Bismuth Coordination Polymers with 2,4,6-Pyridine Tricarboxylic Acid: High-Throughput Investigations, Crystal Structures and Luminescence Properties

Article abstract of DOI:10.1002/ejic.201800154

Four new coordination polymers (CPs) were obtained under hydrothermal reaction conditions using 2,4,6-pyridinetricarboxylic acid (H₃PTC) and Bi(NO₃)₃·5H₂O. The systematic high-throughput investigation of the system Bi³⁺/H₃PTC/NaOH/HNO₃/H₂O led to the compounds [Bi(PTC)(H₂O)₂] (1), (H₃O)[Bi₂(PTC)(HPTC)₂(H₂O)₂] (2), α-[Bi(PTC)] (3) and β-[Bi(PTC)] (4), which were structurally characterised by single-crystal X-ray diffraction. Compounds 1 and 2 crystallise in 2D layered structures, whereas 3 and 4 form 3D coordination networks. Employing the nomenclature proposed by Cheetham et al. 1 and 2 are classified as I¹O¹ (mixed inorganic–organic layers), 3 as I⁰O³ (3D coordination polymers) and 4 as I¹O² (mixed inorganic–organic 3D framework). In all cases the nitrogen atom of the linker is coordinated to the Bi³⁺ ion, which therefore acts as a tridentate pincer-type ligand. All title compounds were obtained as phase-pure products employing conventional or microwave-assisted heating, but the reproducibility of the synthesis depends on reactor size and material. In addition, the luminescence properties of 1 and 2 were studied resulting in a yellow and blue–green luminescence under UV light with emission maxima at 570 nm (λ_ex = 343 nm) and 483 nm (λ_ex = 347 nm) for 1 and 2, respectively. The differences in the spectroscopic properties could be assigned to the distinct coordination and chemical environments of the Bi³⁺ ions within these compounds.

Full text of DOI:10.1002/ejic.201800154

A Journal of
Accepted Article
Title: Bismuth Coordination Polymers with 2,4,6-Pyridine Tricarboxylic
Acid − High-Throughput Investigations, Crystal Structures and
Luminescence Properties
Authors: Timo Rhauderwiek, César dos Santos Cunha, Huayna
Terraschke, and Norbert Stock
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201800154
Link to VoR: http://dx.doi.org/10.1002/ejic.201800154

10.1002/ejic.201800154
European Journal of Inorganic Chemistry
Bismuth Coordination Polymers with 2,4,6-Pyridine Tricarboxylic
Acid − High-Throughput Investigations, Crystal Structures and
Luminescence Properties
Timo Rhauderwiek,[a] César dos Santos Cunha,[a,b] Huayna Terraschke,[a] and Norbert Stock *[a]
Abstract: Four new coordination polymers (CPs) were obtained
under hydrothermal reaction conditions using
reported on the use of 2,4,6-pyridinetricarboxylic acid (H3PTC) for
the synthesis of Bi-CPs, although this linker has been successfully
used in the synthesis of luminescent CPs employing various di-
and trivalent transition metals and trivalent lanthanide ions (Tab.
S1).[5b, 9] Such luminescent coordination polymers are of scientific
importance due to their wide range of applications in areas such
as the development of new luminophores for energy-saving
technology, as probes for biomolecules,[10] or as materials in
photocatalysis and electroluminescent devices.[6c, 6d, 10-11]
2,4,6-pyridinetricarboxylic acid (H3PTC) and Bi(NO3)3∙5H2O. The
systematic high-throughput investigation of the system Bi3+/
H3PTC/ NaOH/ HNO3/ H2O led to the compounds [Bi(PTC)(H2O)2]
(1), (H3O)[Bi2(PTC)(HPTC)2(H2O)2] (2), α-[Bi(PTC)] (3) and β-
[Bi(PTC)] (4) which were structurally characterised by single-
crystal X-ray diffraction. 1 and 2 crystallise in 2D layered
structures while 3 and 4 are 3D coordination networks. Employing
the nomenclature proposed by Cheetham et al.[1] 1 and 2 are
classified as I1O1 (mixed inorganic-organic layers), 3 as I0O3 (3D
coordination polymers) and 4 as I1O2 (mixed inorganic-organic 3D
framework). In all cases the nitrogen atom of the linker is
coordinated to the Bi3+ ion, which therefore act as a tridentate
pincer-type ligand.[2] All title compounds were obtained as phase
pure products employing conventional or microwave-assisted
heating, but reproducibility of the synthesis depends on reactor
size and material. In addition, the luminescence properties of 1
and 2 were studied resulting in a yellow and blue-green
luminescence under UV light with emission maxima at 570 nm (λex
= 343 nm) and 483 nm (λex = 347 nm) for 1 and 2, respectively.
The differences in the spectroscopic properties could be assigned
to the distinct coordination and chemical environments of the Bi3+
ions within these compounds.
The relatively small number of structurally characterized bismuth
carboxylates could be due to the complex solution chemistry and
the low solubility of bismuth salts. The latter can be increased by
heating of the reaction mixture or addition of acids like nitric
acid,[12] as well as the usage of microwave-irradiation or
ultrasonication during the synthesis.[13] High-throughput (HT)
methods have been demonstrated to be a highly versatile tool for
the investigation of such challenging chemical systems[14] and
they have also been successfully employed in the synthesis of
new bismuth carboxylates. They have allowed the systematic
study of the influence of synthesis parameters like molar ratios,[14c,
15]
pH,[15-16] temperature, time,[17] metal source[14c] and
concentration[15, 16b] in the product formation in a fast, cheap and
efficient manner.[14a] In addition they allow to establish synthesis-
structure relationships.
