New Zn(II) coordination polymers constructed from amino-alcohols and aromatic dicarboxylic acids: Synthesis, structure, photocatalytic properties, and solid-state conversion to ZnO

Article abstract of DOI:10.1021/cg501604c

Four new coordination polymers have been obtained solvothermally from the reactions of Zn(NO₃)₂·6H₂O with 1,2-, 1,3-, or 1,4-benzedicarboxylic acids in the presence of various amino-alcohols: 1 [Zn₂(Htea)₂(1,2-bdc)] (1), 1 [Zn(H₃tris)(1,3-bdc)(CH₃OH)] (2), 3 [Zn₅(Htea)₂(1,3-bdc)₃(H₂O)]·2.6H₂O (3), and 3 [Zn₃(H₂dea)₂(1,4-bdc)₃] (4) (H₃tea = triethanolamine, H₃tris = tris(hydroxymethyl)aminomethane, H₂dea = diethanolamine, 1,2-H₂bdc =1,2-benzenedicarboxylic acid, 1,3-H₂bdc =1,3-benzenedicarboxylic acid, and 1,4-H₂bdc =1,4-benzenedicarboxylic acid). Their crystal structures, thermogravimetric analyses, solid-state transformation to ZnO and characterization of the resultant zinc oxide particles are reported. Compounds 1 and 2 show three-dimensional (3D) supramolecular architectures, generated from the interconnection of the zigzag (in 1) and respectively the linear (in 2) chains through hydrogen bonding interactions. The crystal structure of 3 revealed the presence of five different types of zinc atoms that are successively linked through carboxilato or alkoxo bridges in a helicoidal chain running along the crystallographic a axis. Both right-handed (P) and left-handed (M) helices are present in the crystal, and they are alternately interconnected by pairs of isophthalato bridges, resulting in channels of hexagonal shape, filled with water molecules. Compound 4 has a 3D structure in which linear centrosymmetric {Zn₃(H₂dea)₂}⁶⁺ nodes are joined by terephthalate bridges. Owing to its porous network, compound 3 was tested in two selective reactions: photooxidation of phenol to hydroquinone and aerobic photooxidative condensation of benzylamine to N-benzylidenebenzylamine.

Full text of DOI:10.1021/cg501604c

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Article
New Zn(II) coordination polymers constructed from amino-
alcohols and aromatic dicarboxylic acids: synthesis, structure,
photocatalytic properties and solid-state conversion to ZnO
Carmen Paraschiv, Andrei Cucos, Sergiu Shova, Catalin Maxim, Augustin M. Madalan,
Diana Beatrice Visinescu, Bogdan Cojocaru, Vasile Parvulescu, and Marius Andruh
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg501604c • Publication Date (Web): 19 Dec 2014
Downloaded from http://pubs.acs.org on December 23, 2014
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New Zn(II) coordination polymers constructed from amino-alcohols and aromatic
dicarboxylic acids: synthesis, structure, photocatalytic properties and solid-state
conversion to ZnO
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,†
†
‡
§
§
Carmen Paraschiv,* Andrei Cucos, Sergiu Shova, Augustin M. Madalan, Catalin Maxim,
┴
#
,#
,§
Diana Visinescu, Bogdan Cojocaru, Vasile I. Parvulescu,* and Marius Andruh*
†
National Institute for Research and Development in Electrical Engineering ICPE-CA, Splaiul
Unirii 313, 030138 Bucharest, Romania
‡
“
Petru Poni” Institute of Macromolecular Chemistry of the Roumanian Academy, Aleea Grigore
Ghica Voda 41-A, RO-700487 Iasi, Romania
§
Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava
Rosie 23, 020464 Bucharest, Romania
┴
Coordination and Supramolecular Chemistry Laboratory, “Ilie Murgulescu” Institute of
Physical Chemistry, Romanian Academy, Splaiul Independentei 202, 060021 Bucharest,
Romania
#
Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis,
University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest, Romania
*
Authors to whom correspondence should be addressed. E-mail: carmenparaschiv@yahoo.com
C.P.), vasile_parvulescu@g.unibuc.ro (V.I.P.), marius.andruh@dnt.ro (M.A.)
(
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Abstract
Four new coordination polymers have been obtained solvothermaly from the reactions of
Zn(NO ) ·6H O with 1,2-, 1,3- or 1,4-benzedicarboxylic acids in the presence of various amino-
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∞
∞
∞
alcohols:
[Zn (Htea) (1,2-bdc)] 1,
[Zn(H tris)(1,3-bdc)(CH OH)] 2,
[Zn (Htea) (1,3-
3 5 2
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∞
bdc) (H O)]·2.6H O 3,
[Zn (H dea) (1,4-bdc) ] 4 (H tea = triethanolamine, H tris =
3
2
2
3
3
2
2
3
3
3
tris(hydroxymethyl)aminomethane,
H dea
2
=
diethanolamine,
1,2-H bdc
=
1,2-
2
benzenedicarboxylic acid, 1,3-H bdc = 1,3-benzenedicarboxylic acid, 1,4-H bdc = 1,4-
2
2
benzenedicarboxylic acid). Their crystal structures, thermogravimetric analyses, solid-state
transformation to ZnO and characterization of the resulted zinc oxide particles are reported.
Compounds 1 and 2 show three-dimensional supramolecular architectures, generated from the
interconnection of the zigzag (in 1) and respectively the linear (in 2) chains through hydrogen
bonding interactions. The crystal structure of 3 revealed the presence of five different types of
zinc atoms, that are successively linked through carboxilato or alkoxo bridges in a helicoidal
chain running along the crystallographic a axis. Both right-handed (P) and left-handed (M)
helices are present in the crystal and they are alternately interconnected by pairs of isophthalato
bridges, resulting in channels of hexagonal shape, filled with water molecules. Compound 4 has
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+
a 3D structure in which linear centrosymmetric {Zn (H Dea) } nodes are joined by
3
2
2
terephthalate bridges. Owing to its porous network, compound 3 was tested in two selective
reactions: photo-oxidation of phenol to hydroquinone and aerobic photo-oxidative condensation
of benzylamine to N-benzylidenebenzylamine.
