1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study

Article abstract of DOI:10.1021/acs.cgd.0c00287

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036-0.056 min-1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet-singlet electronic excitations to the fluorescence, indicating that metal-intraligand transitions are responsible for luminescence in both complexes.

Full text of DOI:10.1021/acs.cgd.0c00287

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Article
1
D and 2D silver-based coordination polymers with thiomorpholine-4-
carbonitrile and aromatic polyoxoacids as co-ligands: structure,
photocatalysis, photoluminescence and TD-DFT study
Predrag Risti#, Tamara R. Todorovic, Vladimir Blagojevi#, Olivera R. Klisuric, Ivana
Marjanovi#, Berta Barta Holló, Predrag Vulic, Mihaela Gulea, Morgan Donnard, Miguel
Monge, María Rodríguez-Castillo, Jose M. Lopez-De-Luzuriaga, and Nenad R. Filipovic
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.0c00287 • Publication Date (Web): 20 May 2020
Downloaded from pubs.acs.org on May 20, 2020
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D and 2D silver-based coordination polymers with thiomorpholine-4-
carbonitrile and aromatic polyoxoacids as co-ligands: structure,
photocatalysis, photoluminescence and TD-DFT study
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a
a,
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Predrag Ristić , Tamara R. Todorović *, Vladimir Blagojević , Olivera R. Klisurić ,
c
c
d
e
f
Ivana Marjanović , Berta Barta Holló , Predrag Vulić , Mihaela Gulea , Morgan Donnard ,
g
g
g
h
Miguel Monge , María Rodríguez-Castillo , José M. López-de-Luzuriaga , Nenad R. Filipović
a
University of Belgrade - Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia
bInstitute of Technical Sciences of the Serbian Academy of Sciences and Arts, Knez Mihailova
5/IV, 11000 Belgrade, Serbia
3
c
University of Novi Sad, Faculty of Sciences, Trg Dositeja Obradovića 4, 21000 Novi Sad,
Serbia
dFaculty of Mining and Geology, University of Belgrade, Đušina 5, 11000 Belgrade, Serbia
eUniversité de Strasbourg, CNRS, LIT – UMR 7200, Faculty of Pharmacy, 67000 Strasbourg,
France
fUniversité de Strasbourg, Université de Haute-Alsace, CNRS, LIMA – UMR 7042, ECPM,
67000 Strasbourg, France
g
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis
Química (CISQ), Complejo Científico-Tecnológico, 26004-Logroño, Spain
hUniversity of Belgrade - Faculty of Agriculture, Nemanjina 6, 11000 Belgrade, Serbia
*
-
Corresponding author: Tamara R. Todorović, PhD, Associate Professor, University of Belgrade
Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia; E-mail:
tamarat@chem.bg.ac.rs
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Abstract
Four silver-based coordination polymers {[Ag(L) ](BF )} (1), {[Ag(H BTC)(L)]×(H BTC)}
∞
2
4
∞
2
3
(
2), {[Ag (H BTEC)(L) ] × 3.33H O } (3) and [Ag(H 5SSA)(L)] (4) were synthesized using
2 2 2 2 ∞ 2 ∞
thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as co-
ligands: trimesic (H BTC), pyromellitic (H BTEC) and 5-sulfosalicylic acid (H 5SSA).
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Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-
monodentate ligand, while Ag(I) ion is three-coordinated in 2, and four-coordinated in all the
other compounds. Tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of
intermolecular interactions with the metal center. All compounds show reasonable photocatalytic
activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in 0.036‒0.056
–
1
min range. Changes in the reaction rates can be correlated with the type and coordination of the
co-ligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence
at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of
singlet parentage, where transitions are allowed. TD-DFT study determined the contributions of
individual singlet-singlet electronic excitations to the fluorescence, indicating that metal- intra
ligand transitions is responsible for luminescence in both complexes.
Keywords: Silver complexes; Coordination polymers; Intermolecular interactions;
Photoluminescence; Photocatalysis; TD-DFT.
1. INTRODUCTION
The investigation of coordination polymers (CPs) is a rapidly growing field of material
science. 1D–3D CPs have been studied because of the wide range of potential applications,
predominantly in catalysis, gas storage and separation, optoelectronics and sensors, molecular
electronics, nanomaterial synthesis, illumination and photodetection.1–15 Silver is among the top
ten metals used for the preparation of 2D CPs,16,17 while 8 % of all CPs (1D–3D) deposited in
18
CSD MOFs subset are Ag-CPs. The ability to adopt coordination numbers from 2 to 6, thus
offering various coordination geometries, makes silver a viable metal of choice for the synthesis
1
9
of CPs. In addition, coordination numbers higher than six have been observed in some of Ag-
CPs.20,21 Structural diversity of Ag-CPs is not only influenced by supramolecular Ag···ligand,
Ag···π, C‒H···π, π-π stacking and anion interactions, as well as H-bonds,22,23 but also by
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argentophilic (Ag···Ag) and Ag···C interactions.24,25 Finally, the structures of Ag-CPs are
heavily influenced by the nature of the anion of the starting silver salt.26–30 In the case of 1D Ag-
2
2
CPs, linear, zigzag, helical, ladder and 1D coordination tubes have been identified. In 2013, the
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first ribbon topology was observed for one 1D Ag-CP. More recently, the structure with metal
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cluster topology was discovered, making rotaxane topology the only unrealized topology type
of 1D Ag-CPs up to now. On the other hand, representative topologies of 2D Ag-CPs include sql
and hcb.18
Ag-CPs may undergo structural transformation induced by light,33 heating,34,35
solvation,36–40 desolvation, guest molecule
35
40,41
and anion exchange26,36,42,43 stimuli. They can be
used as precursors for the preparation of Ag nanoparticles by heating25,44 or ultrasonic
irradiation.45 Some of the investigated Ag-CPs form metallogels28,46–52 showing interesting
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properties, such as the ability to sense hazardous gases. Metallogels can also act as precursors
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46
for Ag-based nanoparticles which can be obtained in situ, spontaneously or upon exposure to
light.50 These nanoparticles exhibit luminescence properties,51 as well as the ability to be
reversibly assembled or disassembled by various stimuli.52 Finally, Ag-CPs metallogels can
display thixotropic behavior,47 stimuli-responsive to some anions as well as antibacterial
properties.47 A wide variety of functional properties makes Ag-CPs useful for different
applications. These properties include antibacterial activity,47,53 gas sensing,49 proton
conductivity, high capacitance and good cycling ability,54,55 and chemical sensing.19,56 Moreover,
Ag-CPs might play a significant role in environmental remediation,57–59 as they have been
tailored to achieve a particular mechanism of oxoanion exchange to maximize their
effectiveness.60 Most recently, there were several reports on Ag-CPs manifesting excellent
catalytic and photocatalytic properties.61–64 Environmentally friendly and recyclable Ag-CP with
9,10-anthraquinone-1,4-dicarboxylate acid catalyzed the reaction of the visible-light-driven
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aerobic oxidation of alkynes into 1,2-diketones under ambient conditions. 1D Ag-CPs with
N',N'-2,2-tetrakis(diphenylphosphanylmethyl)thiocarbohydrazide showed exceptional
performance as a photocatalyst for degradation of organic dyes in water, while generating higher
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photocurrent response than molecular complexes with the same ligand. Nano-microstructured
Ag-CPs offer performance at a level competitive with known semiconductors in photocatalytic
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water splitting and degradation of organic pollutants and dyes. They exhibit a highly reactive
valence band potential and could be readily recycled, maintaining high activity after four uses.
