Silver(i)-organic frameworks assembled with flexible supramolecular synthons with a pendant ethynide arm attached to the heteroaryl skeleton

Article abstract of DOI:10.1039/c3ce41752b

The reactions of flexible supramolecular synthons with a pendant ethynide arm attached to a heteroaryl skeleton and different silver(i) salts under solvent evaporation conditions yielded four silver-organic frameworks. In 1-4, the Ag₇, Ag₈ and Ag₉ aggregates are fused together through trifluoroacetate groups and/or Ag-N coordination bonds to generate a 2D layer, and finally linked into 3D supramolecular networks by argentophilic interactions or hydrogen bonding. The diversities of the present structures also indicate that both solvent and the anionic component play vital roles in the assembly of silver(i)-ethynide complexes. In addition, their luminescence behaviors have been studied in the solid state.

Full text of DOI:10.1039/c3ce41752b

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Silver(I)–organic frameworks assembled with
flexible supramolecular synthons with a pendant
ethynide arm attached to the heteroaryl skeleton†
Cite this: CrystEngComm, 2014, 16,
23
7
ab
a
a
a
Bo Li, Ren-Wu Huang, Hong-Chang Yao, Shuang-Quan Zang*
ac
and Thomas C. W. Mak*
The reactions of flexible supramolecular synthons with a pendant ethynide arm attached to a heteroaryl
skeleton and different silver(I) salts under solvent evaporation conditions yielded four silver–organic
frameworks. In 1–4, the Ag , Ag and Ag9 aggregates are fused together through trifluoroacetate groups
Received 31st August 2013,
Accepted 21st October 2013
7
8
and/or Ag–N coordination bonds to generate a 2D layer, and finally linked into 3D supramolecular
networks by argentophilic interactions or hydrogen bonding. The diversities of the present structures
also indicate that both solvent and the anionic component play vital roles in the assembly of silver(I)–
ethynide complexes. In addition, their luminescence behaviors have been studied in the solid state.
DOI: 10.1039/c3ce41752b
www.rsc.org/crystengcomm
3
,11–13
(
σ, π and mixed σ, π) interactions have been obtained.
Introduction
Other groups have recently explored pyridyldiethynides or
pyrimidinylethynides, in which the relative positions and bond-
ing preference between the ethynide group and ring nitrogen
atom act as controlling factors to produce various structural
building units for the formation of multidimensional coordina-
The design, assembly and study of silver(I)–ethynide
complexes have attracted much interest owing to their struc-
1
–3
tural diversity
and promising application as luminescence
4
5
materials, and rigid-rod molecular wires. To the best of our
knowledge, the most intriguing features in these complexes
are the diverse coordination modes of the alkynyl moiety and
the tendency to form argentophilic interactions. Among
3g,i,j,14
tion networks.
Because the nitrogen or sulfur atom have
a strong ability to coordinate to the silver ion, we wonder if the
adjacent flexible silver ethynide unit and nitrogen or sulfur
atom can be associated together through such an interaction
to construct new coordination networks. Following this idea
and continuing our research program, we have designed two
new conformational flexible heteroaryl ligands; 1-(prop-2-
ynyloxy)-1H-benzo[d][1,2,3]triazole (HL1) and 2-(2-(prop-2-
ynyloxy)phenyl)benzo[d]thiazole (HL2) with one substituent
bearing a terminal ethynyl group on the triazole and phenyl
ring, respectively (Scheme 1). The reaction of the crude starting
1
0
10
them, the argentophilic interaction, namely the d –d
closed-shell attractive interaction that promotes the aggrega-
tion of Ag centers, has been used to construct intriguing
2
–9
silver–organic architectures.