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INTRODUCTION
The chemistry of multifunctional coordination polymers (CPs) has rapidly become one of the
most challenging and appealing research areas due to their potential in both traditional and
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emerging applications: gas storage,
separation,
catalysis,
luminescence,
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recognition,
bioactive molecules
and magnetism.
A rich variety of structures and
topologies have been rationally designed and synthesized by judicious selection of connectors
(metal ions or metal clusters) and linkers (organic molecules, inorganic anions or
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metalloligands).
The sum of the distinctive characteristics of the inorganic and organic
components and their possible synergistic action could provide novel and intriguing properties
for the resulting materials. Furthermore, the final architecture can be influenced by auxiliary
ligands, solvent molecules, temperature, pH, coordinated or uncoordinated anions.
Numerous multitopic ligands with two or more discrete metal-binding sites have been
used in the construction of coordination polymers. Conventional linkers are usually organic
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compounds containing donor atoms or groups of donor atoms (polycarboxylates,
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68-80
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90-
phenolates,
amines,
pyridyl derivatives,
sulfonates,
phosphonates,
azolates
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3
). In particular, carboxylate-based systems, especially three-dimensional porous metal organic
frameworks (MOFs) constructed with rigid aromatic backbones (benzene-, naphthalene-,
anthracene-, and pyrene-based derivatives), have attracted considerable attention due to the
tunability of their structures and properties and their suitability for hydrogen storage, sorption,
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separation and sensing.
The node-and-spacer approach
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proved to be a successful strategy for the synthesis
of coordination polymers. In a series of papers, we developed an extension of the classical
approach, showing that alkoxo-bridged Cu(II) cationic species can be used as nodes in
constructing extended structures by connecting them through a large variety of spacers (neutral
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or anionic).
As a follow-up to this research, we decided to employ the Zn(II) ion for the
construction of coordination polymers based on amino-alcohols and different multitopic ligands.
10
The spherical d configuration is correlated with a flexible coordination environment and
various geometries of Zn(II) complexes are possible: from tetrahedral through trigonal
bipyramidal and square pyramidal to octahedral, with more or less severe distortions of these
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ideal polyhedra. Alkoxo-bridged Zn(II) systems are scarce,
and coordination polymers
consisting of alkoxo-bridged Zn(II) cores and anionic polycarboxylate spacers have not been
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reported until recently.
A series of Zn(II)-trimesate metal organic frameworks (MOFs)
obtained under solvothermal conditions in the presence of various aminoalcohols has been
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described, while the reaction of zinc nitrate, terephthalic acid and triethanolamine afforded
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another MOF with formula [Zn (H tea) (1,4-bdc) ]·2(MeOH). Another study presents several
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discrete Zn(II)–triethanolamine–acetate complexes, which were further used as precursors for
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ZnO nanoparticles.
Many polymeric zinc complexes are characterized by robust and thermally stable open-
framework structures and some of them were already evaluated as heterogeneous photocatalysts,
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due to their versatility in a wide range of reactions.
Selective oxidation using recoverable
heterogeneous catalysts has become an important target of the last decades, representing the most
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important strategy to selectively introduce oxygen atoms in organic molecules.
The
development of new types of heterogeneous catalytic systems for liquid-phase oxidations
represents an excellent example of green chemistry where environmentally friendly oxidants
125
(
hydrogen peroxide and air) lead to an unprecedented increase of the e-factor.
N-
benzylidenebenzylamine and hydroquinone are important intermediate molecules that are
expected to be manufactured via this strategy. Particularly, the selective aerobic oxidative
condensation of benzylamine to N-benzylidenebenzylamine is an important reaction in organic
chemistry since the product of reaction is a valuable intermediate in organic synthesis with direct
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applications in the production of fine chemicals, pharmaceutics, agrochemicals, etc.
To
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replace the stoichiometric oxidants,
heterogeneous metal catalysts (Ru, Rh, Pt, Ir, Pd, Ag,
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Au) deposited on supports at relatively high temperatures have been used.
More recently,
an iron(III)-1,3,5-benzenetricarboxylate MOF containing N-hydroxyphthalimide as a guest in the
intracrystalline space was reported as a heterogeneous catalyst for the aerobic oxidation of
1
34
benzylamine and its derivatives to their corresponding benzylimines.
In the case of
dihydroxybenzenes, several M (BTC) metal-organic frameworks (M = Cu(II), Co(II), Ni(II),
3
2
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35,136
BTC = 1,3,5-benzenetricarboxylate) or Fe-MOF-74 were employed as catalysts.
Another recent application of CPs is their use in the preparation of oxide materials. The
potential of Zn(II) molecular compounds as precursors for ZnO phases has been investigated and
it has been shown that particles with controlled morphologies could be generated. Thermal
decomposition represents a suitable way to tailor the properties of the ZnO–based materials, and
both the starting compound and the thermal treatment play a key role in the features and
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properties of the obtained materials.
By employing ligands available in large quantities at a
low cost for the synthesis of CPs, this strategy for obtaining ZnO materials is relatively cheap
and accessible.
∞
In this work, we report the synthesis of four CPs:
[Zn (Htea) (1,2-bdc)] 1,
1 2 2
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∞
∞
∞
1[
3[
Zn(H tris)(1,3-bdc)(CH OH)]
2,
[Zn (Htea) (1,3-bdc) (H O)]·2.6H O
3,
=
3
3
3
5
2
3
2
2
Zn (H dea) (1,4-bdc) ]
4
(H tea
=
triethanolamine,
H tris
3
3
2
2
3
3
tris(hydroxymethyl)aminomethane,
H dea
2
=
diethanolamine,
1,2-H bdc
=
1,2-
2
benzenedicarboxylic acid, 1,3-H bdc = 1,3-benzenedicarboxylic acid, 1,4-H bdc = 1,4-
2
2
benzenedicarboxylic acid). The three dicarboxylic acids were employed to explore and establish
the effect of the position of carboxyl groups on the network topologies in the isolated products.
The crystal structures of the four compounds, thermogravimetric analyses, solid-state
transformation to ZnO and characterization of the resulted zinc oxide particles are reported. The
porous network of compound 3 prompted us to test it in two selective reactions: photo-oxidation
of phenol to hydroquinone and aerobic photo-oxidative condensation of benzylamine to N-
benzylidenebenzylamine.