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Two Ag-CPs constructed using Co-metalloligands act as recyclable heterogeneous catalysts for
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the A3–coupling reactions of aldehydes, secondary amines and alkynes, where the relative
position of substituted pyridyl ring affected both the resulting coordination polymer structures
and their catalytic activity.
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Luminescent CPs are of great interest since they have been employed in sensing (metal
ions, solvents and explosives) and (bio)imaging.6
5–68
Some of the investigated Ag-CPs showed
potential for ion19,21,56,59 and solvent69 sensing. In that sense, the goal of our work is the
preparation of novel Ag-CPs, characterization of their luminescent properties at both low and
room temperature, and explanation of its origin using TD-DFT. For the preparation of Ag-CPs,
we used thiomorpholine-4-carbonitrile (L) and aromatic polyoxoacids as co-ligands (trimesic
acid, H BTC; pyromellitic acid, H BTEC and 5-sulfosalicylic acid, H 5SSA, Figure 1). L was
3
4
3
chosen as a ligand since it belongs to the class of bis-monodentate ligands which are able to form
Ag-CPs70–72, although it has never been used for this purpose. On the other hand, selected co-
ligands showed photoluminescent properties73–75 and can easily form Ag-CPs56,73,84,85,76–83
photoluminescent in some cases.76–83,85,86
–
Figure 1. Structures of L and aromatic polyoxoacids co-ligands.
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2
. EXPERIMENTAL
2.1. Materials and methods
All the employed reagents and solvents were of analytical grade and used without further
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purification. AgNO (≥ 99.0 %), AgBF (98 %), 1,2,4,5-benzenetetracarboxylic acid (96 %) and
3
4
5
-sulfosalicylic acid dihydrate (≥ 99.0 %) were obtained from Aldrich (Sigma-Aldrich Chemie
GmbH, Steinheim, Germany). 1,3,5-benzenetricarboxylic acid (≥ 95.0 % ) was obtained from
Merck. Elemental analyses (C, H, N, S) were performed by the standard micro-methods using
the ELEMENTARVario ELIII C.H.N.S=O analyzer. Infra-red (IR) spectra were recorded on a
Thermo Scientific Nicolet 6700 FT-IR spectrometer by the Attenuated Total Reflection (ATR)
−1
technique in the region 4000−400 cm . Abbreviations used for IR spectra: vs, very strong; s,
strong; m, medium; w, weak. The NMR spectra were performed on a Bruker Avance 500
equipped with a broad-band direct probe.
2
.2. Synthesis of the ligand thiomorpholine-4-carbonitrile (L)
The ligand was synthesized according to a modified literature procedure. In a round bottom
flask, thiomorpholine (1 equiv., mmol), acetonitrile (0.5 M, mL) and
8
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1
2
tetramethylethylenediamine (232 mg, 2 equiv., 2 mmol) were mixed together. Then CuCN (179
mg, 2 equiv., 2 mmol) was added and the mixture was flushed with oxygen. The reaction
solution was then let to stir under 1 atmosphere of O for 18 h. After a short filtration over
2
Celite® that was rinsed thrice with AcOEt (3 × 3 mL), the crude mixture was concentrated under
vacuum and purified by flash column chromatography (Pentane/AcOEt, SiO ) to afford the
2
entitled product. Yield 0.12 g (94%). White solid; m.p.: 41‒43 °C. Anal. Calcd. for C H N S
5
8
2
(MW = 128.19): C, 46.85; H, 6.29; N, 21.85; S 25.01 %. Found: C, 46.65; H, 6.73; N, 21.74; S
1
13
2
5.12 %. H NMR (CDCl , 500.26 MHz) δ : 2.70 (t, 4H), 3.46 (t, 4H); C NMR (CDCl , 126
3 H 3
MHz) δ : 26.1, 50.8, 117.4.
C
2
.3. Synthesis of {[Ag(L) ](BF )} (1)
2 4 ∞
A mixture of AgBF (38.00 mg, 0.195 mmol) and L (50.00 mg, 0.393 mmol) dissolved in H O (5
4
2
ml) was placed in amber round bottom flask. Reaction mixture was refluxed for 1 h. Colorless
single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation and
separated by filtration from colorless water solution. Yield: 0.017 g (19 %). Anal. Calcd. for
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C H AgBF N S (FW = 451.07): C, 26.63; H, 3.58; N, 12.42; S 14.22 %. Found: C, 27.04; H,
1
0
16
4
4 2
‒
1
3.65; N, 12.80; S, 14.38 %. IR (ATR, νmax/cm ): 3384 (w), 2998 (w), 2978 (w), 2928 (w), 2867
w), 2225 (vs), 1446 (m), 1393 (m), 1343 (m), 1285 (m),1161 (m), 1098 (m), 1059 (s), 979 (m),
46 (m), 714 (w), 531 (w), 507 (w).
