)}.DMF.H2O]n (1). The
hydrothermal reaction of H2L1 with zinc(II) nitrate hexahydrate in the presence of DMF-methanol
and ammonium hydroxide forms [Zn(L1)(H2O)]n (2), whereas the reaction with Cd(NO3)2.4H2O in
5
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 26
1
2
3
DMF, 1,4-dioxane and water mixture produces [Cd(L1)]n (3) [L1
=
5-{(pyridin-4-
4
5
ylmethyl)amino}isophthalate] (Scheme 2).
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
Scheme 2
In the IR spectra of 1-3, the characteristic strong bands of the coordinated carboxylate groups
appear at 1604–1619 cm-1 for the asymmetric stretching and 1363-1384 cm-1 for the symmetric
one.7 The C–O stretching of coordinated carboxylate group is observed between 1243 and 1253 cm-1.
For H2L1 the strong band at 1720 cm-1 is due to ν(CO) of uncoordinated carboxylic acid groups,56
whereas ν(NH) of the amine group appears at 3072 cm-1. Due to their insolubility in common NMR
solvents, these frameworks were only characterized by single crystal X-ray diffraction and elemental
analyses.
Crystal Structure Analyses
The single crystal X-ray analysis of 1 reveals that it crystallizes in the monoclinic P21/n space group
and is a bilayer type two dimensional framework constructed by Cu(II) ions and deprotonated L12-
ligands. The asymmetric unit contains a Cu2+ ion, one deprotonated ligand (L12-) and the coordinated
DMF, as well as one of non-coordinated DMF and water molecules (Figure 1A). The Cu(II) centre has
a distorted trigonal bipyramidal (τ5 = 0.32)57 geometry, the equatorial positions being occupied by
three carboxylate oxygens from two L12- ligands [Cu1–O1, 2.464 (3) Å, Cu1–O2, 1.963(2) Å and Cu1–
O3, 1.936(2) Å] and the axial positions being coordinated by one DMF and one pyridyl-N groups
[Cu1–O5, 1.979(3) Å and Cu1–N2, 2.000(3) Å] (Figure 1B). Selected bond distances and angles of 1
are listed in Table S3 (supporting information). The organic ligand is not planar, the isophthalate and
pyridyl parts being almost perpendicular to each other with the angle of 84.11o and the C7-N1-C9-
C10 torsional angle of -69.32o. Each L12- ligand coordinates to three copper(II) ions and one
carboxylate coordinates in a monodentate fashion while the other one chelates in a bidentate mode.
In 1, the distance between two neighbouring copper(II) ions is 8.5869(9) Å. The 2D polymeric
architecture of 1 also has open channels with approximate dimension of 7.59 x 7.00 Å2, which are
occupied by the non-coordinated water and DMF molecules (Figure 1C).
The non-coordinated water and DMF molecules are stabilized by a number of hydrogen bonding
interactions. These involve the hydrogens of a non-coordinated water molecule O7 (as donor) and
6
ACS Paragon Plus Environment

Page 7 of 26
Crystal Growth & Design
1
2
3
4
5
6
7
8
the carboxylate oxygen O4 (as bifurcated acceptor). The amine NH- is also involved in hydrogen
bonding with carboxylate oxygen via N1-H1A∙∙∙O1 (dD–A 2.961(4) Å; <D–H∙∙∙∙A 171˚) interaction.
Relevant hydrogen bond distances and angles are listed in Table S2 (supporting information).
Moreover, a number of C−H⋅⋅⋅O interactions are present in this structure which helps its expansion
to the third dimension (Figure 1D).
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
Single crystal X-ray analysis reveals that the 2D framework 2 crystallizes in the monoclinic P21/n
space group. The asymmetric unit contains a Zn2+ ion, one deprotonated ligand (L12-) and one
coordinated water molecule (Figure 2A).
Cu
O
O
Cu
N
NH
O
O
N
O
Cu
O
N
A
B
C
D
Figure 1: (A) The asymmetric unit of framework 1 with partial atom labelling scheme. (B) Schematic
representation of the asymmetric unit of 1. (C) Two dimensional structure of framework 1 (water
molecules are indicated as red balls). (D) Three dimensional packing view of framework 1.
The Zn(II) ion has a tetrahedral (τ4 = 0.91)58 coordination geometry occupied by two monodentate
carboxylate oxygens from two L12- ligands [Zn1–O1, 1.973(2) Å and Zn1–O3, 1.974(2) Å], one water
molecule [Zn1–O5, 1.985(4) Å] and one pyridyl-N of L12- ligand [Zn1–N1, 2.050(3) Å] (Figure 2B).
Selected bond distances and angles are listed in Table S3 (supporting information). The minimum
Zn∙∙∙Zn distance reaches 10.3492(8) Å. The L12- ligand is not planar, the isophthalate and pyridyl part
almost perpendicular with the angle of 80.12o and the C4-N3-C8-C9 torsional angle of 76.43o. A
close inspection of the 2D structural arrangement in 2 indicates that the metals are assembled via
bridging oxygen atoms in one dimensional chains. These chains are then interconnected by the
pyridyl-N of L12‒ ligand giving rise to a 2D square grid type framework with the approximate
7
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 26
1
2
3
4
5
6
7
8
dimension of 10.7 X 11.0 Å2 that runs diagonally along the crystallographic ac-plan (Figure 2C). The
framework 2 contains a void space of 27.5% per unit cell according to PLATON.55 Moreover, the
intermolecular organization in the crystal is characterized by hydrogen bonding interactions
involving the carboxylate groups as acceptors and the coordinated water molecule as donor,
expanding the structure to the third dimension (Figure 2D, Table S2).
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
Zn
N
NH
O
O
OH2
O
O
Zn
Zn
N
O
A
B
C
D
Figure 2: (A) The asymmetric unit of framework 2 with partial atom labelling scheme. (B) Schematic
representation of the asymmetric unit of 2. (C) Two dimensional structure of framework 2. (D) Three
dimensional packing view of framework 2.
The single crystal X-ray analysis of 3 reveals that it is a three dimensional framework constructed by
Cd(II) ions and deprotonated L12- ligands which crystallize in the orthorhombic Aba2 space group.
The asymmetric unit contains a Cd2+ ion and one deprotonated L12- ligand (Figures 3A and 3B). The
Cd(II) ion has a hexa-coordinated geometry where five coordination sites are occupied by five
carboxylate oxygen atoms from three neighbouring L12- ligands [Cd1-O1, 2.385(4); Cd1-O2, 2.354(5);
Cd1-O3, 2.344(4); Cd1-O4, 2.463(4); Cd1-O1’, 2.475(4)] and the remaining position is coordinated
axially by one pyridyl-N group [Cd1-N2, 2.311(5)] (Figure 3B). Selected bond distances and angles are
listed in Table S3 (supporting information). In this framework, the L12- is bent and the pyridyl group is
8
ACS Paragon Plus Environment