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EXPERIMENTAL SECTION
Materials. All chemicals were of reagent grade quality and were used as received from
commercial sources without further purification.
Physical Measurements. FT-IR spectra were recorded on KBr pellets in the 4000-400
0
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cm range using a Bruker TENSOR 27 FTIR Spectrometer. Elemental analyses (C, H, N) were
performed on EuroVector EA3000 CHNS-O Elemental Analyzer. HPLC measurements were
performed on Agilent Technologies 1260 Infinity with DAD detector, Column Eurosphere C18,
flow rate 1 mL/min, CAN: H O = 40: 60, λ = 274.5 nm, V = 10 µL. The Total Organic Carbon
2
inj
(TOC) analysis was carried out with a HiPerTOC Thermo Electron analyzer that allows both the
measurement of Total Carbon and Total Inorganic Carbon. GC measurements were performed
on a K072320 Thermo Quest Chromatograph equipped with a FID detector and a capillary
column of 30 m length with DB5 stationary phase). Raman spectra were recorded with a Horiba
JobinYvon – Labram HR UV-Visible-NIR Raman Microscope Spectrometer. PXRD diffractions
patterns were recorded on a Bruker D8 ADVANCE diffractometer. SEM measurements were
carried out on a Carl Zeiss SMT FESEM-FIB Workstation Auriga. The TG/DTG/DTA+FTIR
measurements were performed on a Netzsch STA 409 PC thermal analyzer coupled to a Bruker
Tensor 27 FTIR spectrometer equipped with a TG-IR gas cell. Samples weighing approx. 20 mg
-1
were placed in a cylindrical Al O holder and heated in synthetic air flow (100 ml min , purity
2
3
-1
99.999%), from room temperature to 600 °C, at a heating rate of 10 °C min . An empty Al O
2
3
holder was used as reference. The FTIR spectra were collected continuously during
-1
-1
measurements in the wavenumber range 4000 – 650 cm at a resolution of 4 cm .
X-ray crystallography. Single crystal X-ray diffraction measurements were performed
on STOE IPDS II diffractometer operating with a Mo-Kα (λ = 0.71073 Å) X-ray tube with a
graphite monochromator for complexes 2 and 4 and on an Xcalibur Eos 455 diffractometer
operating with Mo Kα (λ = 0.71073 Å) X-ray tube with 456 graphite monochromator for
complexes 1 and 3. The structures were solved by direct methods and refined by full-matrix least
2
squares techniques based on F . The non-H atoms were refined with anisotropic displacement
140
parameters. Calculations were performed using SHELX-97 crystallographic software package.
A summary of the crystallographic data and the structure refinement for 1-4 is given in Table 1.
CCDC reference numbers: 1031382 – 1031385.
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Syntheses
∞1[
Zn (Htea)(1,2-bdc)] 1 A mixture of Zn(NO ) ·6H O (0.3 g, 1 mmol), H tea (0.6 g, 4
mmol), 1,2-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et N (0.2 g, 2 mmol) in methanol
2
3 2
2
3
3
(20 ml) was sealed in a Teflon-lined stainless steel container and heated at 110 ºC for 20 hours,
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then slowly cooled to room temperature. The resulted colorless crystals were washed with
methanol and dried in air. Yield: 45%. Elemental chemical analysis: 38.12% C, 3.66% H, 3.18%,
-1
N (calcd); 37.9% C, 3.64% H, 3.19%, N (found). IR (cm , KBr): 3252 w, 2960 m, 2910 w, 2853
m, 1604 s, 1582 vs, 1561 vs, 1486 m, 1446 m, 1406 vs, 1382 s, 1271 w, 1087 m, 1069 m, 1023
m, 896 m, 775 m, 695 m, 656 w, 622 w, 510 w, 485 w.
∞1[
Zn(H tris)(1,3-bdc)(CH OH)] 2 was synthesized with a procedure similar to that
3
3
used for 1 except that equal moles of H tris were used in place of H tea. Yield: 5%. Elemental
3
3
chemical analysis: 40.8% C, 5% H, 3.66%, N (calcd); 40.8% C, 4.85% H, 3.69%, N (found). IR
-1
(
cm , KBr): 3457 br, 3310 m, 3249 s, 2943 w, 1622 s, 1622 s, 1601 m, 1578 s, 1550 m, 1435 s,
405 m, 1373 s, 1078 m, 1051 m, 1026 m, 751 m, 717 s, 636 w.
∞3[
Zn (Htea) (1,3-bdc) (H O)]·2.6H O 3: A mixture of Zn(NO ) ·6H O (0.3 g, 1 mmol),
H tea (0.3 g, 2 mmol), 1,3-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et N (0.2 g, 2 mmol)
1
5
2
3
2
2
3 2
2
3
3
in methanol (20 ml) was sealed in a Teflon-lined stainless steel container and heated at 110ºC
for 20 hours, then slowly cooled to room temperature. The resulted colorless crystals were
washed with methanol and dried in air. Yield: 34%. Elemental chemical analysis: 36.75% C,
-1
3
.7% H, 2.38%, N (calcd); 37% C, 3.64% H, 2.39%, N (found). IR (cm , KBr): 3070 w, 2963 w,
2897 w, 2854 w, 1608 s, 1558 s, 1448 m, 1395 s, 1276 w, 1064 m, 891 m, 743 s, 714 m.
∞
[Zn (H dea) (1,4-bdc) ] 4: A mixture of Zn(NO ) ·6H O (0.3 g, 1 mmol), H dea (0.21
3
3
2
2
3
3 2
2
2
g, 2 mmol), 1,4-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et N (0.2 g, 2 mmol) in
3
methanol (15 ml) was sealed in a Teflon-lined stainless steel container and heated at 110ºC for
20 hours, then slowly cooled to room temperature. The resulted colorless crystals were washed
with methanol and dried in air. Yield: 57%. Elemental chemical analysis: 42.76% C, 3.81% H,
-1
3.12%, N (calcd); 42.1% C, 3.89% H, 3.15%, N (found). IR (cm , KBr): 3497 w, 3272 w, 1602 s,
1504 m, 1371 s, 1069 m, 1053 m, 1017 w, 847 w, 826 m, 812 m, 750 s, 534 m.