(
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2.4. Synthesis of {[Ag(H BTC)(L)]×(H BTC)} (2), {[Ag (H BTEC)(L) ] × 3.33H O } (3) and
2
3
∞
2
2
2
2
∞
[
Ag(H 5SSA)(L)] (4)
2 ∞
A mixture of H BTC (82.00 mg, 0.390 mmol) in EtOH (5 ml), H BTEC (99.00 mg, 0.389 mmol)
3
4
in MeOH (5 ml) or solid H 5SSA (98.00 mg, 0.400 mmol) was added to the mixture of AgNO
3
3
(66.00 mg, 0.388 mmol) and L (50.00 mg, 0.393 mmol) in H O (10 ml) and placed in amber
2
round bottom flask. Reaction mixture was refluxed for 1 h. White single crystals of 2 and pale-
yellow single crystals of 3 and 4, suitable for X-ray diffraction analysis, were obtained by slow
evaporation and separated by filtration from colorless water solution.
2
: Yield 0.058 g (29.5 %). Anal. Calcd. for C H AgN O S (FW = 655.33): C, 42.15; H, 2.92;
23 19 2 12
‒
1
N, 4.27; S, 4.89 %. Found: C, 41.90; H, 2.90; N, 4.25; S, 4.95 %. IR (ATR, νmax/cm ): 3128 (m),
927 (m), 2650 (m), 2527 (m), 2227 (vs), 1694 (vs), 1607 (m), 1447 (s), 1393 (s), 1363 (s), 1282
(s), 1213 (s), 1157 (s), 1121 (s), 1031 (m), 982 (m), 943 (s), 739 (m), 698 (m), 675 (m), 656 (m),
2
5
32 (m), 509 (m).
3
: Yield 0.146 g (68 %). Freshly prepared sample: Anal. Calcd. for C H Ag N O S ×3.33H O
2
0
20
2
4
8
2
2
(FW = 784.31): C, 30.63; H, 3.43; N, 7.14; S, 8.18 %. Found: C, 30.70; H, 3.21; N, 7.27; S, 8.10
. Sample dried in desiccator for seven days: Anal. Calcd. for C H Ag N O S (FW = 724.26):
%
2
0
20
2
4
8 2
C, 33.17; H, 2.78; N, 7.74; S, 8.85 %. Found: C, 33.05; H, 2.91; N, 7.57; S, 8.76 %. IR (ATR,
‒
1
νmax/cm ; dried sample): 2931 (w), 2824 (w), 2511 (w), 2222 (s), 1822 (w), 1676 (vs), 1608 (s),
490 (s), 1420 (s), 1378 (s), 1285 (s), 1169 (s), 1128 (s), 988 (s), 945 (s), 911 (s), 767 (s), 947
m), 552 (m), 470 (w).
1
(
4
6
2
1
: Yield 0.111 g (52 %). Anal. Calcd. for C H AgN O S (FW = 453.23): C, 31.80; H, 2.89; N,
12 13 2 6 2
‒
1
.18; S, 14.15 %. Found: C, 31.52; H, 2.78; N, 6.12; S, 14.20 %. IR (ATR, νmax/cm ): 3000 (w),
793 (m), 2581 (w), 2500 (w), 2244 (m), 1666 (s), 1610 (m), 1179 (m), 1434 (m), 1370 (m),
285 (m), 1233 (m), 1200 (m), 1166 (vs), 1118 (s), 1023 (s), 942 (m), 835 (w), 804 (w), 780 (w),
757 (w), 715 (w), 663 (w), 588 (s), 534 (w).
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.5. X- ray crystallography
X-ray diffraction data for 13 were collected at room temperature using Graphite-
monochromated CuKα radiation ( = 1.54184 Å) on an Oxford Diffraction Gemini S
8
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diffractometer. CrysAlisPro and CrysAlis RED software packages were used for data collection
and data integration. X-ray diffraction data for 4 were collected at 173 K on the Bruker APEX-II
CCD diffractometer. Graphite-monochromated MoKα radiation ( = 0.71073 Å) was used to
measure diffraction from suitable single crystals of 4. Bruker APEX2 and Bruker SAINT
software packages89 were used for data collection and data integration. Space group
determinations for 14 were based on analysis of the Laue class and systematically absent
reflections. Collected data for 13 were corrected for absorption effects using analytical numeric
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2
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8
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2
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2
3
4
5
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9
0
9
0
absorption correction applying a multifaceted crystal model, while for 4 we used the multi-scan
method, applying an empirical absorption correction using spherical harmonics as implemented
8
9
in SADABS. Structure solution and refinement for 14 were carried out with the programs
SHELXT91 and SHELXL-2018/3,92 respectively. MERCURY93 was employed for molecular
9
4
graphics and WinGX software was used to prepare material for publication. Non-hydrogen
atoms were refined anisotropically while hydrogen atoms in 1 and 2 were treated by constrained
isotropic refinement. On the other hand, hydrogen atoms in 3 and 4 were treated by a mixture of
independent and constrained refinement. Even though complex 3 has disordered crystalline water
molecules we presented its structure as it is, using SHELXL DFIX instructions to restrain OH
bond lengths. Crystal data and refinement parameters for 14 are summarized in Table 1. We
9
5
also treated complex 3 by the SQUEEZE routine, implemented in Platon , to remove the
disordered water molecules and presented crystal data and refinement parameters in Table S1
(Electronic supplementary material, ESI). Topological analysis was performed with the
ToposPro program package and the TTD collection of periodic network topologies.96
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
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5
5
6
Table 1. Crystallographic data and refinement parameters for 14.