Here we present the results of systematic HT investigation of the
system Bi3+/ H3PTC/ NaOH/ HNO3/ H2O in the synthesis of Bi-CPs.
In addition, the detailed structural characterization and
luminescence properties under UV irradiation are reported.
Introduction
Coordination polymers (CPs) are an interesting class of materials
due to their diverse and tunable sorption,[3] catalytic,[4] magnetic[3d,
Results and Discussion
5]
and optical[5b, 5d, 6] properties. Many different metal ions were
Coordination polymers containing Bi3+ ions (Bi-CPs) have been
synthesised using various organic linker molecules, mainly
containing –COOH groups.[4b, 7] They exhibit a large structural
diversity due to the variability in coordination number and
environment of the Bi3+ ions.[7c] Thus small changes in the reaction
conditions often lead to structural different Bi-CPs.[18] In the
current study, four new Bi-CPs were obtained from the system
Bi3+/ H3PTC/ NaOH/ HNO3/ H2O by changing the molar ratios of
the starting materials and using reaction temperatures of 160 and
180 °C and reaction times of 6 and 48 h.
Synthesis. The system Bi3+/ H3PTC/ NaOH/ HNO3/ H2O was
studied using HT methods and Teflon inserts with a maximum
volume of 2.0 mL. The molar ratios Bi3+ : H3PTC : NaOH : HNO3
were varied in the range 0.1-2 : 1 : 1-8 : 1-8 (Fig. 1 and S1a). The
results of the HT investigations, based on powder X-ray diffraction
(PXRD) data, for a reaction time of 6 h are shown in Figure 1.
Further results for a reaction time of 48 h are presented in Figure
S1a. According to the PXRD patterns, four different phases and
mixtures thereof are obtained.
used in the synthesis of such materials but the number of bismuth
carboxylates reported in the last years is still limited to a few
7]
dozen structures (Tab. S2).[4b,
For example, the two linker
molecules pyridinedicarboxylic acid (H2PDC)[7b,
benzenetricarboxylic acid (H3BTC)
and
7d, 7e, 7g]
[4b, 7c, 7h]
led to various new
compounds which were also investigated for their optical
properties (Tab. S2).[7c, 7e, 8] In contrast, no results have been
[a]
T. Rhauderwiek, C. S. Cunha, H. Terraschke, N. Stock
Institute of Inorganic Chemistry
Christian-Albrechts-Universität
Max-Eyth Straße 2, 24118 Kiel, Germany
E-mail: stock@ac.uni-kiel.de
[b]
C.S. Cunha
Institute of Chemistry, University of São Paulo
Av. Prof. Lineu Prestes 748, 05508-000 São Paulo-SP, Brazil
Supporting information for this article is given via a link at the end of the
document. CCDC 1566579-1566582 contains 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/getstructures.
While for compound 2 a well-defined parameter space in which 2
occurs phase pure is observed, 1, 3 and 4 are often obtained in
1
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
form of product mixtures. Therefore, during the HT-investigation
optimized synthesis conditions could only obtained for 2. Title
compound 1 was obtained at metal to linker ratios between 1 : 1
and 1.5 : 1 and 2 was obtained at ratios between 0.1 : 1 and 0.5 :
1 after 6 h reaction time. The pH value regulated by the amount
of added 2M HNO3 and NaOH has no dominant influence on
product formation (Fig. 1). Further synthesis optimization
reactions carried out employing 7 mL glass vials resulted in
optimized synthesis conditions for 1 and 2 (at 160 °C for 6 h)
employing molar ratios of Bi3+ to H3PTC to HNO3 to NaOH of 1 :
1 : 4 : 2 and 0.2 : 1 : 4 : 2, respectively. Compounds 3 and 4 are
mostly obtained as microcrystalline mixtures or phase pure only
in Teflon vessels after a reaction time of 48 h and employing a
metal to linker ratio between 0.2 : 1 and 1.4 : 1.
with Ro a reported value of the Bi-O/N distance, Rij the
experimentally observed Bi-O/N distance and the constant b
reported for Bi-O = 0.37 and Bi-N = 0.35 (Tab. 2).[20]
[Bi(PTC)(H2O)2] (1) crystallizes in a 2D layered structure and its
asymmetric unit consists of one Bi3+ ion, one PTC3- ion and two
water molecules (Fig. 2). In 1, each Bi3+ ion is coordinated by
three H2O molecules and three PTC3- molecules which leads to a
coordination number of CN = 9 (distorted monocapped square
antiprism, Fig. 2, b). The inorganic building unit (IBU) consists of
chains of edge sharing BiNO8 polyhedra (Fig. 2, c) interconnected
by the fully deprotonated PTC3- molecules (Fig. 2, d).
Each linker molecule coordinates to three Bi3+ ions through the
nitrogen and two oxygen atoms in a pincer-type fashion (N1, O1,
O3) and a chelating carboxylate group (O5, O6). Edge-sharing
between the BiNO8 polyhedra is accomplished through µ-oxygen
atoms (O3, O8) (Fig. 2, a). The C-O distances in 1 are in the range
of 1.236(7) – 1.291(8) Å which is consistent with the presence of
21]
–COO- groups (1.238(9) – 1.283(10) Å).[9a,
The layers are
connected to each other by hydrogen bonds between -COO- and
coordinating H2O molecules (O1···O7) as indicated by a donor
acceptor distance of 2.740(7) Å (Tab. 2, Fig. 2e).