Catalytic tests
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Selective photo-oxidation of phenol. In a typical phenol oxidation experiment, 15 mg of
photocatalyst 3 were added to a 10 mL aqueous solution of 40 ppm phenol. Samples were
irradiated for three hours and 30 ꢀL of solution were collected at 30 min intervals for high
performance liquid chromatography.
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9
0
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9
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0
Photo-oxidative condensation of benzylamine to N-benzylidenebenzylamine. The
benzylamine selective photo-oxidation experiments were solvent free. This matches one of the
requirements of green chemistry. In a typical experiment 50 mg of 3 were added to 2 mL of
benzylamine. Samples were irradiated for two hours with 30 ꢀL collected after each hour for gas
chromatography analysis.
Both sets of reactions were carried out by irradiation in the following conditions: under
UV with a UV lamp centered at 365 nm (2x120W Vilber Lourmat VL-340.BL, 11520 Lm,
33672 lx), and under visible with a visible lamp (150W Philips Master Colour CDM-T
150W/830, 13500 Lm, 5810 lx). Control experiments were carried out testing substrates
irradiated without catalysts and with catalysts stirred in the darkness. In all these cases the
conversion of substrates was zero.
The reaction efficiency (conversion) was calculated from the area of peaks from the
chromatograms (which is proportional with the moles of transformed phenol or amine):
Ai − Af
C =
×100
(1)
Ai
where: A = area of the peak of the substrate subject of the reaction; A = area of the peak
i
f
of the substrate in the reaction mixture. TOF values were calculated on this basis.
The selectivity to the product of interest was calculated from the area of the peaks of the
products:
Api
S =
×100
(2)
∑A
p
where: A = area of the peak of the product of interest; ΣA = sum of area of all the
pi
p
products.
Stability of the photo-catalyst 3
The stability of the catalyst paralleled with the evolution of the reaction was checked by
ex-situ experiments using Raman spectroscopy. Raman calibration was achieved using the Si
-1
5
20.7cm peak. The reaction suspension was analyzed every 15 minutes at 514 nm in the
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-1
extended spectral region from 300 up to 1500 cm The suspension was taken from the test tube
.
and poured in a liquid Macro-CH-Vis cell accessory. The analysis of the solid was carried out in
-1
the 150 – 4000 cm spectral region using a 633 nm laser. Before analysis, the solid was removed
from the reaction mixture and dried.
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RESULTS AND DISCUSSION
Crystal Structure Description
∞
[Zn (Htea)(1,2-bdc)] 1. Solvothermal treatment of phthalic acid with zinc(II) nitrate in
1
2
the presence of triethanolamine led to a one-dimensional coordination polymer (Figure 1a).
Compound 1 crystallizes in the P 2 /c monoclinic space group, with cell parameters and
1
1
structure refinement details given in Table 1. The asymmetric units consists of two
crystallographically independent Zn(II) ions, one doubly deprotonated triethanolamine molecule
2
-
2-
(
Htea ) and one 1,2-bdc anion. The two carboxylato groups belonging to the phthalate ligand
1
1
exhibit different coordination modes: one acts as a syn-syn bridge (ꢀ −η :η ), while the second
2
1
0
one coordinates in the monodentate mode (ꢀ −η :η ). The Zn1 atom is five-coordinated,
1
showing a slightly distorted trigonal bipyramidal geometry (the value of the distortion parameter
141
2-
τ
is 0.92). The equatorial plane is occupied by the three oxygen atoms from the Htea ligand
[Zn1−O5 = 1.979(2) Å; Zn1−O6 =1.981(2); Zn1−O7 = 2.131(2)], while the amino nitrogen
Zn1−N1 = 2.146(3) Å] and one carboxylato oxygen [Zn1−O1 = 1.975(2) Å] fill the axial
[
positions. The Zn2 atom displays a tetrahedral stereochemistry, with two alkoxo oxygen atoms
from two triethanolamine molecules and two carboxylato oxygens, one from the syn-syn bridge
and one from a monodentate group. The Zn2–O distances are in the 1.923(2) – 2.007(2) Å range.
The zinc atoms are connected through one syn-syn carboxylato and two alkoxo bridges,
resulting in zigzag chains running along the crystallographic c axis. The Zn···Zn separations are
3.414 and 3.535 Å. The chains are further interconnected (Figure 1b) through hydrogen bonds
2
-
established between the protonated OH groups from the Htea molecules and the uncoordinated
oxygen atoms of the phthalate ligands (O7’···O3 = 2.7 Å, ’ = 1-x, 1-y, 1-z).
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1
1
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2
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6
(
a)
0
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0
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1
2
3
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9
0
1
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5
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7
8
9
0
(b)
Figure 1. (a) Fragment of the zigzag chain in 1 with atom numbering scheme (symmetry code: ’
= x, 1.5-y, -0.5+z); (b) packing diagram showing the interchain hydrogen bonding interactions.
∞1[
H tris, and isophthalate anion led to the formation of a one-dimensional coordination polymer, in
Zn(H tris)(1,3-bdc)(CH OH)] 2. The self-assembly process involving zinc(II) ion,
3
3
3
2
+
which the bridging isophthalato ligands connect [Zn(H tris)(CH OH)] nodes (Figure 2a). The
3
3
two carboxylato groups belonging to the isophthalate anion exhibit different coordination modes:
bidentate chelating and monodentate. The zinc ion is hexacoordinated with a strongly distorted
octahedral geometry: one nitrogen and one oxygen atoms from a H tris molecule [Zn1–N1 =
3
2
.070(4); Zn1–O7 = 2.206(4) Å], three carboxylato oxygens [Zn1–O1 = 2.015(3); Zn1–O3 =
2.449(3); Zn1–O4 = 2.046(3) Å] and a coordinated methanol molecule [Zn1–O1M = 2.085(4) Å].