As is known, besides the
silver–ethynide and argentophilic interaction, hydrogen
bonding can also dominate in molecular association, and
packing, thus playing an increasingly important role as a
persistent structural motif in the construction of solid-state
1
0
frameworks. Over the last dozen years, our group has been
engaged in the design and construction of coordination
networks based on new silver–ethynide supramolecular
synthons. By utilizing them, a series of silver(I)–organic
networks stabilized by argentophilic and silver–ethynide
material [AgL]
and silver trifluoroacetate–tetrafluoroborate generated four
new silver–organic networks, namely, [(AgL1)·(AgCF CO (1),
n
with water, water–acetonitrile, water–DMSO,
3
2 4 n
) ]
a
College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou 450001, People's Republic of China. E-mail: zangsqzg@zzu.edu.cn
b
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal
University, Nanyang 473061, PR China
c
Department of Chemistry and Center of Novel Functional Molecules, The Chinese
University of Hong Kong, Shatin, New Territories, Hong Kong SAR,
People's Republic of China
†
Electronic supplementary information (ESI) available: Tables S1–S3. CCDC
13997–914000 for compounds 1–4. For ESI and crystallographic data in CIF or
9
Scheme 1 Structural formulas of the ligands used in forming new
silver(I)–ethynide complexes.
other electronic format see DOI: 10.1039/c3ce41752b
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[
(AgL1)·(AgCF CO ) ·(H O)] (2), [(AgL2) ·(AgCF CO ) ·(H O)
]
[(AgL2) ·(AgCF CO ) ·(H O) ] (3)
2 3 2 5 2 1.5 n
3
2 4
2
n
2
3
2 5
2
1.5 n
(
3), and [(AgL2) ·(AgNO ) ·(DMSO) ] (4).
4 3 5 3 n
The procedure is similar to the synthesis of 2 except that
AgL2]n (0.020 g, 0.05 mmol) was used instead of [AgL1]n.
After several days, colorless block crystals of 3 were deposited
in about a 50% yield. Anal. calcd for C83
C, 26.66; H, 1.24; N, 1.50. Found: C, 26.62; H, 1.30; N, 1.52.
[
Experimental section
Materials and physical measurements
H
30 4 27 4
46Ag14F N O S :
−
1
Commercially available 1-hydroxybenzotriazole, 2-(2-hydroxyphenyl)
benzothiazole, propargyl bromide (80% in toluene), and K CO
IR spectrum: 2122 cm (w, νCC).
2
3
were used without further purification. All synthetic reactions
yielding organic ligands and polymeric starting materials were
carried out under a nitrogen atmosphere. Elemental analysis
for C, H, and N was performed on a Perkin-Elmer 240 elemen-
tal analyzer. The FT-IR spectra were recorded from KBr pellets
in the range from 4000 to 400 cm on a Bruker VECTOR22
spectrometer. Luminescence spectra for the solid samples were
recorded on a FluoroMax-4 fluorescence spectrophotometer.
Caution! Silver ethynide complexes are highly potentially
explosive in the dry state when subjected to heating or mechani-
cal shock, and should be handled in small amounts with
extreme care.
[
(AgL2)
4 3 5 3 n
·(AgNO ) ·(DMSO) ] (4)
AgNO (0.34 g, 2 mmol) was dissolved in 1 mL DMSO. [AgL2]n
(
for about half an hour, the solution was filtered and
transferred to a test tube and then, water was layered over
the solution. After several days, colorless block crystals of 4
were obtained in about a 45% yield. Anal. calcd for
3
0.025 g, 0.07 mmol) was added to the solution. After stirring
−1
70 9 9 22 7
C H58Ag N O S : C, 32.68; H, 2.27; N, 4.90. Found: C, 32.62;
H, 2.33; N, 4.96. IR spectrum: 2110 cm (w, νCC).
−
1
Results and discussion
Syntheses
The neutral ligands HL1 and HL2 were synthesized according to
the literature method. The reaction of 1-hydroxybenzotriazole
and 2-(2-hydroxyphenyl)benzothiazole, respectively, with
propargyl bromide in acetone in the presence of K CO
2 3
afforded 1-(prop-2-ynyloxy)-1H-benzo[d][1,2,3]triazole (HL1)
and 2-(2-(prop-2-ynyloxy)phenyl)benzo[d]thiazole (HL2). The
X-ray crystallographic analysis
17
Selected crystals were used for data collection on an OXFORD
Diffraction Gemini Single Crystal diffractometer. An empirical
absorption correction was applied using the SADABS
1
5
program. The structures were solved by direct methods and
2
refined by full-matrix least-squares on F using the SHELXTL
polymeric starting material [AgL]
to the literature method.