Page 9 of 26
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
almost perpendicular to the isophthalate group as observed in the previous complexes. The angle
between them is 89.00o and the C4-N1-C9-C10 torsional angle is -79.69o. In the ligand L12-, one
carboxylate coordinates to a single metal center in a chelating fashion whereas the other
carboxylate group coordinates two different Cd(II) ions via a μ2-chelating mode. In this framework a
dinuclear Cd(II) cluster acts as a secondary building block unit. Each dinuclear unit is coordinated by
six different L12- ligands whereas each L12- ligand connected with four different Cd(II) ions. The Cd(II)
ions are assembled via bridging carboxylate oxygen atoms in a two dimensional chain and these
chains are further interconnected by the pyridyl-N giving rise to 3D framework. This 3D polymeric
architecture of 3 also has some open channels with approximate dimension of 9.4 X 6.6 Å2 (Figures
3C and 3D) and a void space of 45.5% per unit cell according to PLATON55 after removing the non-
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
coordinated solvent molecules. Moreover, a number of C
−H
⋅⋅⋅O interactions are present in this
structure helping its stabilization.
A
B
C
D
Figure 3: (A) The asymmetric unit of framework 3 with partial atom labelling scheme. (B) Schematic
representation of an asymmetric unit of 3. (C) Three dimensional structure of framework 3. (D) View
of packing diagram of 3 along a-axis.
9
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 26
1
2
3
4
5
6
7
8
9
It is worth mentioning that this ligand has previously been utilized to synthesize a few 3D polymers
of manganese(II) by Bharadwaj et el.48,49 The ligand therein is coordinated to four Mn(II) centres to
form catena-(bis(μ4-5-((pyridin-4-ylmethyl)amino)isophthalato)-mono/di-manganese(II) polymers
whereas in our cases (1-3) it connects three metal centres to yield catena-(bis(μ3-5-((pyridin-4-
ylmethyl)amino)isophthalato) polymers.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
To improve the description of the crystal structures of 1-3 we performed their topological analysis by
reducing their multidimensional structures to simple node-and-linker nets where the metallic nodes
and the organic linkers represent secondary building units (SBUs). We have carried out these
analyses by using TOPOS 4.0.59 In the particular case of H3L1+Cl-, each protonated H3L1+ unit is
hydrogen bonded with four different H3L1+ and each Cl- anion is halogen bonded with three different
H3L1+. H3L1+Cl- represents a 3,4-connected 2-nodal net with the topological type 3,4L83 (Figure 4A).
Topological analysis of framework 1 reveals that it has a 3-connected uninodal net with a topological
type fes (Shubnikov plane net) and point symbol (4.82) (Figure 4B). Similarly, framework 2 has also 3-
connected uninodal net with a topological type hcb (Shubnikov hexagonal plane net) and the point
symbol (63) (Figure 4C). In case of framework 3, we have considered the dinuclear Cd(II) unit as a
single node and connected with six different L12- ligands and each ligand connected with three Cd(II)
centres. Thus, framework 3 represents a 3,6-connected binodal net structure with topological type
flu-3,6-I41cd (Figure 4D).
A
B
10
ACS Paragon Plus Environment

Page 11 of 26
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
C
D
Figure 4 Node-and-linker-type descriptions of: (A) the 2D hydrogen bonded frameworks in H3L1+Cl-
(H3L1+ represented in pink color and Cl- in green color); (B) the 2D coordination frameworks in 1; (C)
the 2D coordination framework in 2; (D) the 3D coordination frameworks in 3. The metal nodes are
represented in red color and the carboxylate linker in blue color.
Catalytic applications of MOFs
Compounds 1−3 are catalysts for the solvent-free microwave (MW) assisted oxidation of primary or
secondary alcohols (benzyl alcohol or 1-phenylethanol as model substrates) to the corresponding
aldehydes or ketones as well as for the nitroaldol (Henry) reaction between several benzaldehydes
and nitroalkanes (Scheme 3).
OH
O
H
TBHP
MW
NO2
Cu-, Zn-
Water, 70oC
or Cd-MOF
OH
TBHP
MW
OH
NO2
anti
+
OH
O
NO2
syn
Scheme 3
In Oxidation of Alcohols
Compounds 1−3 were tested as heterogeneous catalysts for the solvent-free microwave (MW)
assisted oxidation of benzyl alcohol or 1-phenylethanol to benzaldehyde or acetophenone,
11
ACS Paragon Plus Environment

Crystal Growth & Design
Page 12 of 26
1
2
3
respectively, with aqueous tert-butyl hydroperoxide (tBuOOH, TBHP
, aq. 70%, 2 eq) as oxidizing
4
5
agent (Scheme 3), at 100 ºC typically during 0.5 h of irradiation.
The optimized results, in terms of yield, selectivity and turnover frequency (TOF, moles of
product/mol of catalyst per hour), are presented in Table 1. Benzaldehyde or acetophenone is the
only product detected in the assayed conditions for the oxidation of benzyl alcohol or 1-
phenylethanol, respectively. The best results were obtained with the copper(II)-based MOF 1 (Table
1, entries 1 and 7, respectively). Under the above conditions, 81 or 98% yield of benzaldehyde or
acetophenone and TOF of 811 or 983, respectively, are obtained in the absence of any additive. The
reactions performed under the same conditions but in the presence of the other MOFs resulted in
much lower yields (between 13 and 19%, Table 1) and TOFs (between ca. 130 and 190, Table 1) in
benzaldehyde or acetophenone.
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
Table 1. Selected dataa for the solvent-free MW-assisted oxidation of benzyl alcohol and 1-
phenylethanol using 1 - 3 as catalysts.
Entry
MOF or precursor salt
Yieldb /%
81.1
17.2
15.3
6.8
TOFc /h-1
811
172
153
68
Selectd /%
1
2
3
4
5
6
1
>99
77
99
66
98
85
Cu(NO3)2.3H2O
2
Zn(NO3)2.6H2O
3
12.8
5.9
128
59
Cd(NO3)2.4H2O
7
8
1
98.3
23.1
19.2
8.3
983
231
192
83
>99
67
Cu(NO3)2.3H2O
9
2
>99
74
10
11
Zn(NO3)2.6H2O
3
16.1
161
99
12
ACS Paragon Plus Environment