Figure 1. Results of the HT investigation of the system Bi3+/ H3PTC/ NaOH/
HNO3/ H2O using a reaction time of 6 h at 180 °C. Based on the PXRD
measurements the Bi-CPs [Bi(PTC)(H2O)2] (1), (H3O)[Bi2(PTC)(HPTC)2(H2O)2]
(2), α-[Bi(PTC)] (3) and β-[Bi(PTC)] (4) and mixtures thereof are formed. The
amount of linker was always set to a value of 1.
Crystal Structure. All compounds were obtained in form of single
crystals (Fig. S3-S6) and thus their structures could be
determined from single crystal X-ray diffraction data. To confirm
phase purity PXRD patterns were collected and Pawley fits were
performed for all title compounds (Tab. S7 and S8, Fig. S8-S11).
The results of the crystal structure determinations are listed in
Table 1, Tables S3-S6 summarize bond distances and angles.
Figure 2. Graphical representation of the crystal structure of [Bi(PTC)(H2O)2]
(1). a) The asymmetric unit b) the BiNO8 polyhedron (distorted monocapped
square antiprism), c) the IBU consists of chains of edge-sharing BiNO8
polyhedra, d) two interconnected chains, view along [100] and e) connection of
the layers through hydrogen bonds along the b-axis. Assigned hydrogen bonds
are represented by red dashed lines, bismuth atoms and Bi-O-N polyhedra are
shown in turquois, carbon in grey, oxygen in red, nitrogen in blue and hydrogen
in white.
CCDC
1566579-1566582 contains
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/getstructures.
(H3O)[Bi2(PTC)(HPTC)2(H2O)2] (2) crystallizes also in a 2D
layered structure (ABA sequence) and its asymmetric unit
consists of two Bi3+, two HPTC2-, one PTC3- and one H3O+ ion, as
well as two H2O molecules (Fig. S7c). Bi1 is coordinated by four
HPTC2- molecules and Bi2 by two PTC3-, one HPTC2- and two
H2O molecules resulting for both metal ions in a coordination
number of CN=8 (distorted square antiprism, Fig. 3, b). The IBU
consists of chains of alternating edge- and corner-sharing BiNO7
and BiN2O6 polyhedra interconnected by the fully deprotonated
PTC3- ions (Fig. 3, c). The resulting layers are interconnected by
four types of hydrogen bonds indicated by donor acceptor
distances between 2.671(13) and 2.747(12) Å (Fig. 3, d, Tab. 2).
Between the layers H3O+ ions (O21) are located which form three
hydrogen bonds to neighbouring oxygen atoms of carboxylate
groups (Fig. 3, d). The existence of H3O+ ions in Bi3+ carboxylates
has been discussed in the literature[7e] and is strongly supported
by looking at the H-bonding pattern. The H3O+ ion acts three times
as a H-bond donor and is connected to two deprotonated
In the following paragraphs, the structures of the four title
compounds (Fig. 2-6) are described in detail. In all four title
compounds, the nitrogen atom of the linker is coordinated to the
Bi3+ ion thus acting a tridentate pincer-type ligand.[2] Furthermore,
the coordination environment of the Bi3+ ion in 1 and 4
(monocapped square antiprism) and 2 and 3 (square antiprism)
are identical. To have a closer look on the different coordination
modes observed in the title compounds, the Harris-notation was
applied (Fig. S7a-S7e).[19] It has the format [A,XY], the value A is
the number of metal ions coordinated by the carboxylate group
and X and Y are the number of bonds every oxygen shares with
a metal ion.[19] It is noteworthy that nearly every possible
coordination mode ([3,21], [2,21], [2,11], [2,20], [1,11], [1,10] and
[0,00]) is observed in the title compounds. In addition bond
valence sums for all title compounds were calculated to evaluate
the most reasonable coordination sphere. The bond valence sum
s given as the sum of every bond valence v with v = exp[(Ro-Rij)/b,
2
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
carboxylate groups and one H2O molecule (O8, O17 and O20,
respectively) (Fig. 3, d, Tab. 2). Another hydrogen bond is formed
between two carboxylic acid group (O2, O15) of two layers (Fig. 3,
d, Tab. 2). Each linker molecule coordinates to Bi3+ ions through
the nitrogen and two oxygen atoms in a pincer-type fashion.
Edge- and corner-sharing between the BiNO7 and BiN2O6
polyhedra is accomplished through µ-oxygen atoms (O6, O13 and
O12, Fig. 3, b).
the carboxylate groups. Each dimeric IBU is coordinated by ten
PTC3- molecules to 24 further dimeric IBUs. Edge-sharing
between the BiNO7 polyhedra is accomplished through the µ-
oxygen atom O6 (Fig. 4, b).
Figure 4. Graphical representation of the crystal structure of 3. a) The
asymmetric unit, b) the two edge-sharing BiNO7 polyhedra (distorted square
antiprism) forming the IBU, c) one IBU with all 10 coordinating PTC3- ions and
d) the connection to adjacent Bi2N2O12-dimers. The carbon atoms in each linker
molecule in c) and d) are represented in different colours for clarity. Bismuth
atoms and polyhedra are represented in turquois, carbon in different colours,
oxygen in red, nitrogen in blue and hydrogen in white.