Crystal data
Compound
1
2
3
4
C
×
30 3 6 12 3
H30Ag N O S
5H O
2
Chemical formula
2(C
5
H
8
Ag0.50
N
2
S)·BF
4
C
23
H
19AgN
2
O
12
S
C
12 2 6 2
H13AgN O S
FW
451.07
Tetragonal
P‒42
655.33
1176.47
Monoclinic
P2 /n
453.23
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
0
1
2
3
4
5
6
7
8
9
0
Crystal system
Triclinic
Monoclinic
Space group
1
m
P‒1
1
1
P2 /n
a (Å)
b (Å)
c (Å)
 (°)
13.1613 (6)
13.1613 (6)
4.4326 (6)
90
9.6126 (5)
9.8212 (10)
26.3006 (4)
16.2293 (3)
90
12.8066 (4)
8.7191 (3)
13.4239 (6)
90
11.9927 (8)
12.1218 (6)
67.755 (6)
78.686 (5)
68.517 (6)
1200.86 (14)
2
1.812
8.20


(°)
(°)
90
93.666 (10)
90
4183.51 (11)
97.048 (3)
90
1487.61 (10)
90
3
V (Å )
767.81 (13)
2
1.951
Z
4
4
−
3
D
x
(Mg m )
1.868
13.24
2.024
1.67
0
0
−
1
µ (mm )
13.49
.40 × 0.20 ×
.15
Crystal size (mm)
Data collection
0.28 × 0.08 × 0.07
0.13 × 0.10 × 0.09
0.37 × 0.16 × 0.07
Absorption correction Analytical
0.178, 0.466
Analytical
Analytical
Multi-scan
T
min, Tmax
0.487, 0.606
7362
0.094, 0.482
16229
0.651, 0.746
29703
Reflections collected 3187
Independent reflections 799
Observed reflections
4504
7963
5109
7
44
4022
6801
4548
[I > 2σ(I)]
R
int
0.034
0.025
0.026
0.018
Range of h, k, l
h=−16→13
k=−15→7
l=−5→4
h=−11→11
k =−14→14
l=−14→11
h=−12→11
k=−32→20
l=−19→19
h=−19→19
k=−12→12
l=−19→19
θmax = 32.0, θmin
θ values (°)
θmax = 72.8, θmin = 4.8
θmax = 72.6, θmin = 4.0 θmax = 71.7, θmin = 3.2
=
2.1
Refinement
R[F > 2σ(F )], wR(F ) 0.0373, 0.0955
2
2
2
0.0326, 0.0828
0.0375, 0.0865
1.025
0.0326, 0.0786
0.0393, 0.0823
1.031
0.0222, 0.0525
0.0276, 0.0567
1.086
R[all data], wR2
Goodness-of-fit (S)
0.0410, 0.0998
1.058
No. of reflections
799
4504
7963
5109
No. of parameters
No. of restraints
59
0
357
0
574
136
216
0
−
3
Δρmax, Δρmin (e Å )
0.48, −0.39
0.48, −0.39
0.76, −0.73
0.52, −0.51
CCDC no.
1987944
1987947
1990303
1987949
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The X-ray powder diffraction experiment was conducted on Rigaku Smartlab X-ray
diffractometer in θ-θ geometry (the sample in horizontal position) in parafocusing Bragg-
Brentano geometry using D/teX Ultra 250 strip detector in 1D standard mode with
CuKα1,2 radiation source (U = 40 kV and I = 30 mA). The XRPD patterns were collected in 5-65°
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
2
θ range, with a step of 0.01°, and the data collection speed of 5 °/min with horizontal sample
rotation of 20 rpm. For every compound, a small amount of single-crystal sample was
pulverized, and low background single crystal silicon sample holder was used to minimize the
background. The crystal phases present in the samples were identified in dedicated Rigaku
PDXL 2.0 software, comparing them with user database comprised of CIFs previously obtained
by a single crystal X-ray diffraction.
2.6. Hirshfeld surface analysis and intermolecular interaction energies
Hirshfeld surface analysis was carried out using the Crystallographic Information File.
Before calculating the surfaces, the lengths of the bonds which include hydrogen atoms were
normalized to standard values determined by neutron diffraction. The Hirshfeld surfaces
visualization and the presentation of the results as dnorm, shape index, and curvedness, as well as
the calculation of 2D fingerprint plots with d and d distances were pefrormed by Crystal
e
i
Explorer v.17.5.97,98 The parameter dnorm represents the sum of the distance of the nearest nucleus
external to the surface (d ) and the distance from the surface to the nearest nucleus internal to the
e
surface (d ), normalized by the van der Waals radius of the atom. The surfaces were mapped over
i
a standard color scale, with the corresponding 2D fingerprint plots calculated using d and di
e
values in the range 0.4‒2.8 Å. The intermolecular interaction energies were determined using
CrystalExplorer v17.5, with the wavefunction calculated using Gaussian09 software99 with
B3LYP method and DGDZVP basis set.100 The model systems were built from supercells of
different size by creating a non-polymeric system. This was achieved by removing the metal
centers, preserving whole ligand molecules, and capping eliminated covalent bonds with
hydrogen atoms to preserve the charge balance.
2
.7. TGA-DSC analysis
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1
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1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Thermal data were collected using the TA Instruments SDT Q600 thermal analyzer. The
‒
1
decomposition was followed from room temperature to 400 °C at 10 °C min heating rate in
3
‒1
argon carrier gas (flow rate = 30 cm min ). Sample holder/reference is alumina crucible/empty
alumina crucible. The sample mass was 3‒5 mg.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
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2
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3
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9
0
2.8. Photocatalytic and photophysical properties
Mordant blue (MB9), a widespread environmental pollutant, is a commonly used dye in
the textile industry. A volume of 50 ml of dye solution in water (c = 0.5 mol/L), was mixed with
50 mg of each of the complexes. The powdered complexes were added to the water solution
under constant stirring and left in the dark for 15 min to equilibrate. The samples were
illuminated by a spotlight source (Hamamatsu LC5) from a distance of 1 cm (light intensity 5.2
2
mW/cm ). The decomposition rate of MB9 as a function of irradiation time was measured by a
Varian Cary 50 Scan UV-Vis spectrophotometer. A lamp with the emission in the UV and
visible part of the spectrum was turned on, followed by the extraction of 5 ml of solution at
regular intervals later measured in a UV/VIS spectrometer. MB9 has two main absorption
regions: around 330 and around 530 nm. The relative concentration of MB9 is tracked using
absorption intensities in these regions. The measured absorption intensities were used to
calculate relative concentrations of MB9 dye and the corresponding rate constants for the
photocatalytic degradation reaction of MB9 dye.101
Diffuse reflectance UV-vis spectra of pressed powder samples diluted with KBr were
recorded on a Shimadzu (UV-3600 spectrophotometer with a Harrick Praying Mantis accessory)
and recalculated following the Kubelka−Munk function. Excitation and emission spectra in the
solid state were recorded with a Jobin-Yvon Horiba Fluorolog 3–22 Tau-3 spectrofluorimeter.
