Silver(I)-organic networks assembled with propargyl-functionalized di- and trihydroxybenzenes

Article abstract of DOI:10.1021/om2000162

A series of four new ligands bearing terminal ethynide moieties attached via pendant arms to a benzene skeleton have been used in the syntheses of four silver(I) complexes: [(Ag₂L1)₂?(AgCF ₃CO₂)₁₀?(CH

Full text of DOI:10.1021/om2000162

ARTICLE
pubs.acs.org/Organometallics
Silver(I)-Organic Networks Assembled with
Propargyl-Functionalized Di- and Trihydroxybenzenes
Bo Li,a Shuang-Quan Zang,*,a Ran Liang,a Yang-Jie Wu,a and Thomas C. W. Mak*,a,b
aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China
bDepartment 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
S Supporting Information
b
ABSTRACT: A series of four new ligands bearing terminal
ethynide moieties attached via pendant arms to a benzene skeleton
have been used in the syntheses of four silver(I) complexes:
[(Ag2L1)2 (AgCF3CO2)10 (CH3CN)2 (H2O)4 (μ2-H2O)2]
3
3
3
3
3
(AgBF4) (1), [(Ag2L2) (AgCF3CO2)7 (CH3CN) (H2O)] (2),
3
3
3
{[(Ag2L3) (AgCF3CO2)10 (CH3CN)6 (H2O)2 (OH)2]
3
3
3
3
3
(H2O)} (3), and [(Ag3L4)2 (AgCF3CO2)13 (CH3CN)5
3
3
3
(H2O)] (4) (H2L1 = 1,2-bis(prop-2-ynyloxy)benzene, H2L2 =
1,3-bis(prop-2-ynyloxy)benzene, H2L3 = 1,4-bis(prop-2-ynyloxy)
benzene, H3L4 = 1,2,3-tris(prop-2-ynyloxy)benzene). In these
compounds, the invariable appearance of the μ4- and μ5-ligation
modes of the ethynide moiety affirms the general utility of the
silver-ethynide supramolecular synthon Agn⊂CtCCH2OC6H4OCH2CtC⊃Agn (n = 4, 5) in coordination network assembly.
Additionally, several conventional and unconventional silver-ethynyl, argentophilic, hydrogen-bonding, silver-aromatic, and π-π
interactions play an important role in stabilizing their framework structures. In 1, Ag15 aggregates are fused together by argentophilic
interaction to yield thick silver rods, which are further linked through interchain hydrogen bonds into a 2D network. In 2, butterfly-shaped
Ag4 baskets are fused into silver(I) columns, which are further associated by external Ag(CF3COO)2 units and argentophilic interactions to
give a metal-organic sheet; adjacent layers are then linked into a 3D metal-organic framework through face-to-face aromatic π-π
interactions. In 3, Ag6-phenyl ring-Ag6 structural units are interconnected by a pair of μ4-η2,η2 trifluoroacetate groups to yield silver
columns, which are further united by hydrogen bonds to give a 3D metal-organic network. Two kinds of silver rods in parallel orientation
are bridged by three μ3-η1,η2 and one μ4-η2,η2 trifluoroacetate groups to generate a two-dimensional metal-organic network of 4, in
which the trianion exhibits the unprecedented μ20-coordination mode.
’ INTRODUCTION
networks stabilized by argentophilic15 and silver-ethynide
(σ, π and mixed σ, π) interactions. Recently, we have explored the
employment of several ligands with an ethynide ethynyl group
attached to a phenyl, biphenyl, or naphthyl skeleton via a flexible -
CH2-O- link for the construction of MOFs consolidated by both
silver(I)-ethynide and silver(I)-aromatic interactions.16
In continuation of our research program, we have designed four
new conformational flexible ligands, 1,2-bis(prop-2-ynyloxy)-
benzene (H2L1), 1,3-bis(prop-2-ynyloxy)benzene (H2L2),
1,4-bis(prop-2-ynyloxy)benzene (H2L3), and 1,2,3-tris(prop-2-
ynyloxy)benzene (H3L4), with two or three flexible substituents
bearing terminal ethynyl groups at variable positions on the
aromatic ring (Scheme 1). The reaction of crude starting materi-
als [Ag2L1]n (5), [Ag2L2]n (6), [Ag2L3]n (7), and [Ag3L4]n (8)
with water-soluble silver trifluoroacetate/tetrafluoroborate gen-
Crystal engineering of metal-organic frameworks (MOFs) is a
current trend in view of the discovery of interesting topologies and
crystal-packing motifs, as well as their potential application as
functional materials.1-3 In contrast to the abundance of supramo-
lecular architectures constructed with silver(I)-ligand coordina-
tion bonds,4 the assembly of crystal-engineered organosilver(I)
networks is much less developed. Recently, metal-ethynide com-
plexes have attracted much interest owing to their structural
diversity5-7 and promising application as precursors of nonlinear
optical materials,8 luminescence materials,9 and rigid-rod molecular
wires.10
Following our investigation of the coordination chemistry of
silver ethynediide (Ag2C2),11 we have conducted systematic
studies on various complexes containing silver(I) 1,3-butadiyne-
diide (Ag2C4).12 Furthermore, utilizing new metal-ligand su-
pramolecular synthons of the type R-CtC⊃Agn (R = aryl or
alkyl; n = 4, 5)13 and Agn⊂CtC-R-CtC⊃Agn (R = o-, m-, p-
C6H4; n = 4, 5),14 we have obtained a series of metal-organic
erated four new metal-organic networks, namely, [(Ag2L1)2
3
Received: January 17, 2011
Published: March 03, 2011
r
2011 American Chemical Society
1710
dx.doi.org/10.1021/om2000162 Organometallics 2011, 30, 1710–1718
|