β -[Bi(PTC)] (4) is a 3D coordination polymer and a polymorph of
3. Its asymmetric unit (Fig. 5, a) consists also of one Bi3+ ion and
one PTC3- molecule. In contrast to the connectivity observed in 3,
in 4 each Bi3+ ion is coordinated by five PTC3- molecules which
leads to a coordination number of CN = 9 (monocapped square
antiprism, Fig. 5 b). The IBU consists of dimers of edge-sharing
BiNO8 polyhedra which are further connected to form 1D chains
along [001] (Fig. 5 c). These chains are interconnected by the
deprotonated linker PTC3- forming a 3D CP (Fig. 5 d). Each linker
molecule coordinates to six Bi3+ ions through the nitrogen and two
oxygen atoms in a pincer-type fashion (N1, O1, O6) and the other
oxygen atoms of the carboxylate groups. Edge- and corner-
sharing between the BiNO8 polyhedra is accomplished through
the µ-oxygen atoms O4 and O1, respectively (Fig. 5, c).
Figure 3. Graphical representation of the crystal structure of 2. a) the two
symmetry independent corner-sharing BiNO7 (left) and BiN2O6 (right) polyhedra
(distorted square antiprisms) form Bi2N3O13-dimers, b) the IBU along [100],
consists of chains of Bi2N3O13-dimers, c) connection of the IBUs by linker
molecules along [001] and interconnection of the layers by hydrogen bonds (red
dashed lines and d) enlarged section showing the hydrogen bonds in more
detail. For clarity, the carboxylic acid groups of the bottom layer are marked in
blue (oxygen and carbon atoms in dark and bright blue) and of the top layer in
green (oxygen and carbon atoms in bright and dark green). The red oxygen
atom represents the H3O+ ion which is between the layers and forms three
different hydrogen bonds. Two additional hydrogen bonds are formed between
two carboxylic acid groups of 2.685(18) Å each. Bismuth atoms and polyhedra
are represented in turquois, carbon in grey, oxygen in red, nitrogen in blue and
hydrogen in white.
Due to the fact that the positions of the hydrogen atoms could not
be determined, the C-O/ C=O distances were taken into account
and compared to literature values[7f] to unequivocally identify the
carboxylic acid groups (C5, O3, O4 and C13, O9, O10). Thus the
atoms O19 and O20 were assigned to H2O molecules. This
assignment is also supported by the broad OH band in the IR
spectrum around 3450 cm-1 (Fig. 11).
α-[Bi(PTC)] (3) is a 3D coordination polymer and its asymmetric
unit (Fig. 4, a) consists of one Bi3+ ion and one PTC3- molecule. In
3 each Bi3+ ion is coordinated by six PTC3- molecules which leads
to a coordination number of CN = 8 (distorted square antiprism,
Fig. 4, c). The IBU consists of dinuclear units of edge-sharing
BiNO7 polyhedra interconnected by the fully deprotonated PTC3-
molecules (Fig. 4, b and d). Each linker molecule coordinates to
six Bi3+ ions through the nitrogen and two oxygen atoms in a
pincer-type fashion (N1, O1, O6) and the other oxygen atoms of
Figure 5. Graphical representation of the crystal structure of 4. a) The
asymmetric unit, b) the BiNO8 polyhedron (monocapped square antiprism), c)
IBU consisting of edge-sharing BiNO8 polyhedra which are further connected to
chains by corner-sharing along the c-axis, d) view of the IBUs along [001] with
interconnecting PTC3- ions. Bismuth atoms and polyhedra are represented in
turquois, carbon in grey, oxygen in red, nitrogen in blue and hydrogen in white.
3
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
Thermal stability. To investigate the thermal stability of the title
compounds, thermogravimetric measurements (TG, Fig. 6,
Tab. 3) and variable temperature powder X-ray diffraction studies
(VT-PXRD, Fig. S12-S13) were performed. In case of 1 and 2,
two steps of weight loss are observed in the TG curves, which are
due to the loss of coordinated and intercalated water molecules
in a first step and the decomposition of the coordination polymer
in the second step. The decomposition takes place at 350 °C and
300 °C for 1 and 2, respectively. In case of 3 and 4 only one
characteristic step of weight loss is observed at about 400 °C,
which is due to the decomposition of the coordination polymer.
Combining these values with the results of the VT-PXRD studies,
we can state that the complete loss of crystallinity in 1 already
takes place (280 °C, Fig. S12, left) before decomposition of the
linker (350 °C). For 2, a structural change around 150°C is
observed, which is due to the loss of inter-layer water molecules.
Loss of crystallinity takes place around 325 °C, which is supported
by the TG data. For compounds 3 and 4 the complete loss of
crystallinity takes place between 400 and 450 °C, which also
corresponds to the result of the TG data.
Table 1. Crystallographic data of the title compounds 1 ([Bi(PTC)(H2O)2]), 2
((H3O)[Bi2(PTC)(HPTC)2(H2O)2]), 3 (α-[Bi(PTC)]) and 4, (β-[Bi(PTC)]).