Page 13 of 26
Crystal Growth & Design
1
2
3
12
Cd(NO3)2.4H2O
3.9
39
81
4
5
a
Reaction conditions: 2.5 mmol of benzyl alcohol or 1-phenylethanol, 5 μmol (0.2 mol % vs.
6
7
8
9
substrate) of 1 - 3, 5 mmol of TBHP (2 equiv, 70 % in H2O), T = 100 ºC, t = 0.5 h, MW irradiation (5 W
b
c
power). Moles of benzaldehyde or acetophenone per 100 moles of alcohol substrate. Number of
moles of benzaldehyde or acetophenone per mole of catalyst per hour. d Moles of benzaldehyde or
acetophenone per mole of converted substrate.
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
Blank tests were performed under the same reaction conditions but in the absence of MOFs and no
significant conversion of benzyl alcohol or 1-phenylethanol was observed. Moreover, the
replacement of 1 - 3 by their precursor salts, M(NO3)2.xH2O (M = Cu, Zn or Cd; x =3, 6 or 4), resulted
in a drastic decrease of activity (compare e.g., entries 1 and 2, Table 1) suggesting a significant role
of the ligand L1 in the catalytic oxidation of the tested alcohols. The reaction catalyzed by the most
active compound (1) appears to proceed mainly via a radical mechanism, which involves oxygen- and
carbon-radicals since a strong inhibiting effect on the catalytic activity was observed upon addition,
to the reaction mixture, of Ph2NH or CBrCl3, well known60 oxygen- or carbon-radical traps,
respectively. The benzaldehyde yield decreased from 81% (entry 1, Table 1) to 3.8% or 1.3%,
respectively, in the presence of Ph2NH or CBrCl3. Similarly, the formation of acetophenone (98%
yield, entry 7, Table 1) catalyzed by 1 was significantly reduced to 2.6% or 2.9%, respectively, when
Ph2NH or CBrCl3 was added to the reaction medium. Hence, the oxidation mechanism may involve
the metal-assisted generation of radicals tBuOO● (upon oxidation of BuOOH by a Cu(II) centre) and
t
t
tBuO● (upon reduction of BuOOH by the formed Cu(I) centre), which behave as hydrogen atom
abstractors from the alcohols. The mechanism conceivably is similar to those proposed in other
cases, which are also of a radical type.61,62 The ligand L1 can assist proton transfer steps involved in
the fundamental steps of the above reaction,61,62 improving the catalytic activity of its complexes.
The present system, in particular in the presence of 1, leads to much higher yields of oxidized
products in an exceptionally short reaction time compared with those reported for MW-assisted32,33
or conventional heating63 peroxidative oxidations of secondary alcohols or TEMPO-assisted aerobic
oxidations of primary alcohols64-70 in the presence of other metallic MOFs. Moreover, our catalytic
system exhibits good activity for both primary and secondary alcohols, a feature that is also
noteworthy. For example, it was found67,68 that copper MOFs based on carboxylate ligands,
[Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate), which are able to catalyze the TEMPO-assisted
aerobic oxidation of benzyl alcohol (leading to 99% yield of benzaldehyde after 16 h reaction at 70
ºC67 or to 100% yield of benzaldehyde after 10 h if used as mesocellular MOFs68), are not effective
when applied to the aerobic oxidation of secondary alcohols, such as 1-phenylethanol or
benzhydrol.67
In Henry Reaction
We have also tested the catalytic activity of compounds 1-3 as solid heterogeneous catalysts in the
nitroaldol (or Henry) reaction of nitroethane with various aldehydes. Previously, we have reported
various Zn(II) and Cu(II) coordination polymers and complexes which are significantly active for such
a type of reaction.40-45 In 1-3, the presence of amine group (which can promote the reaction) and the
structural rigidity (which can improve the selectivity) encouraged us to apply them to such a
reaction.
13
ACS Paragon Plus Environment

Crystal Growth & Design
Page 14 of 26
1
2
3
4
5
6
By using benzaldehyde as a test compound, we have found that 1 showed a higher activity than the
other frameworks, after the same reaction time and at the same temperature. Consequently, the
optimization of the reaction conditions (temperature, reaction time, amount of catalyst and solvent)
was carried out in a model nitroethane–benzaldehyde system with catalyst 1 (Table 2).
7
8
9
A blank test was carried out with benzaldehyde in the absence of any metal catalyst, at 75˚C in
water. No considerable amount of β-nitroalkanol was detected after a reaction time of 40 h. The
nitroaldol reaction also did not take place by using compound H2L1 instead of the metal catalyst
(Table 2, entry 23). We have also checked the reactivity of Cu(NO3)2.3H2O, Zn(NO3)2.6H2O and
Cd(NO3)2.4H2O in water medium and the obtained reaction yields are in the range of 9-14% (entries
20-22, Table 2), much lower than those achieved in the presence of the MOF.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
When 2 mol% of 1 is used as catalyst, a conversion of 84% (syn:anti = 82:18) of benzaldehyde into β-
nitroalkanol is reached (entry 7, Table 2). With 2 and 3, conversions of 71% (syn:anti = 81:19) and
69% (syn:anti = 79:21) were obtained, respectively (entries 17-18, Table 2). Extending the reaction
time to 48 h did not increase the yield of the reaction. The plot of yield versus time for the Henry
reaction of benzaldehyde and nitroethane with framework 1 is presented in Figure 5.
Figure 5 Plot of β-nitroalkanol yield vs. time for the Henry reaction of benzaldehyde and nitroethane
in presence of catalyst 1 (black curve) and after filtering off the catalyst 1 (red curve).
Table 2. Optimization of the parameters of the Henry reaction between benzaldehyde and nitroethane with
1
as the catalysta
Entry
Catalyst
Time (h) Amount of
Catalyst
T (˚C)
Solvent
Yield
(%)b
Selectivity
(syn/anti)c
TONd
(mol%)
1
2
3
4
1
1
1
1
1
2
5
8
2.0
2.0
2.0
2.0
75
75
75
75
H2O
H2O
H2O
H2O
25
36
48
56
84:16
79:21
80:20
82:18
12
18
24
28
14
ACS Paragon Plus Environment