Lifetime measurements were recorded with a Datastation HUB-B with a nanoLED controller and
DAS6 software. The nanoLED employed for lifetime measurements were of 320 nm with pulse
lengths of 0.8–1.4 ns. The lifetime data were fitted with the Jobin-Yvon software package.
2
.9. Computational details
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Single point DFT and TD-DFT calculations were carried out for models 3 and 4. In both
the ground-state calculations and the subsequent calculations of the electronic excitation spectra,
the B3LYP functional102–104 as implemented in TURBOMOLE105 was used. The excitation
energies were obtained at the density functional level by using the time dependent perturbation
theory approach (TD-DFT),106–109 which is a DFT generalization of the Hartree-Fock linear
response (HF-LR) or random-phase approximation (RPA) method.110 In all calculations, the
Karlsruhe split-valence quality basis sets augmented with polarization functions111,112 were used
for the light elements (SVP) whereas the def2-TZVP bases sets were used for Ag.113 The
Stuttgart effective core potential in TURBOMOLE was used for Ag.114
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
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8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
. RESULTS AND DISCUSSION
3
.1 Molecular and crystal structures of 1‒4
Complex 1 crystallizes in the tetragonal P‒42 m space group. The asymmetric unit of 1
1
contains a Ag(I) and a tetrafluoroborate anion, both of a quarter occupancy, as well as a half of
the L ligand. Ag(I) atoms are situated on a 2-fold axis along which two mirror planes intersect
(Wyckoff position 2c, site symmetry 2.mm). Moreover, L lies on the (110) mirror plane
(Wyckoff position 4e, site symmetry ..m) with half-occupancy, except for the C2 and C3 atoms
in general positions. The F1 atom of the tetrafluoroborate anion is in a general position, while the
quarter-occupancy B1 atom is located at the Wyckoff 2a position (site symmetry –4..). The part
of infinite structure of 1 depicted in Figure 2A shows that Ls form a distorted tetrahedron around
1
15
the Ag(I). The geometric index of distortion is τ = 0.86. Each of the Ag(I) ions in 1 is
4
coordinated to two nitrogen and two sulfur atoms from four different L ligands. Selected bond
lengths are given in Table 2. L acts as a bridging ligand with bis–monodentate coordination
connecting the Ag(I) ions to form a two-dimensional coordination network (Figure 2B). The
crystal packing of 1 comprises of 2D layers stacked along c-axis with a thickness of 4.57 Å
(Figure 2C).
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2
3
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0
9
3
Figure 2. (A) ORTEP drawing (generated by MERCURY ) of the part of infinite structure of 1
with labeled non-H atoms. The atoms of the asymmetric unit are labeled in black. Displacement
ellipsoids are shown at the 50% probability level, while the H atoms are drawn as spheres of
arbitrary radii. Symmetry codes: (1) −x+1, −y, z; (2) y, −x+1, −z; (3) −y+1, x−1, −z. Lengths of
bonds labeled as 1 and 2 (in blue) are given in Table 2. (B) The crystal packing of 1 viewed
along c-axis. (C) Stacked layers viewed along b-axis. All hydrogen atoms (B, C) and
tetrafluoroborate anions (C) are omitted for clarity.
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Table 2. Selected bond lengths for 14.
Compound Bond label Bond type
Bond length (Å)
1
Ag1–N1, Ag1–N11 2.327(9)
1
2
3
2
Ag1–S1 , Ag1–S1 2.555(2)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
3
Ag1–N1
Ag1–S19
Ag1–O1
Ag1–N1
Ag1–O1
Ag1–S311
Ag1–O512
Ag2–N2
Ag2–O5
Ag2–S113
Ag2–O114
Ag3–N3
Ag3–O9
Ag3—S2
Ag3–O915
Ag1–N1
Ag1–O1
Ag1–S1
2.180(3)
2
4
2.4164(7)
2.406(2)
5
6
2.221(3)
7
2.340(2)
8
2.4309(11)
2.479(3)
9
10
2.245(3)
1
1
2.333(2)
3
12
2.4321(10)
2.467(3)
1
3
14
2.216(3)
1
5
2.343(2)
16
2.4341(11)
2.494(3)
1
7
18
2.1818(15)
2.4576(11)
2.4903(4)
2.6170(1)
1
9
4
20
2
1
Ag1–O2
Symmetry codes: (1) −x+1, −y, z; (2) y, −x+1, −z; (3) −y+1, x−1, −z; (9) x−1, y, z; (11) −x+2, −y+1, −z+1; (12)
x+1, −y+2, −z+1; (13) −x+1, −y+1, −z+1; (14) x+1, y, z; (v) x+1/2, −y+3/2, z+1/2; (15) x−1/2, −y+3/2,
z−1/2.
−
Complex 2 crystallizes in the triclinic P‒1 space group. The asymmetric unit consists of a
‒
Ag(I) ion, one of each L and H BTC ligands, as well as one neutral non-coordinated H BTC
2
3
molecule. The part of infinite structure of 2, shown in Figure 3A, reveals that the Ag(I) ion tri-
coordinated by a nitrogen and a sulfur atom from two different L ligands and one deprotonated
‒
carboxylate oxygen atom from H BTC . This gives rise to a distorted trigonal planar geometry
2
9
9
with values of N1–Ag1–O1, N1–Ag1–S1 , and O1–Ag1–S1 angles of 93.77(12)°, 149.25(11)°,
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
and 116.24(6)°, respectively. Selected bond lengths are given in Table 2. The coordination mode
‒
of H BTC is monodentate, while L behaves as a bis-monodentate ligand creating a
2
centrosymmetric 1D chain parallel to the a-axis (Figure 3B). Non-coordinated H BTC molecule
3
‒
and H BTC ligands are connected by the OH···O hydrogen interactions (Table 3).