The Zn···Zn distance within the resulted linear chain is 10.23 Å. This is very close to that
found (10.13 Å) within a linear {Zn(1,3-bdc)} chain in the complex [Zn(ꢀ-3,3’-bpp)(1,3-
n
141
bdc)] ·nCH OH·2nH O (3,3’-bpp = 2,2’-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene).
n
3
2
The linear chains run along the crystallographic a axis and they are interconnected
through hydrogen bonds involving the uncoordinated OH groups from the H tris molecules and
3
two carboxylato oxygen atoms from an adjacent chain [O6–O1’ = 2.640 Å; O5–O4’ = 2.857 Å;
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(
’ = x, 1+y, z)], resulting in layers parallel to the crystallographic ab plane (Figure 2c). These
layers are further interconnected into a complex non-covalent 3D network through strong
hydrogen bonds established between the uncoordinated OH groups of the H tris ligand with the
3
coordinated ones and also with the oxygen atoms from the methanol ligands [O6–O7’” = 2.630
Å; O5–O1M” = 2.673 Å; (” = 1-x, 1-y, 1-z; ’” = 0.5-x, 0.5+y, 0.5-z)] (Figure 2b).
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(
a)
(c)
Figure 2. (a) Coordination environment of the zinc ion in 2 with the atom labeling scheme [’ = -
(
b)
1
+x, y, z]; (b) and (c) packing diagrams showing the hydrogen bonding interactions leading to
the 3D and 2D respectively supramolecular networks.
∞3[
space group, with cell parameters and structure refinement details given in Table 1. The
Zn (Htea) (1,3-bdc) (H O)]·2.6H O 3. Compound 3 crystallizes in the P-1 triclinic
5
2
3
2
2
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5
5
5
6
2-
asymmetric unit consists of five crystallographically independent Zn(II) ions, two Htea anions,
2
-
three 1,3-bdc anions and 3.6 water molecules (Figure 3). The investigation of the crystal
structure reveals the formation of a zigzag chain, which can be viewed as being constructed by
alternating {Zn } and {Zn } secondary building units (SBUs), involving Zn1, Zn2 and Zn3
3
2
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1
2
3
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9
0
atoms and Zn4 and Zn5 atoms, respectively. In the trinuclear {Zn } SBU the two terminal zinc
3
atoms, Zn1 and Zn3, show a coordination number of 5, but their coordination geometries are
different. Both triethanolamine molecules are doubly deprotonated and coordinate as tetradentate
ligands to Zn1 and Zn3. The Zn1 ion displays a distorted square pyramidal geometry, with the
trigonal distortion parameter τ = 0.43. The basal plane is defined by two alkoxo oxygen atoms,
one amino nitrogen, and one oxygen atom from one 1,3-bdc ligand [Zn1–O16 = 2.018(5); Zn1–
O17 =1.991(5); Zn1–N2 = 2.155(6); Zn1–O15 = 1.969(5) Å], while the fifth coordination site is
2
-
occupied by the protonated oxygen atom from the Htea molecule [Zn1–O18 = 2.089(5) Å].
The value of the τ parameter for Zn3 ion is 0.87, indicating a slightly distorted trigonal
bipyramidal geometry. The equatorial plane is occupied by the three oxygen atoms from the
triethanolamine molecule [Zn3–O7 = 2.031(5); Zn3–O8 = 2.062(5); Zn3–O9 = 1.990(5) Å],
while the amino nitrogen and one oxygen atom from a carboxylato bridge fill the axial positions
in a nearly linear arrangement [O10–Zn3–N1 = 173.4°].
Figure 3. The asymmetric unit in 3 with the atom labeling scheme [’ = 1+x, y, z].
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The coordination environment of the central atom of the trinuclear SBU, Zn2, is a slightly
distorted octahedron and consists of six oxygen atoms: three from 3 isophthalate ligands [Zn2–
O11 = 2.079(5); Zn2–O13 = 2.075(5); Zn2–O14 = 2.121(5) Å], two alkoxo bridges [Zn2–O9 =
2.148(5); Zn3–O16 = 2.084(5) Å], and one terminal aqua ligand [Zn2–O1W = 2.166(5) Å].
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The binuclear {Zn } unit is a [Zn (COO) ] SBU that was also found within other
2
2
3
1
18,142-145
compounds.
Both Zn4 and Zn5 atoms show a tetrahedral stereochemistry, with four
oxygen atoms arising from one alkoxo and three isophthalato bridges. The Zn4–O distances vary
between 1.927(5) and 1.948(5) Å, while the Zn5–O bonds are in the 1.905(4) – 1.992(5) Å range.
The binuclear and trinuclear secondary building units are alternately connected by alkoxo
bridges into helicoidal chains running along the crystallographic a axis, with a helical pitch of
2
-
1
3.66 Å (Figure 4a). Each Htea ligand acts as a bridge between three zinc atoms, similarly as
1
20
reported with the tetranuclear Zn (Htea) Ac cluster. The Zn···Zn separations within the
4
2
4
chains vary from 3.258 to 3.397 Å.
(
a)
(b)
Figure 4. (a) Fragment of the helicoidal chain in 3 running along the crystallographic a axis; (b)
2
-
helices of opposite chirality interconnected by pairs of isophthalato bridges (the Htea molecules
and the carbon atoms of the aromatic rings have been omitted for clarity).
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1
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2
2
2
2
2
2
2
2
2
3
3
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3
3
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3
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5
5
5
5
5
5
5
6
Both right-handed (P) and left-handed (M) helices are present in the crystal and they are
alternately interconnected by pairs of isophthalato bridges (Figure 4b), resulting in a 3D porous
network. There are three crystallographically different types of isophthalate anions: two of them
1
1
1
1
have all the four O atoms coordinated to four zinc ions (ꢀ −η :η :η :η mode), while the third
4
0
1
2
3
4
5
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9
0
1
2
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3
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8
9
0
1
1
2
one presents a ꢀ −η :η :η coordination mode. An inspection of the packing diagram along the
4
crystallographic a axis reveals channels of hexagonal shape (Figure 5). The edges of the hexagon
1
1
1
1
are equal to 8.36, 8.57 and 9.47 Å, respectively. The shorter edges correspond to ꢀ −η :η :η :η
4
1
1
2
isophthalato bridges, while the longest ones arise from the ꢀ −η :η :η bridges.
4
The cavities are filled with water molecules and have diameters of 7.4 Å, as found by
1
46
PLATON (taking into account the van der Waals radii of the atoms). The solvent-accessible
3
volume of 3 calculated by PLATON (excluding all water molecules from the pores) is 747.4 Å ,
corresponding to 29.3% of the unit cell volume.