1
2
3
4
Crystal
system
a [Å]
b [Å]
c [Å]
ortho-
rhombic
12.319(3)
13.395(3)
9.819(2)
90
90
90
1620.3(6)
triclinic
triclinic
monoclinic
6.0702(12)
9.0908(18)
9.3376(19)
83.33(3)
81.98(3)
77.09(3)
10.030(2)
11.870(2)
13.470(3)
78.60(3)
77.70(3)
69.70(3)
1456.1(6)
9.850(2)
5.2000(10)
14.990(3)
90
94.20(3)
90
α [°]
β [°]
γ [°]
V [Å3]
Space
group
Tot.,
495.41(18)
765.7(3)
̅
P1
̅
P1
P21/n
Pbcn
15408,
6911,
0.073
22933,
1855,
0.136
7754, 2356,
0.101
11211,
1831, 0.043
uniq. data,
Rint
Observed
data
2059
5303
1674
1692
[I>2σ(I)]
R1, wR2
(gt) [%]
GOF
2.9, 7.2
1.02
5.7, 13.7
1.05
2.4, 5.5
1.13
4.0, 9.1
1.36
Taking the nomenclature proposed by Cheetham et al. into
account title compounds 1 and 2 are classified as I1O1 (mixed
inorganic organic layers), 3 is classified as I0O3 (3D coordination
polymers) and 4 is classified as I1O2 (mixed inorganic organic 3-
D framework).[1] Compounds 3 and 4 are polymorphs. Although
many different reactions were tested, such as thermal treatment
in protic or aprotic solvents at elevated temperatures, we were not
able to transform one polymorph into the other.
The C-C, C-N and C-O bond lengths observed in 1, 2, 3 and 4 are
similar to the ones reported for other metal salts of H3PTC and
H2PDC. For the C-C and C-N distances values of 1.349(16) -
1.528(10) and 1.322(14)
-
1.368(16) Å were observed,
21]
respectively (Lit.[9a,
:
1.324(13) 1.598(17), 1.302(13)-
-
1.355(10) Å). For the C=O bonds values from 1.224(9) to
1.297(14) Å and for the C-OH bond in 2 values of 1.300(19) and
Figure 6. Thermogravimetric curve of 1 (black), 2 (red), 3 (blue) and 4 (green).
Evaluation of the measurement reveals a molar ratio of metal : linker : H2O =
1.1 : 1.0 : 2.2 (1), 2.0 : 3.0 : 2.7 (2), 1.1 : 1.0 : 0.0 (3) and 1.1 : 1.0 : 0.0 (4, Table
3).
1.317(13) Å were found, respectively (Lit.[9a, 21]:1.238(9)
–
1.283(10), 1.318(4) – 1.339(17) Å[7f]). The Bi-O and Bi-N bonds
are in a range of 2.198(6) - 2.799(5) and 2.313(6) - 2.450(8) Å,
respectively, and are also in a good agreement with the literature
values of 2.095(4) – 2.631(5)[7c, 7g] and 2.637(7) – 2.843(7) Å[7g]
.
Table 3. Results of the thermogravimetric measurements of all obtained
compounds. The number of solvent molecules per formula unit and resulting
metal to linker ratios are shown in brackets.
Two Bi-O bond distances in 4 are 3.095(7) (O4) and 3.215(6) Å
(O1) long, and thus represent weak Bi-O interactions. These
atoms were added to the coordination sphere due to the fact that
the bond valence sums resulted in a too low value of 2.71, but by
adding these two interactions a more reasonable value of 2.83
was obtained (Tab. 2). For the other title compounds bond
valence sums of 2.97 (1), 2.85 and 2.98 (Bi1 and Bi2 of 2) and
2.88 (3) were obtained. Bond valence sums of Bi-complexes and
-oxides are often observed in a range between 2.8 and 3.3
depending on the covalent character of the bonds.[22]
mass loss
250-800 °C
meas. [%]
mass loss
250-800 °C
calc. [%]
mass loss RT-
250 °C [%] and
H2O per Bi3+
residual
mass [%]
1
2
3
50.5
41.1
55.5
41.7 (1.1:1)
54.5 (2:3)
44.6 (1.1:1)
45.3 (1:1)
54.9 (2:3)
49.6 (1:1)
7.9 (2.2 H2O)
4.2 (2.7 H2O)
4
56.7
44.4 (1.1:1)
49.3 (1:1)
Luminescence measurements. The luminescent properties of 1,
2 and the H3PTC linker were characterized by measurements of
the respective excitation and emission spectra at 300 K.
Compounds 3 and 4 did not show any luminescence, and were
therefore not further characterized. In Figure 7, the luminescence
spectra of the H3PTC linker shows an intense emission band with
a maximum at 435 nm, monitoring at the maximum excitation
wavelength at 360 nm. This emission band in the blue and near
UV spectral region is characteristic for organic molecules with
multiple bonds and pairs of conjugated free electrons, such as
aromatic or heteroaromatic rings, due to the transitions n → π* or
π → π*.[23]
Table 2. Bond valence sums[20a, 22] and H-bond donor acceptor distances
(D···A) of all title compounds.
1
2
3
4
bond valence
sum s
2.85
2.98
2.97
2.88
2.83
2.685(18) O2-O15
2.747(12) O21-O17
2.732(10) O21-O8
2.671(13) O21-O20
H-bond D∙∙A
distances [Å]
2.737(7)
O1-O7
-
-
4
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
The chemical environment and coordination number of the Bi3+
ion in 1 and 2 are different and may explain the considerable
displacement of the emission band and the different values of
Stokes Shift.[28] According to Steensel et al., a larger coordination
number can lead to a higher Stokes shift value, as well as a higher
degree of covalency of the bonds between the Bi3+ ion and the
neighbouring oxygen or nitrogen atoms can decrease the energy
of the 1S0 → 3P1 transition.[28b] The coordination number of the Bi3+
ions in 1 is nine, with a Stokes shift of approximately 11649 cm-1,
while 2 with coordination number eight for both Bi3+ ions exhibits
a Stokes shift of 8119 cm-1, agreeing with the expected increase
in the Stokes shift value with the coordination number.