n
was prepared according
While sufficiently crystalline
materials of 1–3 were obtained by slowly evaporating the
crude polymeric starting material [AgL] in a concentrated
aqueous, water–acetonitrile or AgBF /AgCF CO solution,
1
6
−
program package. Most of the CF moieties of the CF CO
2
18
3
3
groups in these compounds were disordered, and the SADI
command was used to fix them in the refinements. In 2, the
silver atoms Ag4 and Ag5 are located in two disordered
positions with an occupancy ratio of 0.48 : 0.52 and 0.74 : 0.26,
respectively. The crystallographic data and selected bond
lengths and angles for 1–4 are listed in Tables S1 and S2.†
n
4
3
2
respectively, growing crystals of 4 in a size and quality
suitable for single-crystal X-ray diffraction required precipita-
tion under diffusion control. All of the complexes 1–4 are
stable at room temperature in the solid state.
[
(AgL1)·(AgCF CO ) ] (1)
3 2 4 n
Description of crystal structures
AgCF CO (0.44 g, 2 mmol) and AgBF (0.382 g, 2 mmol) were
3
2
4
dissolved in 1 mL of water. Then, the [AgL1]n (0.020 g,
.07 mmol) solid was added to the solution. After stirring for
[(AgL1)·(AgCF CO ) ] (1). In the crystal structure of
3 2 4 n
compound 1, there is one independent L1 anion and four
0
about 2 h, the solution was filtered and the filtrate allowed to
stand in the dark at room temperature. After several days,
colorless block crystals of 1 were deposited in about a 40%
yield. Anal. calcd for C H Ag F N O : C, 17.55; H, 0.52;
trifluoroacetate groups. The ethynide group composed of C1
and C2 is capped by a square-pyramidal Ag
basket in the
-η ,η ,η ,η ,η coordination mode, as shown in Fig. 1. The
peripheral Ag5 and Ag6 atoms are hitched to the Ag basket
by the trifluoroacetate group in the μ -O,O,O′,O′ modes
(O8–O9). With the inversion center located at the center of
baskets share an edge to
5
1
1
2
2
2
μ
5
1
7
6
5 12 3 9
5
N, 3.61. Found: C, 17.53; H, 0.59; N, 3.65. IR spectrum:
4
−
1
2
067 cm (w, νCC).
the Ag2⋯Ag2#1 bond, two Ag
5
engender a Ag aggregate, as shown in Fig. 2a. The distances
8
3 2 4 2 n
[(AgL1)·(AgCF CO ) ·(H O)] (2)
between the silver atoms range from 2.812(1) to 3.154(1) Å,
suggesting the presence of significant argentophilic interac-
The procedure is similar to the synthesis of 1 except that
acetonitrile (0.3 mL) was added. After several days, colorless
needle crystals of 2 were deposited in about a 45% yield.
1
9
tions. The adjacent Ag8 aggregates are fused together by
three pairs of trifluoroacetate groups (O2–O3, O4–O5, O6–O7,
Anal. calcd for C17
Found: C, 17.25; H, 0.75; N, 3.62. IR spectrum: 2074 cm
w, νCC).
H
8
Ag
5
F
12
N
3
O
10: C, 17.28; H, 0.68; N, 3.56.
3
O2#2–O3#2, O4#2–O5#2 and O6#2–O7#2) in the μ -O,O′,O′
mode to generate an infinite silver column (Fig. 2b). Such
silver columns are interconnected together by Ag–N interactions
−
1
(
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ethynide, we obtained complex 2 from the crystallization of
[
AgL1]n in a mixed water–acetonitrile solution of AgCF CO ,
3 2
3 2
instead of an aqueous solution of AgCF CO as in complex 1.
The asymmetric unit of 2 contains five crystallographically
independent Ag(I) ions, four trifluoroacetate ions and
one coordinated water molecule. In the crystal structure of 2,
the anionic ligand L1 adopts a non-planar conformation,
in which the torsion angle C2–C3–O1–N1 is −88.08(2)°.