Page 15 of 26
Crystal Growth & Design
1
2
3
4
5
6
5
6
7
1
1
1
12
24
40
2.0
2.0
2.0
75
75
75
H2O
H2O
H2O
64
74
84
81:19
81:19
82:18
32
37
42
7
8
9
8
9
1
1
1
40
40
40
1.0
3.0
5.0
75
75
75
H2O
H2O
H2O
56
83
84
79:21
77:23
78:22
56
28
17
10
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
11
12
13
1
1
1
40
40
40
2.0
2.0
2.0
75
75
75
THF
49
78
5
81:19
76:24
77:23
24
39
3
MeOH
CH3CN
14
15
16
1
1
1
40
40
40
2.0
2.0
2.0
25
50
H2O
H2O
H2O
15
51
77
85:15
80:20
75:25
7
26
38
100
17
18
2
3
40
40
2.0
2.0
75
75
H2O
H2O
71
69
81:19
79:21
35
34
19
20
21
22
23
Blank
40
40
40
40
40
-
75
75
75
75
75
H2O
H2O
H2O
H2O
H2O
-
11
9
-
-
6
5
7
-
Cu(NO3)2.3H2O
Zn(NO3)2.6H2O
Cd(NO3)2.4H2O
H2L1
2.0
2.0
2.0
2.0
82:18
78:22
80:20
-
14
-
aReaction conditions: 2.0 mol% of catalyst 1, benzaldehyde (1.0 mmol), nitroethane (0.3 mL, 4.0 mmol) and water
(2.0 mL). Number of moles of β-nitroalkanol per 100 moles of aldehyde. c Calculated by H NMR. d Number of
b
1
moles of β-nitroalkanol per mole of catalyst.
We have also tested the effect of catalyst amount, solvent and temperature. An increase of the
catalyst amount from 1.0 and 2.0 mol% enhances the product yield from 56 to 84%, respectively
(entries 8 and 7, Table 2), but a further rise of that amount did not improve the reaction yield
(entries 9 and 10, Table 2).
To select the most suitable solvent, experiments with various solvents (CH3CN, THF, MeOH and H2O)
have been carried out with catalyst 1 (entries 7 and 11–13, Table 2) and the results indicate that
water (84% yield) is the best solvent, whereas the worst one is CH3CN (5% yield). In methanol and
THF, the yields of 78% or 49%, respectively, were obtained (entries 12 and 11, Table 2).
Ranging the temperature from 25 to 75˚C improved the yield of β-nitroalkanol from 15 to 84%
(entries 7 and 14–15, Table 2) but further increase in the reaction temperature had a negative effect
(entry 16, Table 2). The systems exhibit diastereoselectivity towards the syn isomer, typically leading
to syn:anti molar ratios in the range of 85:15 to 77:23 using nitroethane as substrate.
We have also compared the activities of catalyst 1 in the reactions of a variety of substituted
aromatic and aliphatic aldehydes with nitroethane, producing the corresponding β-nitroalkanols
with yields ranging from 41 to 98% (Table 3). Aryl aldehydes bearing an electron-withdrawing group
exhibit higher reactivities (Table 3, entries 1 and 3) as compared to those having electron-donating
15
ACS Paragon Plus Environment

Crystal Growth & Design
Page 16 of 26
1
2
3
4
5
6
moieties (Table 3, entries 2 and 5-7), what may be related with an increase of the electrophilicity of
the substrate in the former case.
Table 3. Henry reaction of various aldehydes and nitroethane with catalyst 1a
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
Entry
Aldehyde
Yield(%)b
Selectivityc
(syn/anti)
79:21
TONd
1
2
3
4
5
6
7
8
9
4-Nitrobenzaldehyde
4-Methoxybenzaldehyde
4-Chlorobenzaldehyde
4-Hydroxybenzaldehyde
4-Methylbenzaldehyde
2-Methylbenzaldehyde
3-Methylbenzaldehyde
Acetaldehyde
98
41
78
72
64
51
59
90
85
49
21
39
36
32
26
30
45
42
82:18
81:19
79:21
85:15
84:16
81:19
82:18
Propionaldehyde
83:17
aReaction condition: 2.0 mol% of catalyst 1, aldehyde (1.0 mmol), nitroethane (0.3 mL, 4.0 mmol) and
water (2.0 mL) at 75oC for 40 h. Number of moles of β-nitroalkanol per 100 moles of aldehyde.
b
c
Calculated by 1H NMR. d Number of moles of β-nitroalkanol per mole of catalyst.
To probe whether the catalytic reaction occurred inside the pores or on the surface of the solid
catalyst, substrates of increasing dimensions were tested for 1. We systematically varied the
molecular sizes of nitrolalkanes [nitromethane (2.0 Å X 3.3 Å), nitroethane (2.2 Å X 3.9 Å) and
nitropropane (2.2 Å X 5.6 Å)] and aldehydes [benzaldehyde (4.8 Å X 5.9 Å), naphthaldehyde (5.9 Å X
7.0 Å) and 9-anthraldehyde (6.0 Å X 9.3 Å)] to get an insight into the reaction mechanism and
reaction centre. We have observed that the reaction yield systematically depends on the molecular
size of the nitroalkanes and aldehydes. For example, when we have performed the reaction of
benzaldehyde with nitropropane the yield was merely 42% compared with that of 91% for
nitromethane (entries 3 and 1, Table 4). In the case of nitroethane, the yield was 84% (entry 2, Table
4). The yield decreased in the order of nitromethane (91%) > nitroethane (84%) > 1-nitropropane
(42%). On the other hand, the reaction of benzaldehyde with nitroethane was accomplished with
84% yield after 40 h (entry 2, Table 4). In contrast, the yields for 1-naphthaldehyde and 9-
antraldehyde (with molecular sizes that hamper their fitting in the catalyst cavities) are reduced to
45% and 29% under the same reaction conditions, respectively (entries 4 and 5, Table 4). Therefore,
the yields decrease with the increase of the molecular size of nitroalkanes as well as of aldehydes.
These size-selective behaviours support the assumption that catalysis is promoted by the interior
catalytic sites and not only by the exterior ones.
Table 4. Henry reaction of various aldehydes and different nitroalkanes catalyzed by 1a
16
ACS Paragon Plus Environment