Figure 7. Normalized excitation (black curve) and emission (blue curve) spectra
at room temperature of the pure H3PTC linker, monitoring at the wavelength of
435 and 360 nm, respectively.
Considering that transitions involving singlet states are allowed,
therefore more likely to occur at room temperature, this excitation
and emission can be attributed to the transition between the first
excited singlet state S1 and the fundamental singlet state S0 of the
H3PTC linker at 300 K.
The luminescence spectra of 1 are shown in Figure 8, presenting
an intense emission and with a maximum at 570 nm, monitored
at the highest excitation wavelength at 343 nm. In Figure 9, the
spectra of 2 are presented, which emission band is centered in
the region of 483 nm, monitoring at the excitation wavelength of
347 nm. The emission spectra of the compounds are compared
in S14, emphasizing that the coordination of the linker to the Bi3+
cations in 1 and 2 led to an emission shift to lower energy regions
compared to the emission of the H3PTC linker. The free Bi3+ ion
Figure. 9. Normalized excitation (black curve) and emission (green curve)
spectra at room temperature of 2, monitoring at the wavelength of 483 and 347
nm, respectively.
1
(electronic configuration 6s2) presents ground state S0, excited
3
3
3
1
triplets levels P0, P1, P2 and singlet excited state P1.[24] The
The p orbitals of the oxygen atoms of the carboxylate groups are
in resonance with the orbitals of the carbon atoms, thus the
oxygen atoms of the linker are more polarized, presenting a lower
covalency compared to the oxygen atoms of H2O molecules. Thus,
the increase of the number of H2O molecules and nitrogen atoms
of the H3PTC linker coordinated to the Bi3+ cation play a relevant
role in increasing the degree of covalency of the bonds.[28b] The
main absorption bands are the 1S0→1P1 (allowed transition called
1
C-band) and S0→3P1 (called A-band and allowed by relaxation
1
1
caused by spin-orbit coupling with P1 state) transitions. The S0
3P2 transition (B-band) is forbidden, but can be relaxed by
→
determined vibrational modes of the framework. Finally, the lower
energy 1S0→3P0 transition is strongly forbidden but acts as a low
temperature optical trap.[24-25] At room temperature, the emission
of the Bi3+ ion occurs mainly from the 3P1 state. The energy of the
emission and excitation bands can vary considerably, since they
are very sensitive to the chemical environment and to the
composition of the host material, in case of doped compounds.[26]
Therefore, depending on the studied substances, it is possible to
observe emission from the ultraviolet region to wavelengths larger
than the ones at the red region of the visible spectrum.[27]
1
3
energy of the S0 → P1 transition for 2 (28818 cm-1) is slightly
smaller compared to 1 (29154 cm-1). These results can be
explained by the difference in the coordination sphere of the
compounds. While 1 has only one symmetry independent Bi3+ ion
coordinated by three water molecules and one nitrogen atom (in
addition to the oxygen atoms of the linker), 2 contains two
symmetry independent Bi3+ ions, one containing two molecules of
water and one nitrogen atom, while the other Bi3+ ion is
coordinated by one water molecule and two nitrogen atoms of the
H3PTC linkers. Therefore, the chemical bonds between the Bi3+
and their neighbouring atoms in 2 are expected to present a
higher covalent character than in 1, mainly due to the larger
number of nitrogen atoms bounded to the Bi3+ ion. In these
compounds, the Jahn-Teller effect is expected to be negligible
due to the heavily distorted coordination sites of the Bi3+ ions.[24,
29]
The maxima of the excitation spectra of 1 and 2 (Figures 8 and 9)
are in the range of 340-350 nm and are consistent with the values
observed for systems containing Bi3+ ions, related to excitation in
the A-band (1S0 → 3P1 transition).[30] However, it should be noted
that, in this same spectral region, the excitation band (S0 → Sn) of
the heteroaromatic rings of the linker used for the synthesis of the
materials is also located.[7e, 8, 30a] In this case, the population of the
Figure 8. Normalized excitation (black curve) and emission (orange curve)
spectra at room temperature of 1, monitoring at the wavelengths of 570 and 345
nm, respectively.
5
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
excited states of the linker is expected to be more efficient, since
the S0→Sn transition is spin allowed. A subsequent intersystem
crossing could populate the triplet states of the linker (T1) or the
Bi3+ ions (3P1), leading to a competitive emission between these
two transitions (T1 → S0 and 3P1 → 1S0), which may occur in the
same region of the visible spectrum. However, in order to confirm
the nature of the excitation and emission bands and the
mechanisms of energy transfer, a more in-depth study is
necessary, mainly related to the lifetime measurements of the
excited states, as well as time-resolved spectroscopy at low
temperature. The Commission Internationale d`Eclairage (CIE)
1931 chromaticity coordinates representing the characteristic
emission colours of the pure ligand H3PTC (x = 0.1540, y =
0.0863), 1 (x = 0.4584, y = 0.4805) and 2 (x = 0.1589, y = 0.3852)
have been calculated from the respective emission spectra
presented in Figures 7-9.[31] These coordinates are presented in
Figure 10 as well as the luminescent images of the solid samples
under excitation with UV light.
Figure 11. IR spectra of H3PTC compared with 1, 2, 3 and 4.