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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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
9
3
Figure 3. (A) ORTEP drawing (generated by MERCURY ) of the part of infinite structure of 2
with labeled non-H atoms. The atoms of the asymmetric unit are labeled in black. Displacement
ellipsoids are shown at the 50% probability level, while the H atoms are drawn as spheres of
arbitrary radii. Symmetry codes: (9) x−1, y, z; (10) x+1, y, z. Lengths of bonds labeled as 3–5 (in
blue) are given in Table 2. (B) The crystal packing of 2 viewed along c-axis. Selected hydrogen
bonds are showed as dashed lines. The hydrogen atoms not involved in the selected hydrogen
bonds are omitted for clarity.
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Table 3. Selected hydrogen bond parameters in the crystal packing of 2.
DH···A
DH (Å)
O10—H10···O3i 0.82
H···A (Å)
1.82
D···A (Å)
2.638 (3)
DH···A (°)
172.8
O7—H7···O2
O4—H4···O9ii
O6—H6···O8iii
0.82
0.82
0.82
1.70
1.81
1.95
1.82
2.517 (3)
2.613 (3)
2.698 (3)
2.601 (3)
171.0
166.5
151.9
158.5
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
O12—H12···O1iv 0.82
Symmetry codes: (i) x−1, y+1, z−1; (ii) x+1, y−1, z+1; (iii) x, y−1, z; (iv) x, y+1, z
Complex 3 crystallizes in the monoclinic P2 /n space group. The asymmetric unit
1
contains three crystallographically different Ag(I) ions, three L ligands, one and a half
2
‒
H BTEC ligand and five disordered water molecules. Each Ag(I) ion is coordinated to one
2
sulfur and one nitrogen atom from different L ligands, as well as two deprotonated carboxylate
2
‒
oxygen atoms from different H BTEC ligands. Selected bond lengths are given in Table 2. The
2
2
‒
coordination mode of L is bis-monodentate, while H BTEC behaves as a bis-bidentate bridging
2
ligand. The part of infinite structure is depicted in Figure 4A. The geometry around each of the
Ag(I) ions is distorted tetrahedral with the geometric index of distortion of τ = 0.70 (Ag1),
4
τ = 0.76 (Ag2), and τ = 0.74 (Ag3), thus the structure at each Ag(I) in 3 can be described as
4
4
seesaw.115 The crystal packing comprises of 2D layers of 5.83 Å thickness parallel to the (110)
plane (Figure 4 B,C). A CSD116 search performed by Con-Quest 1.18 showed that 3 is the first
93
2
‒
compound containing H BTEC ligand coordinated to Ag(I).
2
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3
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9
0
1
2
3
4
5
6
7
8
9
0
9
3
Figure 4. (A) ORTEP drawing (generated by MERCURY ) of the part of infinite structure of 3
with labeled non-H atoms. The atoms of the asymmetric unit cell are labeled in bold.
Displacement ellipsoids are shown at the 50% probability level, while the H atoms are drawn as
spheres of arbitrary radii. Lengths of bonds labeled as 6–17 (in blue) are given in Table 2. (B)
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The extended structure of 3 viewed parallel to c-axis. (C) The extended structure of 3 viewed
along a-axis showing two-dimensional layers. All hydrogen atoms are omitted for clarity (B, C).
Complex 4 crystallizes in the monoclinic P2 /n space group. The asymmetric unit
1
–
consists of a single Ag(I) atom and one of each L and H 5SSA ligands. Two sulfonate oxygen
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
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4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
–
atoms from two different H 5SSA ligands are coordinated to Ag(I), as well as a nitrogen and a
2
sulfur atom from two different L ligands. The part of the infinite structure is illustrated in Figure
5
A. As τ = 0.75, the geometry around each of the Ag(I) atoms is seesaw.115 Selected bond
4
–
lengths are given in Table 2. Both H 5SSA and L behave as bis-monodentate ligands, with L
2
creating a centrosymmetric double 1D chain parallel to b-axis. (Figure 5B). The crystal packing
is based on H-interactions (Table 4). A CSD116 search performed by Con-Quest 1.18 showed
93
–
that 4 is the first compound containing H 5SSA ligand coordinated to Ag(I).
2
9
3
Figure 5. (A) ORTEP drawings (generated by MERCURY ) of the part of infinite structure of 4
with labeled non-H atoms. The atoms of the asymmetric unit cell are labeled in black.
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Displacement ellipsoids are shown at the 50% probability level, while the H atoms are drawn as
spheres of arbitrary radii. Lengths of bonds labeled as 18–21 (in blue) are given in Table 2. (B)
The crystal packing of 4 viewed along c-axis. Selected hydrogen bonds are showed as dashed
lines. The hydrogen atoms not involved in the selected hydrogen bonds are omitted for clarity.
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
0
1
2
3
4
5
6
7
8
9
0
Table 4. Selected H-bond parameters in the crystal packing of 4.
DH···A
O5—H5···O3v
DH (Å)
H···A (Å)
1.82 (3)
D···A (Å)
DH···A (°)
0.80 (3)
2.6246 (17)
175 (3)
O6—H6···O4
0.85 (3)
1.76 (3)
2.575 (2)
162 (3)
Symmetry code: (v) x, y+1, z
Topological analysis in standard representation suggests that each Ag(I) in 1 and 4 acts as
a 4-connected node. The overall structure of 1 has a sql, while 4 has (4,4)(0,2) underlying net
topology.117 In contrast, each Ag(I) ion in 2 acts as a 2-connected node with 2C1 underlying net
topology. 117 The structure of 3 can be described as a binodal net. Both Ag(I) ions and H BTEC
2‒
2
ligands act as 4-connected nodes, giving rise to a 4,4L28 underlying net topology.117
All samples correspond to the single-phase X-ray powder patterns (Figure S1, ESI) in
accordance with the structural model obtained by the single-crystal X-ray diffraction.
3
.2. Hirshfeld and 2D fingerprint plot analysis
Visualization and quick and easy understanding of intra- and intermolecular interactions
in the crystal structures can be achieved using Hirshfeld surface and fingerprint plot
analysis.97,118 The Hirshfeld surfaces and the pseudosymmetric 2D fingerprint plots,119 as well
as the existing classical and non-classical interactions in the crystal structures of 1‒4 are depicted
in Figure 6. In all complexes, interactions can be observed in the shape-index plot as red and
blue regions, as well as in the curvature plot as a flat zone in the same position of the surface as
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in the shape-index plot. White circles mark the regions of the surfaces through which the
complexes interact.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
Figure 6. 2D fingerprint plot, Hirshfeld surface mapped with dnorm, shape index and curvedness
for 1‒4. For interaction types see Table 4.