Page 17 of 26
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Entry
1
Aldehyde
Nitroalkane
Yield(%)b
91
Nitromethane
Nitroethane
Nitropropane
2
3
84
42
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
5
Nitroethane
Nitroethane
45
29
aReaction condition: 2.0 mol% of catalyst 1, aldehyde (1.0 mmol), nitroalkane (0.3 mL) and water
(2.0 mL) at 75oC for 40h.
The efficiency of 1 and 2 in comparison with various MOFs that have been used as catalysts in the
Henry reaction is shown in Table 5. There are some reports on copper(II) based MOFs41,71 which are
active in the Henry reaction, but the obtained yields are usually lower than those achieved with 1
(entries 1-3, Table 5). Catalyst 2 shows a better or comparable yield with those of other reported
zinc MOFs (entries 4-8, Table 5).42,44,72,73 Moreover, in most of the reported cases, organic solvents
have been used for this reaction, and only very few examples are known where water has been
applied.74,75 In our system, interestingly, the reaction yield and the selectivity are higher in aqueous
medium than in an organic solvent. The use of an aqueous medium has many advantages owing to
the unique properties of water, such as non-toxic, safe and environmentally benign. In that context,
our complexes are new, effective, recyclable (see below) and environmentally ‘green’ catalysts for
the Henry reaction.
Table 5. Comparison of activities of MOFs as catalysts for the Henry reaction with 4-nitrobenzaldehyde and
nitroethane
Entry
Catalyst
Solvent/Temp/Time
Water/75˚C/40h
Aldehyde
Yield (%)
Selectivity
Ref.
syn/anti
1
2
4-Nitrobenzaldehyde
4-Nitrobenzaldehyde
98
95
79:21
78:22
This
work
1
[Cu4(HLala)2(H2O)4(MeO)4]n
MeOH/70˚C/24h
41
17
ACS Paragon Plus Environment

Crystal Growth & Design
Page 18 of 26
1
2
3
4
5
6
7
8
9
3
4
[Cu3(pdtc)(La)2(H2O)3].2DMF.10H2O
Solvent free/70˚C/36h
Water/75˚C/40h
4-Nitrobenzaldehyde
78
94
Not determined
77:23
72
4-Nitrobenzaldehyde
4-Nitrobenzaldehyde
This
work
2
5
[Zn2(Lb)2(4,4’-
bipyridine)2(H2O)(DMF)]n
MeOH/70˚C/48h
98
80:20
44
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
6
7
[Zn3(TCPB)2∙2H2O]∙ 2H2O∙4DMF
Solvent free/70˚C/72h
4-Nitrobenzaldehyde
4-Nitrobenzaldehyde
4-Nitrobenzaldehyde
15
34
97
Not determined
Not determined
80:20
72
73
42
[Zn(3,3’-TPDC)(DABCO)]∙DMF∙2H2O Solvent free/60˚C/120h
[Zn(Lc)(H2O)2]n MeOH/70˚C/48h
(2S,2′S,2″S)-2,2′,2″-(benzenetricarbonyltris(azanediyl))tripropanoate; La
8
HLala
=
=
(E)-4-(2-(pyridin-4-yl)vinyl)benzoic acid; Lb
=
2-
acetamidoterephthalate; TCPB = 1,3,5-tri(4-carboxyphenoxy)benzene; pdtc = pyridine-2,3,5,6-tetracarboxylate; 3,3’-TPDC = terphenyl-3,3,-
dicarboxylate; DABCO = 1,4-diazabicyclo[2.2.2]octane; Lc = 5-benzamidoisophthalate.
A possible reaction mechanism for the Henry reaction catalyzed by our MOFs involves the activation
of both the aldehyde and nitroethane by the metal centre (with deprotonation of the latter
substrate) followed by the formation of C-C bond upon nucleophilic addition of the nitronate to the
aldehyde carbonyl group, leading to the β-nitroalkanol.40-45 The proton abstraction from the
nitroalkane ligand and the protonation of the C-C coupled species can be assisted by the ligand (with
a carboxylate and an amine group) and also by water (amphoteric behaviour), thus possibly
accounting for the good activity of our catalysts in the presence of water. Besides that, in framework
1, the lability of the DMF ligand and the possible bi- to monodentate carboxylate coordination
should lead to coordinative unsaturation, promoting the catalytic activity which also results from the
high Lewis basic nature of copper(II).
Typical considerable syn/anti selectivities of ca. 4:1 are obtained (maximum of ca. 6:1) for which the
rigidity of the L12- ligand possibly contributes, favoring a parallel type orientation of the coordinated
reacting substrates.
Recyclability and Heterogeneity tests
In order to examine the stability of 1 in alcohols oxidation and the Henry reactions, we also tested
the recyclability of this heterogeneous catalyst.
For this purpose, we scaled up the nitroaldol reaction for easy separation of catalyst 1 after the
reaction. The catalyst was separated upon filtration or centrifugation, washed with methanol and
dried at room temperature before being recycled. As shown in Fig. 6, the catalytic system
maintained constant reactivity for five consecutive cycles.
18
ACS Paragon Plus Environment

Page 19 of 26
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 6 Effect of the catalyst recycling on the yield of β-nitroalkanol from the Henry reaction of
benzaldehyde catalyzed by 1.
In the oxidative media used for the conversion of primary and secondary alcohols to the
corresponding aldehydes and ketones, 1 was also able to be reused without loss of activity during 3
consecutive cycles (Figure 7) while maintaining the selectivity. On completion of a stage, the
products were analyzed as usually and 1 was recovered by hot filtration from the reaction mixture
and dried overnight at 50 º C. The subsequent cycle was initiated upon addition of new standard
portions of all other reagents. Moreover, no leaching was detected during the recycling tests:
negligible additional yield of products was found up to 1 h reaction after catalyst separation by
filtration. This suggests that 1 is a true heterogeneous catalyst, and no catalytically active species
were released into solution.
In order to check the structural integrity of the catalyst 1, in both reactions, we have performed FT-
IR and powder X-ray diffraction of catalyst 1 taken before and after the oxidation of alcohols and
nitroaldol reactions. They indicate that the structure of the solid was retained (Figure S2).
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
Catalytic Cycle
Figure 7 Effect of the catalyst recycling on the yields of acetophenone (
-) and benzaldehyde (ꢀ) from
the oxidation of 1-phenylethanol and benzyl alcohol, respectively, catalyzed by 1.
19
ACS Paragon Plus Environment