Similar to complex 1, the ethynide moiety C1C2 in 2 is also
encapsulated in a square-pyramidal Ag5 basket in the
1
1
2
2
2
μ -η ,η ,η ,η ,η mode (Fig. 3). With the inversion center
5
Fig. 1 Atom labeling and coordination mode of L1 in 1 (50% thermal
located at the center of the Ag1⋯Ag1#1 bond, two Ag
5
ellipsoids are drawn for silver atoms). All hydrogen atoms, and CF
3
−
moieties of CF
3
CO
2
are omitted for clarity. Atom color codes: Ag
baskets share an edge to engender a Ag aggregate, as shown
8
purple, C gray, N blue, O red. Symmetry code: #1 1 − x, 1 − y, −z.
in Fig. 4a. The distances between the silver atoms range
from 2.904(3) to 3.176(2) Å, implying the presence of signifi-
cant argentophilic interactions. Such Ag aggregates are asso-
8
ciated together by three pairs of trifluoroacetate groups
(
O2#1–O3#1, O6–O7, O8–O9, O2#4–O3#4, O6#3–O7#3 and
O8#3–O9#3) via μ -O,O′,O′ and μ -O,O′,O′,O′ coordination
3
4
modes, respectively, leading to an infinite silver chain
along the b axis. Adjacent silver chains are linked by the
Ag–N (Ag3–N3#5 2.176(2) Å) interaction and bridging
trifluoroacetate ligand (O4#6–O5#6) into a two-dimensional
coordination network, as shown in Fig. 4c. Linkage of these
2
D coordination networks through C3–H3A⋯F2 hydrogen
bonding interactions (H3A⋯F2 2.569(4) Å) constructs a 3D
supramolecular structure (Fig. 4d).
[
(AgL2) ·(AgCF CO ) ·(H O) ] (3). In the crystal structure
2 3 2 5 2 1.5 n
of 3, there are two independent L2 anions. As shown in
Fig. 5, the ethynide groups (C1C2 and C3C4) are
enveloped by
a
butterfly-shaped Ag4 basket in the
1
1
2
2
1
1
1
2
μ
4
-η ,η ,η ,η and μ
4
-η ,η ,η ,η coordination modes, respec-
tively. Adjacent Ag
4
baskets coalesce by sharing one vertex
(
Ag4) to yield a Ag7 aggregate. As illustrated in Fig. 6a, the
Ag aggregates are further connected by trifluoroacetate
groups (O3#1–O4#1, O9–O10 and O11–O12) via μ -O,O′,O′
7
3
and μ -O,O,O′,O′ coordination modes, respectively, to furnish
4
an infinite column along the a axis with the L2 ligands on
the two sides. Then, neighboring columns are associated by
Ag–N interactions (Ag1–N2#2 2.268(14) Å, Ag6–N1#3 2.257(13) Å),
resulting in a wave-like two-dimensional (2D) network
parallel to the ab plane. Finally, the association of layers
through relatively weak O1W–H1WB⋯F1 (H1WB–F1 2.486 (2) Å),
Fig. 2 (a) Centrosymmetric Ag
related L1 ligands sharing vertex silver atoms (Ag2 and Ag2#1) and
stabilized by argentophilic interactions (Ag2⋯Ag2#1, 2.813 Å). (b) Ag
aggregates are united together by three pairs of trifluoroacetate
8
aggregate in 1 built from inversion-
8
groups to give an infinite column. (c) 2D metal–organic network of 1.
(
d) 3D network of 1 linked by Ag6–Ag6#3 interactions. All hydrogen
−
atoms and CF
3
moieties of CF
3
CO
2
are omitted for clarity. Symmetry
codes: #1 1 − x, 1 − y, −z; #2 2 − x, 1 − y, −z; #3 2 − x, 2 − y, −z; #4 1 − x,
− y, 1 − z. Color codes: Ag purple, C gray, N blue, O red.
1
(Ag5–N1, Ag5–N1#4 2.133(8) Å), with the assistance of the
trifluoroacetate groups O8–O9, O8#4–O9#4 in the μ -O,O,O′,O′
4
mode to engender a two-dimensional network parallel to the bc
plane (Fig. 2c). Neighboring layers are associated together
through argentophilic interactions (Ag6⋯Ag6#3 3.038(3) Å) to
produce a 3D supramolecular network (Fig. 1d).