The IR spectra of the title compounds, with the exception of 2, are
very similar. In 2 the presence of -COOH groups is supported by
the C=O stretching vibration at 1728 cm-1 which is also observed
in the spectrum of the linker molecule. In all spectra the
-
asymmetric and symmetric stretching vibrations of the –CO2
groups are observed between 1576 - 1668 and 1380-1558 cm-1,
respectively. The bands of the C=C and the C=N stretching
vibrations are located between 1533-1592 and 1314-1445 cm-1,
respectively. Furthermore the characteristic deformation vibration
of the 2,4,6 substitution in the linker is observed around 770 cm-1.
Conclusions
Figure 10. Left: CIE 1931 chromaticity diagram presenting the characteristic
emission colors of H3PTC (x = 0.1540, y = 0.0863), 1 (x = 0.4584, y = 0.4805)
and 2 (x = 0.1589, y = 0.3852). Right: photographs of H3PTC, 1 and 2 under UV
light excitation.
The system Bi3+/ H3PTC/ 2M NaOH/ 2M HNO3 was investigated
using high-throughput methods under hydrothermal conditions.
Through systematic variation of the synthesis parameters, we
were able to obtain four new bismuth carboxylates of composition
[Bi(PTC)(H2O)2] (1), (H3O)[Bi2(PTC)(HPTC)2(H2O)2] (2), α-
[Bi(PTC)] (3) and β-[Bi(PTC)] (4). All compounds were
characterized in detail. The parameter space was thoroughly
investigated regarding temperature, time, pH value, amount of
metal and different synthesis settings. 1 presents a yellow
luminescence under UV light with emission maximum at 570 nm
(λex = 343 nm), while the emission band of 2 is centered at 483
nm (λex = 347 nm), in the blue-green spectral range, which
spectroscopic differences could be assigned to the distinct
chemical environment and coordination numbers around the Bi3+
sites within these compounds.
Compounds 3 and 4 did not show any visible luminescence when
illuminated with an UV lamp (365 nm), and were therefore not
further characterized. Probably, the increased amount of the
bismuth fraction within α-[Bi(PTC)] (3) and β-[Bi(PTC)] (4) in
comparison
to
[Bi(PTC)(H2O)2]
(1),
and
(H3O)[Bi2(PTC)(HPTC)2(H2O)2] (2) is responsible for the observed
concentration quenching effect and degradation of the
luminescence properties of these compounds.
IR-Spectroscopy. IR spectra of the title compounds are
compared with the one of the linker molecule H3PTC in Figure 11.
The assignments of the bands are given in Table S9.[32] In the
following only selected vibrations are discussed. In case of the
linker molecule the N-H stretching vibration at 3591 cm-1 is
observed which is due to the formation of zwitter-ions.
Furthermore the O-H stretching vibrations of the free carboxylic
groups are observed at 3361 cm-1.
Experimental Section
Materials. Bi(NO3)3 ∙ 5 H2O (98 %, Alfa Aesar), NaOH (Grüssing, 99 %)
2 M HNO3 (VWR) were used without further purification. The metal salt
Bi(NO3)3 ∙ 5 H2O was dissolved in 2 M HNO3 to achieve a 1.59 M solution.
NaOH was dissolved in H2O to achieve a 2 M solution. The linker
2,4,6-pyridinetricarboxylic acid (H3PTC) was synthesized according to a
literature procedure[33] starting from 2,4,6-trimethylpyridine (97.5 %,
ABCR) and KMnO4 (99 %, Grüssing). Details are given in the Supporting
Information.
Characterization. All crystal structures were determined from single
crystal X-ray diffraction data. X-ray diffraction data were collected on a
6
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
Stoe IPDS diffractometer equipped with an image-plate detector by using
MoKα radiation (λ=0.7107 nm). The crystal structures were solved by
direct methods with the program SHELXS-2013 and refined using the
program SHELXL-2013.[34] H atoms which are connected to carbon atoms
were placed on calculated positions. H atoms on water and OH groups
could not be localized in the difference Fourier map. For all compounds
numerical absorption corrections were carried out using the program suit
X-Area with the implemented programs X-Shape and X-RED.[35] For the
optimization of synthesis conditions, our high-throughput (HT)
(HPTC)2(H2O)2]. Elemental analysis of 2: calc (%): C 26.3, H 1.1, N 3.8,
found (%): C 26.0, H 1.4, N 3.6.
Due to the fact that 3 and 4 were only occasionally obtained as phase pure
products during high-throughput synthesis, the phase pure samples of 3
and 4, proven by PXRD measurements, were combined for further
characterization. The synthesis had to be repeated several times to
achieve enough product for a complete characterization. 3 and 4 were
occasionally obtained phase pure using the following synthesis conditions:
H3PTC (52.8 mg, 0.25 mmol), H2O (750 µL), 2 M aqueous NaOH solution
(250 μL, 0.50 mmol), 2 M aqueous HNO3 solution (500 μL, 1.00 mmol) and
1.59 M BiNO3 ∙ 5 H2O in 2 M aqueous HNO3 solution (31.5 – 220.5 μL,
0.05 – 0.35 mmol) were added to a 2 mL teflon insert. The insert was
placed in a 24-high-throughput reactor and heated for 48 h at 180 °C and
cooled down to RT in 6 h. The resulting product was filtered off and washed
with H2O. Different yields between 68 and 107 mg, 60 - 90 % (based on
Bi(NO3)3 ∙ 5 H2O) was obtained for 3, α-[Bi(PTC)] and 4, β-[Bi(PTC)].