(a)
(b)
Figure 5. (a) Packing diagram of 3 showing hexagonal channels formed along the
crystallographic a axis; (b) alternating P- and M-helices within the channels (the lattice water,
2
-
the Htea ligands and the carbon atoms of the aromatic rings have been omitted for clarity).
∞3[
Zn (H dea) (1,4-bdc) ] 4. The terephthalate anion is a rigid dicarboxylate linker,
3
2
2
3
which has been extensively used to generate extended structures. The self-assembly process
between Zn(II) ion, diethanolamine and deprotonated terephthalic acid affords a 3D network
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6+
built from centrosymmetric {Zn (H dea) } nodes and terephthalato bridges. The synergistic use
3
2
2
2
-
of diethanolamine and 1,4-bdc linker generates a linear Zn (COO) secondary building unit,
3
6
1
47-161
which was also reported for several Zn(II) systems with various carboxylate ligands.
Compound 4 crystallizes in the monoclinic P2 /n space group. The central Zn1 atom is
1
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surrounded by six carboxylato oxygen atoms in a nearly perfect octahedral geometry, with Zn–O
bond lengths between 2.058(3) and 2.174(5) Å and O–Zn–O bond angles between 89.89(9) and
93.62(9)º (Figure 6). Selected bond distances and angles for compound 4 are collected in Table 2.
The diethanolamine molecule is not deprotonated and coordinates as a bidentate chelating ligand
toward Zn2 ions through the nitrogen atom and one oxygen, while the other OH group remains
uncoordinated. The coordination sphere of the Zn2 ion is defined by one nitrogen and one
oxygen atoms from a diethanolamine molecule and four oxygen atoms from three terephthalate
1
1
anions. Two of the carboxylato groups act as bridges in the ꢀ −η :η −syn-syn mode, while the
2
1
2
third one coordinates in a bridging-chelating ꢀ −η :η fashion. The geometry of Zn2 atoms is a
2
distorted octahedron, with Zn2–O/N bond lengths between 2.008(2) and 2.328(3) Å and bond
angles between 76.94(11) and 103.04(9)º. The distance between the zinc centers within the node
is 3.462 Å.
Figure 6. The trinuclear unit in 4 together with the atom numbering scheme in the
asymmetric unit.
6+
The terephthalate anions connect the {Zn (H dea) } nodes into a 3D network, in which
3
2
2
narrow channels of triangular shape are formed (Figure 7). There are no solvent molecules
within the cavities.
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0
1
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3
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5
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9
0
1
2
3
4
5
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7
8
9
0
Figure 7. Two views of the packing diagram in 4 (the carbon atoms of the aromatic rings have
been omitted for clarity).
Photocatalytic studies. Compound 3 was tested as catalyst in two reactions, namely the
photo-oxidations of phenol and benzylamine.
Photo-oxidation of phenol to hydroquinone. The evolution of phenol photo-oxidation
is presented in figure 8. A conversion of about 20% was achieved after 180 minutes disregarding
the irradiation source (UV or Vis). These results (determined on the basis of the HPLC analysis)
are in a perfect concordance with the TOC (total organic carbon) measurements of the reaction
product. No mineralization or loss of carbon has been identified. The only identified product was
hydroquinone. However, it is important to underline that the investigated photocatalyst 3 led
very similar results under both Vis and UV irradiation conditions. Moreover, under Vis
irradiation, the activity was slightly higher for short reaction times.
25
UV
Vis
20
15
1
0
5
0
0
30
60
90
120
150
180
Time (min)
Figure 8. Photo-oxidation of phenol under UV and visible light irradiation.
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Photo-oxidative condensation of benzylamine to N-benzylidenebenzylamine. A
possible mechanism for the selective photo-oxidation of benzylamine to N-
benzylidenebenzylamine is presented in scheme 1. The photocatalytic activity of 3 can be
associated with absorption of light radiation by the chromophore building blocks, leading to
excited sites. Compound 3 acts as an electron donor for molecular oxygen, which give rise to
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*
+
active oxygen species (superoxide ion) and a positively charged compound (3 ). Benzylamine is
further activated by the electron hole of 3 and reacts with the active oxygen species to form
benzaldehyde and ammonia. Subsequently, the condensation reaction of benzaldehyde with
another benzylamine molecule leads to N-benzylidenebenzylamine. According to previous
162
studies, this second reaction step is not photo catalyzed and may take place even under dark.
However, the phtoactivated first step reaction seems to be faster than the non-photoactivated
second step condensation, as suggested by the catalytic results (Figure 9).
hν
O2
1
*
3
*
*+
+ O2-*
3
3
3
3
NH2
NH2
+*NH2
CHO
N
- NH3
- H O
2
.
..
CO + H O
2
2
Scheme 1. Oxidative condensation of benzylamine catalyzed by compound 3.
The photo-oxidative condensation was performed under both UV and Vis irradiation and
differences in TOF (turn over frequency) and selectivities depending on the two photoactivation
sources were found (Figure 9). Working under visible irradiation, TON (turn over number)
varied in a small range (38 after 0.5 h irradiation versus 40 after 2 h irradiation). However,
during this period of time TOF decreased from 76 to around 20. Under UV irradiation, both TON
and TOF values were initially smaller than under Vis irradiation, but they increased with time
(
TON from 10 after 0.5 h to 70 after 2 h irradiation, and TOF from 19 after 0.5 h to 35 after 2 h
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6
irradiation). Differences were also in the selectivity to N-benzylidenebenzylamine, but only for
long exposure times. In both cases, the selectivity was higher than 99% for exposure times up to
1.5 h, and then it decreased to 97% under UV, and 80% under Vis respectively. The by-product
of this photooxidation was benzylaldehyde. The increase of benzylaldehyde content in the
product mixture (Figure 10), especially under Vis irradiation, can be an indication that first step
of the reaction leading to benzylaldehyde occurs faster than the coupling of benzylaldehyde with
the second molecule of benzylamine (scheme 1), which may cause an accumulation of the
oxidation product with time.