[
(AgL1)·(AgCF CO ) ·(H O)] (2). In order to investigate the
3 2 4 2 n
Fig. 3 Coordination mode of L1 in 2. Symmetry codes: #1 1 − x, −y,
2 − z; #2 x, −1 + y, z.
effect of solvent on the coordination environment of the
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Fig. 6 (a) In the crystal structure of 3, Ag
7
aggregates are united by
bridging trifluoroacetate groups to yield an infinite chain along the a
axis. (b) The silver chains are further interconnected through Ag–N
interactions to give a 2D coordination polymer parallel to the ab plane.
−
All hydrogen atoms and CF
clarity. (c) 3D network of
3
moieties of CF
3
3
CO
2
are omitted for
linked through hydrogen bonding
Fig. 4 (a) Ag
8
aggregates in 2. (b) One-dimensional chain structure. (c)
interactions. Symmetry codes: #1 x + 1, y, z; #2 −x, y − 1/2, −z + 1/2;
#3 −x, y + 1/2, −z + 1/2; #4 − x, −y + 1, −z. Color codes: Ag purple, C
gray, O red, N blue, S yellow.
Layer structure of 2 linked by Ag–N interactions and trifluoroacetate
groups. (d) The view of the three-dimensional supramolecular struc-
ture. Color scheme for atoms: Ag purple, C gray, O red, N blue, F
green. Symmetry codes: #1 1 − x, −y, 2 − z; #2 x, −1 + y, z; #3 1 − x, 1 −
y, 2 − z; #4 x, y + 1, z; #5 2 − x, y, 2.5 − z; #6 1 + x, −y, 0.5 + z; #7 1 −
x, y, 1.5 − z.
1
2
2
2
C7 and C8 by a butterfly-shaped Ag basket in a μ -η ,η ,η ,η
4
4
coordination mode, as shown in Fig. 7. The 5 independent
nitrate groups (N5 to N9) in this complex play diverse roles
in building up the crystal structure, ranging from being a free
anion (N7) to bridging ligand in the μ
modes. Adjacent Ag and Ag baskets coalesce by sharing
vertexes (Ag7 and Ag9) to yield a Ag aggregate, which is also
2
-O,O′ coordination
3
4
9
consolidated by the nitrate groups N8 and N9 in the μ
2
-O,O′
modes. Adjacent Ag aggregates are linked by Ag–N interac-
9
tions to give a 2D network parallel to the ab plane, and such
networks are further bridged by hydrogen bonding between
DMSO (C67 and C68) and the nitrate group N6 to produce a
3-D network (Fig. 8b).
Fig. 5 Atom labeling and coordination mode of L2 in 3 (50% thermal
ellipsoids are drawn for silver atoms). All hydrogen atoms and CF
3
−
moieties of CF
3
CO
2
are omitted for clarity. Atom color codes:
Photoluminescence properties. As reported by other
groups, the emission of silver(I)–ethynide complexes mainly
Ag purple, C gray, O red, N blue, S yellow.
O2W–H2WB⋯F11 (H2WB–F11 2.616(2) Å), O1W–H1WA⋯O2W
H1WA–O2W 2.087(3) Å), and O2W–H2WA⋯O1W (H2WA–O1W
.927(2) Å) hydrogen bonds leads to a 3D supramolecular
framework (Fig. 6c).
(AgL2) ·(AgNO ) ·(DMSO) ] (4). When DMSO was used in
(
1
[
4
3 5
3 n
the place of water, complex 4 was obtained. In the crystal
structure of 4, there are four independent L2 anions. The
triple bond lengths (C1C2, C4C5, and C10C11) are in
the range of 1.202(10)–1.212(10) Å, which is in good
agreement with that observed in other silver ethynide
3
Fig. 7 Atom labeling and coordination mode of L2 in 4 (50% thermal
ellipsoids are drawn for silver atoms). All hydrogen atoms are omitted
for clarity. Atom color codes: Ag purple, C gray, O red, N blue,
S yellow.
complexes. The ethynide groups (C1C2, C4C5, and
C10C11) are capped by a trigonal Ag basket in a
3
1
2
2
3
μ -η ,η ,η coordination mode, and the other one comprising
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2
0
originates from intraligand n → π* and π → π* transitions.