Elemental analysis of 3: calc (%): C 23.0, H 0.5, N 3.4, found (%): C 22.7,
H 0.4, N 3.4 and 4: calc (%): C 23.0, H 0.5, N 3.4, found (%): C 22.8, H
0.4, N 3.4.
methodology employing
a 24-high-throughput reactor system was
used.[14c, 36] The high-throughput PXRD measurements were carried out
with a STOE Stadi-P combi diffractometer equipped with a xy-stage and a
Mythen detector (Cu K훼1 radiation). High resolution PXRD patterns were
measured on a STOE Stadi-P combi powder diffractometer equipped with
a Mythen detector (Cu K훼1 radiation). IR-spectra were recorded using a
Bruker ALPHA-FT-IR A220/D-01 spectrometer equipped with an ATR-unit.
NMR data were measured on a Bruker DRX 500 spectrometer. For the
analysis of the linker molecule, 1H-NMR spectroscopy was employed. The
samples were dissolved in deuterated dimethyl sulphoxide (d6-DMSO).
Thermogravimetric measurements were performed on a NETZSCH STA
409 CD analyzer under a flow of air (75 ml min-1) with a heating rate of
4 °C min-1 in a temperature range between 25 and 800 °C in Al2O3-
crucibles. The data were corrected for buoyancy and current effects. The
luminescence measurements of the solid samples were performed in
Suprasil quartz ampoules at room temperature, applying a HORIBA Jobin
Yvon GmbH fluorescence spectrometer (Fluorolog3) equipped with a
R928P Photomultiplier, an iHR-320-FA Triple Grating Imaging
spectrograph and a 450 W xenon lamp. Colour coordinates were
calculated from the measured emission spectra applying the Spectra Lux
Software v.2.0.[31a]
Acknowledgements
We appreciate the financial support from the Deutsche
Forschungsgemeinschaft (TE 1147/1-1), and the São Paulo
Research Foundation (FAPESP, Process number 2016/03640-9).
The authors thank also M. Radke for the sample photographs,
and Prof. Christian Näther and Inke Jess for the single crystal X-
ray diffraction measurements.
Synthesis. The synthesis of 1 - 4 was studied using high-throughput
methods (Vmax= 2.0 mL per Teflon insert) with H2O as solvent. Different
reaction temperatures between 80 and 180 °C, two different reaction times
of 6 and 48 h and different molar ratios of metal to linker to HNO3 to NaOH
in a range between 0.1 : 1 : 1 : 1 and 2 : 1 : 10 : 10 were employed. The
combination of acid and base was established due to the fact that the linker
is soluble under basic conditions and the metal source Bi(NO3)3 ∙ 5H2O in
nitric acid. In all optimized reactions a molar ratio HNO3 to NaOH of 4 to 2
was used in the starting mixture. Variation of the metal to linker ratio
resulted in the phase pure formation of the four title compounds. The final
pH values of the reaction mixtures were always within the range of pH = 3
to 6, and compound 2 was obtained at the lowest pH. Optimized synthesis
conditions in the HT reactors could be only obtained for 2. In case of 1, 3
and 4, sometimes the pure phase but most often mixtures of the three
phases were obtained. Phase pure 1 and 2 could be obtained using 7 mL
glass vials (Duran, Schott) at temperatures of 160 °C for 6 h. Compounds
3 and 4 could not be obtained in glass vials under these conditions. Hence
for 3 and 4 the parameter space in which the phases were observed during
the high-throughput investigations in 2 mL Telfon reactors is given below.
Keywords: coordination polymers • bismuth •
2,4,6-pyridinetricarboxylic acid • luminescence • high-throughput
methods
Optimized synthesis of 1: H3PTC (52.8 mg, 0.25 mmol), H2O (750 µL), 2
M aqueous solution NaOH (250 μL, 0.50 mmol), 2 M aqueous HNO3
solution (500 μL, 1.00 mmol) and 1.59 M BiNO3 ∙ 5 H2O in 2 M aqueous
HNO3 solution (157.5 μL, 0.25 mmol) were added to a 6 mL glass vial. The
vial was heated for 6 h at 160 °C and cooled down to RT in 6 h. The
resulting product was filtered off and washed with H2O. A yield of 87 mg,
(77 % based on Bi(NO3)3 ∙ 5 H2O) was obtained for 1, [Bi(PTC)(H2O)2].
Elemental analysis of 1: calc (%): C 21.2, H 1.3, N 3.1, found (%): C 21.0,
H 1.3, N 3.1.
Optimized synthesis of 2: H3PTC (52.8 mg, 0.25 mmol), H2O (750 µL), 2
M aqueous solution NaOH (250 μL, 0.50 mmol), 2 M aqueous HNO3
solution (500 μL, 1.00 mmol) and 1.59 M BiNO3 ∙ 5 H2O in 2 M aqueous
HNO3 solution (31.5 μL, 0.05 mmol) were added to a 6 mL glass vial. The
vial was heated for 6 h at 160 °C and cooled down to RT in 6 h. The
resulting product was filtered off and washed with H2O. A yield of 19 mg,
(69 % based on Bi(NO3)3 ∙ 5 H2O) was obtained for 2, (H3O)[Bi2(PTC)
7
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10.1002/ejic.201800154
European Journal of Inorganic Chemistry
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10.1002/ejic.201800154
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Table of Content
Key Topic: High-throughput investigation, Bismuth coordination polymer, luminescence
The systematic high-throughput investigation of the system Bi3+/ pyridine tricarboxylic acid (H3PTC) / NaOH / HNO3
in H2O under solvothermal reaction conditions resulted in the discovery of four new Bi carboxylates exhibiting
various coordination modes, inorganic building units and luminescence properties.
10
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