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1
1
1
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1
2
2
2
2
2
2
2
2
2
2
3
3
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3
4
4
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4
4
4
4
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5
5
5
5
5
5
5
5
5
6
The relative contributions of different types of interactions in 1‒4 are shown in Table 5.
As expected, the O···H interactions are completely absent in 1 since it does not contain any co-
ligand, and therefore no oxygen. On the other hand, the O···H interactions are the most dominant
type in other three complexes with aromatic polyoxoacids acids as co-ligands. Furthermore, 2
exhibits uncommonly high contribution of interactions of hydrogen and oxygen with the metal
center. This can be attributed to proximity of the carboxylic group of the tricarboxylic acid to the
metal (at 2.9 Å and 3.2 Å), which is just slightly longer than the Ag‒O distance of the
coordinated carboxylic group (2.4 Å). This indicates particularly strong interactions of the metal
center with the carboxylic groups perpendicular to the plane of coordination, resulting in a quasi-
3D structure for 2, with 2D planes connected through the strong Ag···O interactions on the
perpendicular axis. This type of interaction is also present in 4, where the Ag···O distances are
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
0
1
2
3
4
5
6
7
8
9
0
2
.6 and 3.4 Å, and the interaction comes primarily from the oxygen atoms bound to the sulfur.
Absence of the Ag···O interactions in 3 can be correlated with the tetrahedral coordination
around the metal.
Table 5. Relative contributions (in %) and (d + d ) values (in Å) of different interaction types in
i
e
the crystal structures of 1‒4.
1
2
3
4
Interaction interaction relative
d
d
i
+
relative
d
d
i
+
relative
d
d
i
+
relative
contribution
3.45
d
d
i
+
number
type
contribution
e
contribution
e
contribution
e
e
1
2
3
4
N···H
S···H
C···H
F···H
O···H
Ag···H
Ag···O
6.4
3.5
3.85
4.85
-
2.9
3.0
-
2.3
0.75
2.1
-
2.2
2.3
-
7.55
2.35
1.65
-
3.6
3.6
-
3.2
3.4
-
2.0
8.65
2.5
-
-
-
-
-
4
5
6
’
13.6
8.3
5.9
1.2
2.4
2.6
17
3.0
-
12.1
2.6
2.2
2.4
-
-
0.45
-
1.3
-
-
-
2.25
3.3. Intermolecular interactions
Different types of intermolecular interactions within the crystal packing play an
important part in the behavior of co-crystals, affecting their photophysical and pharmaceutical
properties.120 Table 6 shows an overview of the calculated values of intermolecular interactions
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in model systems for all four complexes. These values are in a similar range for all systems –
around 40 kJ/mol per monomer unit. However, the relative contributions of different types of
interactions vary from one system to another (Tables S2‒S5, ESI). In 1, the intermolecular
interactions are absolutely dominated by the dispersion interactions (88% contribution of
attractive interactions, Table 7), while the electron interactions are almost negligible. This can be
attributed to the stacking of monomer units in 2D layers. In 2, on the other hand, electron
interactions are more dominant (49% contribution to attractive interactions, Table 7), with
dispersion playing an important part. In 3 and 4, the dispersion interactions contribute 48% and
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
5
5% (Table 7), respectively, while the electron interactions contribute 35% and 31%,
respectively, to the attractive interactions. This can be attributed to the increased role of
hydrogen bonding, particularly between oxygen and hydrogen, in 2‒4. In addition, 2 exhibits the
highest contribution of interactions between hydrogen and metal center, which can be correlated
with its highest contribution of electron interactions. In all complexes, polarizations interactions
contribute 11‒17% (Table 7) to the overall attractive interaction energy, indicating that different
composition and structure has relatively little effect on the role of this type of interactions. In 3,
slightly increased contribution of polarization interactions can be correlated with somewhat
lower overall energy of intermolecular interactions. Differences in contributions of different
types of interactions can be correlated to the spatial arrangement of monomer units in the lattice,
with the location and orientation of hydrogen bonding being the decisive contributor to the
electronic contribution to the value of the energy of attractive interactions. The negligible
contribution of the electron interactions in 1 can be attributed largely to the absence of oxygen in
the structure.
Table 6. Overview of calculated values for intermolecular interactions in model systems of 1‒4.
Complex
Intermolecular
Interactions (kJ/mol)
‒84.6
monomer units
Per monomer unit
(kJ/mol)
‒42.3
1
2
3
4
2
‒682.2
16
8
‒42.64
‒288.3
‒36.04
‒466.9
12
‒38.91
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Table 7. Relative contributions (in %) to attractive interactions in the crystal structures of 1‒4.
Complex
Electron
0.5
Polarization
11.1
Dispersion
88.4
1
2
3
4
48.6
13.8
37.6
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
0
1
2
3
4
5
6
7
8
9
0
35.2
17.0
47.8
30.9
14.0
55.1
3.4. Thermal properties of 1‒4
Based on the thermoanalytical data, 1‒4 do not contain any lattice solvents. Complex 3
crystallizes with 3.33 water molecules per formula unit (Table 1). However, the lattice water
almost completely evaporates during storage in desiccator for seven days. The thermal stability
of the compounds, given by their onset temperatures, is relatively high and increases as follows:
1
73 °C (3) < 188 °C (4) < 192 °C (1) < 237 °C (2). The decomposition mechanism of each CP is
different, in accordance with their different composition and structure. In all cases, the
decomposition is a complex process which occurs in several more or less overlapped steps
(Figure 7A).
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
Figure 7. DTG (A) and DSC (B) curves of 1‒4 in argon.