Crystal Growth & Design
Page 20 of 26
1
2
3
4
5
6
7
8
9
To further clarify if the catalytic process is heterogeneous or homogeneous, the following test for
the nitroaldol reaction was carried out. We performed a controlled experiment with catalyst 1 until
an intermediate yield (ca. 50%) was observed (6 h), then removed the catalyst by centrifugation and
kept the catalyst free reaction solution under the same conditions stirred for additional 35 h. As
shown in Fig. 5, after removal of the solid catalyst, the yield of benzaldehyde did not further increase
appreciably. These results demonstrate that the catalysis is heterogeneous in nature. Additionally,
the filtrated solution, after the separation of the catalyst, was evaporated to dryness and the
amount of copper determined was only 0.01% of the amount used in the reaction, thus ruling out
any significant leaching of the catalyst.
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
Conclusion
We successfully isolated three metal organic frameworks (1 - 3) of Cu(II), Zn(II) and Cd(II) derived
from 5-{(pyridin-4-ylmethyl)amino}isophthalic acid (H2L1) under different synthetic conditions.
Single crystal X-ray diffraction analysis revealed that frameworks 1 and 2 display 2D structures but 3
has a 3D structure. Their construction depends on the particular reaction conditions, which lead to
significant differences in the coordination networks. We have also synthesized the salt (H3L1+Cl-) of
protonated 5-{(pyridin-4-ylmethyl)amino}isophthalic acid and chloride ion and its hydrogen bonding
ability. This salt constructs a 2D hydrogen-bonded network via various halogen and hydrogen
bonding interactions.
These frameworks (1 – 3) exhibit a high activity in an exceptionally short reaction time for the
solvent-free MW-assisted oxidation of primary and secondary alcohols to the corresponding
aldehydes and ketones. These complexes also effectively catalyze the Henry reaction of nitroethane
with various aldehydes in aqueous medium producing the corresponding β-nitroalkanols in high
yields. Among the three frameworks, compound 1 is the most active one. Therefore, we have
synthesized catalysts that are effective in the sequential catalytic conversion of alcohols to
aldehydes followed by the conversion of the latter into nitroalkanes. The use of water instead of an
organic solvent brings a number of benefits because it is safe, economical, environmentally benign
and non-toxic.
We have also proved the stability and recyclability of the catalysts. The copper(II) carboxylate
framework 1 can be considered as an heterogeneous ‘green’ catalyst for the preparation of simple
nitro alcohols. It was also demonstrated that the reaction proceeds mainly inside the pore system of
compound 1 which is stable under the used conditions.
The above observations provide further evidence that simple MOFs can be utilized as effective
heterogeneous catalysts in the important types of reactions of this work. Further studies of the
applications of these porous MOFs are in progress.
Supporting Information
Bond distances, angles, and hydrogen bonding tables for all compounds (H3L1+Cl- and 1-3), Crystal
1
Structure Description of H3L1+Cl-, FT-IR, and PXRD before and after catalysis, H NMR spectra after
the Henry reaction, crystallographic data (CIF).
20
ACS Paragon Plus Environment

Page 21 of 26
Crystal Growth & Design
1
2
3
4
5
Corresponding Authors
*(A.K.) E-mail: anirbanchem@gmail.com.
*(L.M.D.R.S.M.) E-mail: lmartins@deq.isel.ipl.pt.
*(A.J.L.P.) E-mail: pombeiro@tecnico.ulisboa.pt.
Notes
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
The authors declare no competing financial interest.
Acknowledgements
This work has been supported by the Fundação para a Ciência e a Tecnologia (FCT), Portugal (project
UID/QUI/UI0100/2013). Authors A. Karmakar and S. Hazra express their gratitude to the FCT for
post-doctoral fellowships (Ref. No. SFRH/BPD/76192/2011 and SFRH/BPD/78264/2011).
Reference
(1) Zhou H. –C.; Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5415-5418.
(2) Zhang, Z.; Zaworotko, M. J. Chem. Soc. Rev. 2014, 43, 5444-5455.
(3) Zhu, Q. –L.; Xu, Q. Chem. Soc. Rev. 2014, 43, 5468-5512.
(4) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629–1658.
(5) Elsaidi, S. K.; Mohamed, M. H.; Wojtas, L.; Chanthapally, A.; Pham, T.; Space, B.; Vittal, J. J.;
Zaworotko, M. J. J. Am. Chem. Soc. 2014, 136, 5072–5077.
(6) Karmakar, A.; Goldberg, I. CrystEngComm 2011, 13, 339-349.
(7) Karmakar, A.; Goldberg, I. CrystEngComm 2010, 12, 4095-4100.
(8) Karmakar, A.; Oliver, C. L.; Z. Kristallogr. 2013, 228, 330–334.
(9) Karmakar, A.; Baruah, J. B.; Shankar, R. B. CrystEngComm 2009, 11, 832-840.
(10) Liu, J.; Chen, L.; Cui, H.; Zhang, J.; Zhang L.; Su, C. –Y. Chem. Soc. Rev. 2014, 43, 6011-6061.
(11) Karmakar, A.; Titi, H. M.; Goldberg, I. Cryst. Growth Des. 2011, 11, 2621–2636.
(12) Karmakar, A.; Hazra, S.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Dalton Trans. 2015, 44, 268-
280.
(13) Hu, Z.; Deibert, B. J.; Li, J. Chem. Soc. Rev. 2014, 43, 5815-5840.
(14) He, Y.; Zhou, W.; Qian, G.; Chen, B. Chem. Soc. Rev. 2014, 43, 5657-5678.
(15) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353-1379.
(16) Lu, W.; Wei, Z.; Gu, Z. –Y.; Liu, T. –F.; Park, J.; Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle III, T.;
Bosch, M.; Zhou, H. –C. Chem. Soc. Rev. 2014, 43, 5561-5593.
21
ACS Paragon Plus Environment