0
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80
70
60
50
100
95
90
TOF UV
TOF Vis
S% UV
S% Vis
40
8
5
30
20
10
80
75
0.5
1.0
1.5
2.0
Time (h)
Figure 9. Time evolution of TOF and selectivity to N-benzylidenebenzylamine as a
function of the irradiation source.
2
2
1
1
0
0
.5
.0
.5
.0
.5
.0
UV
Vis
0.0
0.5
1.0
1.5
2.0
2.5
Time (h)
Figure 10. Time evolution of the content of benzaldehyde in the reaction mixture.
The stability of 3 as a photocatalyst was investigated using Raman spectroscopy. The
Raman spectra of benzylamine before and after 3 h UV exposure (Figure 11) show a decrease of
-1
163
the intensity of the band at about 879 cm , which is assigned to the C-NH stretch. The band
2
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at about 1004 cm is assigned to the ring breathing and remains unchanged during the reaction.
This results support the fact that only the –NH group was oxidized, while the aromatic ring
2
remained unaltered. Similar spectra were collected under Vis irradiation (Figure S5). Raman
spectra of photocatalyst 3 separated from the reaction mixture at different reaction times
demonstrate no change (i.e. no damage) of its integrity (Figure S6). Further re-use of the catalyst
in a new batch did not change the Raman spectra or catalytic performances.
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59
60
Benzylamine
Benzylamine after reaction
1400
1200
1000
800
600
400
-1
Raman Shift (cm )
Figure 11. Liquid Raman spectra of benzylamine before and after 3 h of UV exposure
The diffractograms and Raman spectra of compound 3 before and after the photocatalitic
reaction confirm its integrity at the end of the process (Figures S7-S8).
Thermal stability studies
In order to investigate the thermal stability of the four coordination polymers, TG-FTIR
experiments were carried out in air between room temperature and 600 °C. Detailed descriptions
along with the TG/DTG/DTA diagrams together with 2D plots of FTIR spectra of evolved gases
from the decomposition of 1–4 are provided in the Supporting Information (Figures S9−S16).
The TG analyses revealed a series of weight losses in the 200–515 ºC range, attributed to the
elimination of benzenedicarboxylate and amino-alcohol molecules. The decompositions are
characterized by several peaks in DTG and DTA respectively. The overall weight loss is
consistent with the zinc oxide formation for all compounds.
Conversion to ZnO
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ZnO-1 – ZnO-4 structures have been generated upon calcinations in air of compounds 1–
at 800 °C for 1 h and they were studied by PXRD and scanning electron microscopy (SEM).
The XRD patterns for ZnO-1 – ZnO-4 are similar and match with the standard pattern of
4
the typical wurtzite structure of ZnO (hexagonal phase, space group P6 mc, with lattice constants
3
0
1
2
3
4
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0
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0
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2
3
4
5
6
7
8
9
0
a = 3.24982(9) Å, c/a = 1.6021 Å, Z = 2, JCPDS No. 36-1451). Since all have similar feature,
only the case of ZnO-3 will be discussed. The sharp diffraction peaks (Figure 12) indicate a good
crystallinity of the ZnO particles. No other peaks related to any impurity were observed.
1
,0
0,8
0
0
0
0
,6
,4
,2
,0
30
40
50
60
70
80
2
θ
Figure 12. XRD pattern for ZnO-3
Investigation of the SEM images of the structures produced by calcinations revealed
aggregates of ZnO crystals with various shapes and sizes (Figure 13). In general, the particles
have asymmetric hexagonal shapes with rounded edges and their diameters range from 60 to 750
nm. The small differences in the morphologies of the four samples show the influence of the
crystal structure of coordination polymers upon the features of materials produced from their
calcinations.
ZnO-1
ZnO-2
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ZnO-3
ZnO-4
Figure 13. SEM images at different magnifications for ZnO-1 – ZnO-4
CONCLUSIONS
The results reported herein illustrate the rich chemistry which can be generated by using rigid
dicarboxylate linkers (linear or angular) together with various amino-alcohols. The combination
of two types of ligands imposed both short and long Zn···Zn separations and led to the obtaining
of coordination polymers with various dimensionalities and solid-state architectures. In the four
compounds, the carboxylate groups exhibit various connectivity modes: monodentate, chelating,
syn-syn bridge, bridging chelating.
The solid-state transformation of the Zn(II) coordination polymers is a facile and
relatively low-cost method for the obtaining of ZnO particles with tunable morphologies, which
may be influenced by the dimensionality and the structural features of the precursors.
Compound 3 proved to be active in the selective photo-oxidation of phenol and, even
more remarkably, in the selective photo-oxydation of benzylamine to form N-
benzylidenebenzylamine. These results are promising and highlight the potential application of
this kind of materials in photocatalysis.
AUTHOR INFORMATION
*E-mail: carmenparaschiv@yahoo.com (C.P.), vasile_parvulescu@g.unibuc.ro (V.I.P.),
marius.andruh@dnt.ro (M.A.).
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ACKNOWLEDGMENTS
Financial support from the Romanian Ministry of Education CNCS-UEFISCDI (Projects PN-
II-RU-TE-2012-3-0390, PNII-ID-PCCE-2011-2-0050) is gratefully acknowledged.
SUPPORTING INFORMATION
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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6
7
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9
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2
3
4
5
6
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8
9
0
1
2
3
4
5
6
7
8
9
0
X-ray crystallographic data in CIF format, calculated and experimental PXRD, Raman spectra,
TG/DTG/DTA curves, 2D plots of FTIR spectra. This material is available free of charge via the
Internet at http://pubs.acs.org.
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Table 1. Crystallographic data, details of data collection and structure refinement parameters for compounds 1 - 4.