Therefore, in the present work, the luminescent properties of
the free ligands and complexes 1–4 were investigated in the
solid state at room temperature. Complexes 1 and 2 exhibited
very weak emissions. As shown in Fig. 9, complexes 3 and 4
in this work displayed weak luminescence in the solid state
at room temperature. For 3 and 4, the peaks of the emission
spectra are located around 412 nm, and which are
blue-shifted compared to the band position of 469 nm for
the free ligand HL2. The blue-shift of the emission maximum
between the complex and the ligand may originate from the
coordination of the ligand to the metal centers.
Influence of solvent and anionic component. Complexes
1
and 2 are obtained from crystallization in water and
water–CH CN, while the double salts 3 and 4 in water and
3
water–DMSO, respectively. In complex 1, the Ag8 aggregates
associated together to generate linear silver chains through
trifluoroacetate groups, which are further connected through
Ag–N coordination bonds and trifluoroacetate groups to
produce 2D grids, and finally linked into 3D supramolecular
networks by argentophilic interactions. Differently from 1,
Fig. 9 Solid-state excitation (dotted line) and emission (solid line)
spectra of HL2 and complexes 3 and 4 at room temperature.
and lead to the diversity of the final structures. In addition, the
trifluoroacetate and nitrate groups exhibited different bonding
modes, indicating that the anionic component is also an impor-
tant factor influencing the final supramolecular frameworks.
the similar two-dimensional network in complex
2 is
connected through hydrogen bonding to give rise to a
three-dimensional supramolecular framework affected by the
coordinated water molecules. In complex 4, we used DMSO
in place of water and acetonitrile. Notably, the solvent
affected the coordination ability of the anionic component,
Conclusions
In summary, the present study has established that ethynide
moieties of the flexible ligands L1 and L2 can adopt μ -, μ -
3
4
5
and μ - ligation modes upon bonding to silver(I) centers.
Structural determinations of these compounds have demon-
strated that Ag–N interactions play a vital role in the assembly
of coordination polymers with increasing dimensionality as
well as stability of the framework structures. The results also
showed that the silver ion is inclined to coordinate with the N
atom, indicating the stronger coordination ability of the N
atom than the S atom. In addition, the coexisting of
solvate also influences the supramolecular assembly. Weak
intermolecular C–H⋯F, O–H⋯F, C–H⋯O, and argentophilicity
interactions also make their appearance in these silver(I)
complexes. By weak intermolecular interactions, complexes 1–4
extend into two-dimensional or three-dimensional networks.
The diversities of the present structures also indicate that
controlling the synthesis by adjusting the silver–ethynide
supramolecular synthons, silver salt or synthetic method is a
facile and effective approach to the design and construction
of novel supramolecular assemblies with distinct structural
features. In the solid state, complexes 3 and 4 synthesized in this
work are emissive at room temperature, which mainly originates
from the coordination of the ligand to the metal centers.
Fig.
8
(a) In the crystal structure of 4, Ag
9
aggregates are
2D network
interconnected through Ag–N interactions to give
a
Acknowledgements
parallel to the ab plane. (b) 3D network of 4 linked by hydrogen
bonding interactions. All irrelevant atoms are omitted for clarity.
Symmetry codes: #1 x + 1, y, z; #2 x + 1/2, y − 1/2, z; #3 x − 1, y, z;
We gratefully acknowledge financial support from the
National Natural Science Foundation of China (no. 20901070,
21371153), Program for Science & Technology Innovation
#
4 x − 1/2, y + 1/2, z. Color codes: Ag purple, C gray, O red, N blue,
S yellow.
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Talents in Universities of Henan Province (13HASTIT008),
Key Scientific and Technological Project of Henan Province
R.-B. Huang and L.-S. Zheng, Chem. Commun., 2010, 46,
8168; (i) D. Sun, Z.-H. Wei, D.-F. Wang, N. Zhang,
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S.-Y. Feng, Z.-W. Zhang, G.-X. Sun and D.-F. Sun,
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(132102210411), Zhengzhou University, and the Hong Kong
Research Grants Council (ref. no. CUHK 402408).
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