Crystal Growth & Design
Page 22 of 26
1
2
3
(17) Mulfort, K. L.; Farha, O. K.; Stern, C. L.; Sarjeant, A. A.; Hupp, J. T. J. Am. Chem. Soc. 2009, 131,
4
5
3866–3868.
6
7
(18) Farha, O. K.; Mulfort, K. L.; Hupp, J. T. Inorg. Chem. 2008, 47, 10223–10225.
8
9
(19) Karabach, Y. Y.; Kopylovich, M. N.; Mahmudov, K. T.; Pombeiro, A. J. L. Microwave-assisted
catalytic oxidation of alcohols to carbonyl compounds, (ch.18) in: Pombeiro, A. J. L. (Ed.), Advances in
Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on
Organometallic Chemistry Celebratory Book, Wiley, 2014, 233–245.
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
(20) Tojo, G.; Fernandez, M. Oxidation of Alcohols to Aldehydes and Ketones, Springer, Berlin, 2006.
(21) Kopylovich, M. N.; Ribeiro, A. P. C.; Alegria, E. C. B. A.; Martins, N. M. R.; Martins, L. M. D. R. S.;
Pombeiro, A. J. L. Adv. Organomet. Chem. 2015, 63, 91-174.
(22) Sutradhar, M.; Martins, L. M. D. R. S.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Coord. Chem.
Rev. 2015, 301-302, 200-239.
(23) Sutradhar, M.; Martins, L. M. D. R. S.; Guedes da Silva, M. F. C.; Alegria, E. C. B. A.; Liu, C. -M.;
Pombeiro, A. J. L. Dalton Trans. 2014, 43, 3966-3977.
(24) Alexandru, M.; Cazacu, M.; Arvinte, A.; Shova, S.; Turta, C.; Simionescu, B. C.; Dobrov, A.;
Alegria, E. C. B. A.; Martins, L. M. D. R. S.; Pombeiro, A. J. L.; Arion, V. B. Eur. J. Inorg. Chem. 2014,
120-131.
(25) Shul’pin, G. B.; Kirillova, M. V.; Shul’pina, L. S.; Pombeiro, A. J. L.; Karslyan, E. E.; Kozlov, Y. N.
Cat. Commun. 2013, 31, 32–36.
(26) Gryca, I.; Machura, B.; Małecki, J. G.; Shul'pina, L. S.; Pombeiro, A. J. L.; Shul'pin, G. B. Dalton
Trans. 2014, 43, 5759-5776.
(27) Morad, M.; Sankar, M.; Cao, E.; Nowicka, E.; Davies, T. E.; Miedziak, P. J.; Morgan, D. J.; Knight,
D. W.; Bethell, D.; Gavriilidis, A.; Hutchings, G. J. Catal. Sci. Technol. 2014, 4, 3120-3128.
(28) Microwaves in Organic Synthesis, ed. Loupy, A. Wiley/VCH, Weinheim, 2002.
(29) Microwave Assisted Organic Synthesis, ed. Tierney J. P.; Lidström, P. Blackwell Publishing/CRC
Press, Oxford, 2005.
(30) Jlassi, R.; Ribeiro, A. P. C.; Guedes da Silva, M. F. C.; Mahmudov, K. T.; Kopylovich, M. N.;
Anisimova, T. B.; Naïli, H.; Tiago, G. A. O.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2014, 4541–4550.
(31) Ma, Z.; Wei, L.; Alegria, E. C. B. A.; Martins, L. M. D. R. S.; Guedes da Silva, M. F. C.; Pombeiro, A.
J. L. Dalton Trans., 2014, 43, 4048-4058.
(32) Nasani, R.; Saha, M.; Mobin, S. M.; Martins, L. M. D. R. S.; Pombeiro, A. J. L.; Kirillov, A. M.;
Mukhopadhyay, S. Dalton Trans. 2014, 43, 9944-9954.
(33) Timokhin, I.; Pettinari, C.; Marchetti, F.; Pettinari, R.; Condello, F.; Galli, S.; Alegria, E. C. B. A.;
Martins, L. M. D. R. S.; Pombeiro, A. J. L. Cryst. Growth Des. 2015, 15, 2303-2317.
22
ACS Paragon Plus Environment

Page 23 of 26
Crystal Growth & Design
1
2
3
(34) Fernandes, R. R.; Lasri, J.; Guedes da Silva, M. F. C.; da Silva, J. A. L.; Frausto da Silva, J. J. R.;
4
5
Pombeiro, A. J. L. J. Mol. Catal. A Chem. 2011, 351, 100–111.
6
7
8
(35) Shixaliyev, N. Q.; Gurbanov, A. V.; Maharramov, A. M.; Mahmudov, K. T.; Kopylovich, M. N.;
Martins, L. M. D. R. S.; Nenajdenko, V. G.; Pombeiro, A. J. L. New J. Chem. 2014, 38, 4807-4815.
9
(36) Li, L.; Matsuda, R.; Tanaka, I.; Sato, H.; Kanoo, P.; Jeon, H. J.; Foo, M. L.; Wakamiya, A.; Murata,
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
Y.; Kitagawa, S. J. Am. Chem. Soc. 2014, 136, 7543−7546.
(37) Shibasaki, M.; Kanai, M.; Matsunaga, S.; Kumagai, N. Multimetallic Multifunctional Catalysts for
Asymmetric Reactions: Bifunctional Molecular Catalysis (ed. Ikariya, T.; Shibasaki, M.), Topics in
Organometallic Chemistry, Springer-Verlag Berlin Heidelberg, 2011, 37, 1-30.
(38) Milner, S. E.; Moody, T. S.; Maguire, A. R. Eur. J. Org. Chem. 2012, 3059–3067.
(39) Luzzio, F. A. Tetrahedron 2001, 57, 915-945.
(40) Karmakar, A.; Hazra, S.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. New J. Chem. 2014, 38,
4837-4846.
(41) Karmakar, A.; Oliver, C. L.; Roy, S.; Öhrström, L. Dalton Trans. 2015, 44, 10156-10165.
(42) Karmakar, A.; Guedes da Silva, M. F. C.; Hazra, S.; Pombeiro, A. J. L. New J. Chem. 2015, 39,
3004-3014.
(43) Hazra, S.; Karmakar, A.; Guedes da Silva, M. F. C.; Dlháň, Ľ.; Boča, R.; Pombeiro, A. J. L. New J.
Chem. 2015, 39, 3424-3434.
(44) Karmakar, A.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Dalton Trans. 2014, 43, 7795–7810.
(45) Rocha, B. G. M.; Mac Leod, T. C. O.; Guedes da Silva, M. F. C.; Luzyanin, K. V.; Martins, L. M. D. R.
S.; Pombeiro, A. J. L. Dalton Trans. 2014, 43, 15192-15200.
(46) Chen, M. –S.; Bai, Z. –S.; Okamura, T.; Su, Z.; Chen, S. –S.; Sun, W. –Y.; Ueyama, N. CrystEngComm
2010, 12, 1935-1944.
(47) Chen, M. –S.; Su, Z.; Chen, M.; Chen, S. –S.; Li, Y. –Z.; Sun, W. –Y. CrystEngComm 2010, 12, 3267-
3276.
(48) Das, M. C.; Bharadwaj, P. K. J. Am. Chem. Soc. 2009, 131, 10942–10949.
(49) Das, M. C.; Bharadwaj, P. K. Chem. Eur. J. 2010, 16, 5070–5077.
(50) Chen, M. –S.; Chen, M.; Takamizawa, S.; Okamura, T.; Fan J.; Sun, W. –Y. Chem. Commun. 2011,
47, 3787-3789.
(51) Bulbule, V. J.; Deshpande, V. H.; Velu, S.; Sudalai, A.; Sivasankar, S.; Sathe, V. T. Tetrahedron
1999, 55, 9325-9332.
(52) Bruker, APEX2 & SAINT, AXS Inc., Madison, WI, 2004.
23
ACS Paragon Plus Environment