Compound
1
2
3
4
Chemical formula
C H NO Zn
441.02
173.05(10)
0.71073
Monoclinic
C H NO Zn
C H N O21.60Zn5
C H N O Zn
3
1
4
16
7
2
13 19
8
36 45.20
2
32 34
2
16
-1
M (g mol )
Temperature, (K)
Wavelength, (Å)
Crystal system
Space group
a(Å)
382.66
293(2)
0.71073
Monoclinic
1178.39
173.05(10)
0.71073
Triclinic
P-1
898.72
173
0.71073
Monoclinic
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
P2 /c
P2 /n
P2 /n
1
1
1
9.3186(3)
13.9878(4)
12.2722(3)
90
102.371(3)
90
10.2338(7)
8.3870(4)
18.4587(14)
90
94.877(6)
90
13.6546(18)
14.2126(18)
14.6377(19)
76.057(11)
86.390(11)
67.910(12)
2553.4(6)
2
9.9286(5)
16.0382(10)
10.6658(5)
90
101.588(4)
90
b(Å)
c(Å)
α
β
(°)
(°)
γ
(°)
V(Å )
3
1562.51(8)
4
1578.59(18)
4
1663.77(15)
2
Z
-
3
D (g cm )
(mm )
F(000)
1.875
3.107
892
1.051
1.610
1.597
792
1.202
1.533
2.388
1196
0.937
1.794
2.227
916
1.021
c
-
1
ꢀ
2
Goodness-of-fit on F
Final R1, wR [I>2σ(I)]
0.0351, 0.0457
0.742, 0.789
0.0436, 0.1210
0.0542, 0.1259
0.0617, 0.1083
0.1299, 0.1445
0.0480, 0.1014
0.1081, 0.1419
2
R1, wR (all data)
2
Largest diff. peak and
-3
0.971, -0.710
0.385, -0.344
0.804, -0.968
1.231, -1.397
hole (eÅ )
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2
2
2
2
2
2
2
2
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3
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4
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Table 2. Selected bond distances (Å) and angles (º) for compounds 1 – 4
1
2
3
4
Zn1-O1
Zn1-O5
Zn1-O6
Zn1-O7
Zn1-N1
Zn2-O2
Zn2-O4
Zn2-O5
Zn2-O6
1.975(2)
1.979(2)
1.981(2)
2.131(2)
2.146(3)
2.007(2)
1.932(2)
1.958(2)
1.923(2)
Zn1-N1
Zn1-O1
Zn1-O3
Zn1-O4
Zn1-O7
Zn1-O1M
2.070(4)
2.015(3)
2.449(3)
2.046(3)
2.206(4)
2.085(4)
Zn1-N2
2.151(7)
Zn3-O7
Zn3-O8
Zn3-O9
Zn3-O10
Zn4-O2
Zn4-O4
Zn4-O6
Zn4-O7
Zn5-O1
Zn5-O3
Zn5-O5
Zn5-O17’
2.033(5)
2.049(5)
1.991(5)
1.996(5)
1.950(5)
1.934(5)
1.943(5)
1.928(5)
1.990(5)
1.943(5)
1.943(6)
1.905(5)
Zn1-O3
Zn1-O5
Zn1-O8’
Zn2-N1
Zn2-O1
Zn2-O3
Zn2-O4
Zn2-O6
Zn2-O7
2.175(2)
Zn1-O15
Zn1-O16
Zn1-O17
Zn1-O18
Zn2-O11
Zn2-O13
Zn2-O14
Zn2-O16
Zn2-O1W
Zn2-O9
1.960(6)
2.009(5)
1.995(5)
2.068(5)
2.078(5)
2.081(5)
2.123(5)
2.085(5)
2.164(5)
2.149(5)
2.157(6)
2.058(2)
2.063(2)
2.179(3)
2.101(2)
2.109(2)
2.328(3)
2.033(2)
2.008(2)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
Zn3-N1
O1-Zn1-N1
O5-Zn1-O6
O5-Zn1-O7
O6-Zn1-O7
O2-Zn2-O6
O2-Zn2-O4’
O2-Zn2-O5’
O6-Zn2-O4’
O6-Zn2-O5’
O4’-Zn2-O5’
Zn2-O5-Zn1
169.51(10)
120.72(9)
113.99(10)
120.55(10)
101.69(9)
101.99(10)
101.99(10)
131.15(10)
106.33(10)
104.37(10)
127.77(12)
O1-Zn1-N1
O1-Zn1-O1M 94.22(16)
O1-Zn1-O3
O1-Zn1-O4
O1M-Zn1-O7 174.70(16)
O3-Zn1-N1
O4-Zn1-N1
N1-Zn1-O7
110.73(14)
O15-Zn1-N2
O17-Zn1-O16
O16-Zn1-O18
O17-Zn1-O18
O18-Zn1-N2
O11-Zn2-O13
O14-Zn2-O1W
O16-Zn2-O9
O10-Zn3-N1
O7-Zn3-O8
174.9(2)
148.7(2)
105.2(2)
101.1(2)
81.5(2)
171.3(2)
176.5(2)
169.01(18)
173.3(2)
118.7(2)
121.2(2)
115.8(2)
116.2(2)
118.5(2)
O6-Zn4-O2
O7-Zn4-O2
O7-Zn4-O4
O7-Zn4-O6
O17-Zn5-O1
O17-Zn5-O3
O17-Zn5-O5
O3-Zn5-O1
O5-Zn5-O1
O5-Zn5-O3
Zn1-O16-Zn2
Zn3-O9-Zn2
Zn4-O7-Zn3
Zn5-O17’-Zn1’
104.1(2)
102.4(2)
104.0(2)
110.6(2)
100.0(2)
107.9(2)
121.4(2)
109.4(2)
103.1(2)
113.5(2)
105.5(2)
109.9(2)
118.1(2)
120.8(3)
O5-Zn1-O3
89.87(9)
O3-Zn1-O8’ 90.51(9)
O5-Zn1-O8’ 93.63(10)
158.95(12)
101.25(13)
O6-Zn2-N1
O6-Zn2-O1
O6-Zn2-O3
O6-Zn2-O4
O7-Zn2-N1
O7-Zn2-O1
O7-Zn2-O3
O7-Zn2-O4
O7-Zn2-O6
91.78(11)
100.46(10)
103.05(9)
162.18(9)
160.88(11)
84.05(10)
101.23(9)
89.29(10)
93.74(10)
89.41(13)
145.35(14)
78.28(14)
O9-Zn3-O7
Zn2”-O6-Zn1 121.98(11)
O9-Zn3-O8
O4-Zn4-O2
O4-Zn4-O6
Zn2-O3-Zn1 107.85(10)
’
= x, 1.5-y, -0.5+z; ” = x, 1.5-
’ = 1+x, y, z
’ = -0.5-x, -0.5+y, 0.5-z
y, 0.5+z
2
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