The simultaneously recorded DSC curves are shown in Figure 7B. As can be seen, the
decomposition of 1 and 4 begins with an exothermic process. Although the thermal
decomposition of tetrafluoroborates in most cases is followed by endothermic heat effects,121–123
in this case, the decomposition is exothermic. This phenomenon may be a result of
+
intramolecular redox reactions between Ag and L which are less pronounced in 2‒4, most likely
−
because of the nature of the co-ligands. Additionally, 1 is cationic complex with BF as counter
4
ion, and all other complexes contain the organic co-ligands coordinated to Ag(I). The oxidative
+
−
124
properties of Ag in the presence of BF are discussed in the literature. The small mass loss of
4
4 at ~200°C, followed by exothermic heat effect is most probably a CO releasing process in
2
accordance with the composition of the compound. Above ~250 °C the thermal decomposition of
4
continues with endothermic processes (Figure 7B). The decomposition process of 2 and 3 is
followed by endothermic effects in the whole temperature range of analysis (Figure 7B).
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1
1
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1
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2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
.5. Photocatalytic properties
Photocatalytic properties of 1‒4 were investigated in the reaction of photocatalytic
degradation of MB9 dye. Since all complexes are insoluble in water, they were tested as
heterogeneous catalysts in powder form for a degradation reaction in water. The progress of
degradation reaction was monitored using UV/VIS spectroscopy (Figure S2, ESI) and the results
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
0
1
2
3
4
5
6
7
8
9
0
are shown in Table 8. A dependence of –ln(C/C ) on time (Figure S3, ESI), where the initial part
0
2
of the curve shows linear dependence (with R > 99%) in all four complexes, indicates that the
reaction of the photocatalytic degradation of MB9 dye can be treated as a first-order reaction.
Apparent first-order rate constants for all four compounds were calculated to be in 0.036‒0.056
min–1 range, which is comparable to the values obtained for ZnO-based photocatalysts in
photocatalytic degradation of organic dyes.125 In addition, this is also comparable to or better
than the reported activities for Ag-based CPs for photocatalytic degradation of organic dyes126–
129.
This indicates that all four complexes exhibit reasonably high photocatalytic activity. The
lowest value was obtained for 1, and the highest for 2. It is interesting to note that 3 has more Ag
atoms per monomer unit (Table 8) than 1, 2 and 4, therefore, the increase in photocatalytic
activity cannot be attributed to higher Ag content. There is also no significant difference in the
accessible free lattice volume for water (all four complexes have 0), suggesting that none of the
structures exhibits porosity. Therefore, the increase in photocatalytic activity can most likely be
correlated with the existence of different co-ligands in the four complexes: 1 does not contain
carboxylic acid as a co-ligand and exhibits the lowest photocatalytic activity, 4 contains H 5SSA
3
and exhibits lower photocatalytic activity than 3 and 2, which contain H BTEC and H BTC,
4
3
respectively. Complex 2 also contains free H BTC molecule in addition to the one coordinated to
3
the metal center. Complex 4 contains one carboxylic group and one hydroxyl group in addition
to sulfonic acid group, 3 contains one tetracarboxylic acid, while 2 contains two tricarboxylic
acids. This suggests that the photocatalytic mechanism most likely includes active hydroxyl
radicals (•OH) as the main reactive species.126,127 The excited state of the complex reacts with
water to form •OH which oxidizes the dye. The oxygen in the system can easily re-oxidize the
reduced complex species making it active again. The presence of more reactive carboxylic
groups in the system enhances the photocatalytic activity of the complexes, and the change
photocatalytic reactivity of these complexes can be roughly correlated with increasing number of
oxygen groups in the structure.
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Table 8. Calculated apparent first-order rate constants corresponding to each compound
Empirical formula Rate constant
Compound General formula
–
1
(
FW)
C H AgBF N S
4 2
(min )
1
0
16
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
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
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
{[Ag(L) ](BF )}
∞
0.036±0.001
2
4
(FW = 451.07)
C H AgN O S
2
3
19
2
12
{[Ag(H BTC)(L)]×(H BTC)}
∞
0.056±0.003
0.055±0.004
0.040±0.002
2
3
(
FW = 655.33)
C H Ag N O S
8 2
2
0
20
2
4
{[Ag (H BTEC)(L) ]}
∞
2
2
2
(
FW = 724.26)
C H AgN O S
6 2
1
2
13
2
[Ag(H 5SSA)(L)]
2
∞
(FW = 453.23)
3
.6. Photophysical properties
While complexes 1 and 2 do not show emissive properties in the solid state at RT or
7 K, complexes 3 and 4 display luminescent emissions in the solid state when they are
7
irradiated with UV light. Complex 3 is not luminescent at RT, but it is luminescent at 77 K,
showing an emission band centred at 522 nm (λexc 340 nm). In contrast, 4 is emissive at RT,
displaying a more energetic emission located at 430 nm (λexc 330 nm). When the temperature is
decreased to 77 K, a very similar emission, without any noticeable energetic shift, is detected for
this complex (Figure 8).
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1
1
1
1
1
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1
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
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5
5
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5
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5
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Figure 8. Excitation and emission spectra in solid state at 77K (A) and room temperature and 77
K (B) for 3 and 4, respectively.
The lifetime obtained for the emission for 3 at 77 K is 8 ns, while for 4 it is 7 and 8 ns at
room temperature and 77 K, respectively. These lifetimes seem to indicate electronic transitions
of singlet parentage for the origin of the experimentally observed emissions. In fact, the
excitation spectra collected in the solid state for 3 and 4 appear included within the wavelength
range of the corresponding absorption spectra in the solid state, suggesting that the transitions are
allowed and, therefore, related to fluorescence processes for both complexes (Figure 9).
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Figure 9. Absorbance (black) and excitation (blue) spectra in the solid state for 3 (A) and 4 (B).
3
.7. Computational studies
DFT and TD-DFT computational calculations were carried out to elucidate the origin of
the luminescent properties displayed by 3 and 4. Tetranuclear model systems were constructed
based on the experimental X-ray diffraction data, keeping all the distances and the angles fixed
and representing all the bonds and interactions found in the coordination polymers (Figure 10).
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Figure 10. Theoretical model systems representing complex 3 (A) and 4 (B).
Single point DFT calculations permit the analysis of the electronic structure for these
complexes. Figures 11 and 12 display the most important frontier molecular orbitals (MOs) as
computed.
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Figure 11. Frontier MOs for model system 3
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