Crystal Growth & Design
Page 24 of 26
1
2
3
4
5
6
7
8
(53) Sheldrick, G. M. Acta Crystallogr. Sect. A 2008, 64, 112-122.
(54) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837-838.
(55) Spek, A. L. Acta Crystallogr. Sect. A 1990, 46, C34.
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
(56) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 5th edn,
Wiley & Sons, New York, 1997.
(57) Munoz-Hernandez, M. -A.; Keizer, T. S.; Wei, P.; Parkin, S.; Atwood, D. A. Inorg. Chem. 2001, 40,
6782–6787.
(58) Yang, L.; Powell, D. R.; Houser, R. P. Dalton Trans. 2007, 955–964.
(59) Blatov, V. A. Struct. Chem. 2012, 23, 955-963.
(60) Mattalia, J. M.; Vacher, B.; Samat, A.; Chanon, M. J. Am. Chem. Soc. 1992, 114, 4111-4119.
(61) Dronova, M. S.; Bilyachenko, A. N.; Yalymov, A. I.; Kozlov, Y. N.; Shul’pina, L. S.; Korlyukov, A. A.;
Arkhipov, D. E.; Levitsky, M. M.; Shubina, E. S.; Shul’pin, G. B. Dalton Trans. 2014, 43, 872-882.
(62) Kirillova, M. V.; Kuznetsov, M. L.; Kozlov, Y. N.; Shul’pina, L. S.; Kitaygorodskiy, A.; Pombeiro, A. J.
L.; Shul’pin, G. B. ACS Catal. 2011, 1, 1511–1520.
(63) Fei, H.; Shin, J. W.; Meng, Y. S.; Adelhardt, M.; Sutter, J.; Meyer, K.; Cohen, S. M. J. Am. Chem.
Soc. 2014, 136, 4965−4973.
(64) Paul, M.; Adarsh, N. N.; Dastidar, P. Cryst. Growth Des. 2014, 14, 1331−1337.
(65) Zhang, X.; Dong, W.; Luan, Y.; Yang, M.; Tan, L.; Guo, Y.; Gao, H.; Tang, Y.; Dang, R.; Li, J.; Wang,
G. J. Mater. Chem. A 2015, 3, 4266–4273.
(66) Zhu, J.; Wang, P. C.; Lu, M. Appl. Catal. A: Gen. 2014, 477, 125-131.
(67) Qi, Y.; Luan, Y.; Yu, J.; Peng, X.; Wang, G. Chem. Eur. J. 2015, 21, 1589–1597.
(68) Peng, L.; Zhang, J.; Xue Z.; Han, B.; Sang, X.; Liu, C.; Yang, G. Nat. Commun. 2014, 5:4465.
(69) Paul, M.; Adarsh, N.N.; Dastidar P. Cryst. Growth Des. 2014, 14, 1331-1337.
(70) Feng X.; Xu, C.; Wang, Z. -Q.; Tang, S-F.; Fu, W. -J.; Ji, B-M.; Wang, L. -Y. Inorg. Chem. 2015, 54,
2088-2090.
(71) Shi, L. –X.; Wu, C. –D. Chem. Commun. 2011, 47, 2928-2930.
(72) Lin, X. -M.; Li, T. -T.; Wang, Y. -W.; Zhang, L.; Su, C. -Y. Chem. Asian J. 2012, 7, 2796-2804.
(73) Gu, J. –M.; Kim, W. –S.; Huh, S. Dalton Trans. 2011, 40, 10826-10829.
24
ACS Paragon Plus Environment

Page 25 of 26
Crystal Growth & Design
1
2
3
(74) Chintala, P.; Ghosh, S. K.; Long, E.; Headley, A. D.; Nia, B. Adv. Synth. Catal. 2011, 353, 2905-
4
5
2909.
6
7
8
(75) Lai, G.; Guo, F.; Zheng, Y.; Fang, Y.; Song, H.; Xu, K.; Wang, S.; Zha, Z.; Wang, Z. Chem. Eur. J.
2011, 17, 1114-1117.
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
25
ACS Paragon Plus Environment

Crystal Growth & Design
Page 26 of 26
1
2
3
4
Table of Contents
5
6
7
8
9
Metal–Organic Frameworks with Pyridyl-Based Isophthalic Acid and
Their Catalytic Applications in Microwave Assisted Peroxidative
Oxidation of Alcohols and Henry Reaction
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
Anirban Karmakara,* Luísa M.D.R.S. Martinsb,* Susanta Hazraa, M. Fátima C. Guedes da Silvaa and
Armando J. L. Pombeiroa*
a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais,
1049–001, Lisbon, Portugal. E-mail: anirbanchem@gmail.com; pombeiro@tecnico.ulisboa.pt
b Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico
de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal E-mail: lmartins@deq.isel.ipl.pt
Synopsis
5-{(pyridin-4-ylmethyl)amino} isophthalic acid is used to synthesize three new copper(II), zinc(II) and
cadmium(II) MOFs which act as heterogeneous catalysts for the peroxidative oxidation of alcohols as
well as for the Henry reaction of different aldehydes in water.
26
ACS Paragon Plus Environment