Organometallics
ARTICLE
Scheme 1. Structural Formulas of Propargyl-Funtionalized
Di- and Trihydroxybenzenes Used As Ligands in Forming
New Silver(I)-Ethynide Complexes
(w, νCtC). Anal. Calcd (%) for C12H10O2: C 77.33; H 5.41. Found:
C 77.30; H 5.47.
1,4-Bis(prop-2-ynyloxy)benzene (H2L3). H2L3 was obtained by the
same procedure using p-dihydroxybenzene. Yield: 1.65 g, 89%. H NMR
(300 MHz, CDCl3): δ 6.93 (4H, benzene); 4.65 (4H, OCH2); 2.52
(2H, CtCH). IR: ν 2051 cm-1 (w, νCtC). Anal. Calcd (%) for
C12H10O2: C 77.33; H 5.41. Found: C 77.40; H 5.39.
1,2,3-Tris(prop-2-ynyloxy)benzene (H3L4). Propargyl bromide
(4.2 mL, 37.5 mmol) and K2CO3 (5.18 g, 37.5 mmol) were added to
a solution of 1,2,3-benzenetriol (1.26 g, 10 mmol) in acetone (30 mL).
The solution was heated under reflux for 24 h under a nitrogen
atmosphere. The precipitate was filtered off, and the filtrate was
evaporated to dryness to yield the crude product as a yellow oil. It was
purified by chromatography on silica gel to afford a pale yellow oil. Yield:
1.9 g, 80%. H NMR (300 MHz, CDCl3): δ 6.54-6.92 (3H, benzene);
4.66-4.81 (6H, OCH2); 2.53 (3H, CtCH). IR: ν 2032 cm-1
(w, νCtC). Anal. Calcd (%) for C15H12O3: C 74.99; H 5.03. Found:
C 74.96; H 5.07.
[Ag2L1]n (5). Silver nitrate (0.91 g, 5.36 mmol) was dissolved in
acetonitrile (30 mL). Then H2L1 (0.6 g, 2.68 mmol) and triethylamine
(0.81 mL, 5.36 mmol) were added with vigorous stirring, and the
mixture was stirred overnight under a nitrogen atmosphere in the dark.
The white precipitate formed was collected by filtration, washed
thoroughly with acetonitrile (2 ꢀ 10 mL) and deionized water (3 ꢀ
10 mL), and then stored in wet form at -10 °C in a refrigerator. Yield:
1.03 g, 80%. IR: ν 2038 cm-1 (w, νCtC).
[Ag2L2]n (6) [Ag2L3]n (7), and [Ag3L4]n (8). These polymeric
materials were prepared by a similar synthetic procedure using H2L2,
H2L3, and H3L4, respectively. Yield: 83%. [Ag2L2]n (6) IR ν 2046 cm-1
(w, νCtC); [Ag2L3]n (7) IR ν 2042 cm-1 (w, νCtC); [Ag3L4]n (8) IR ν
2054 cm-1 (w, νCtC).
(AgCF3CO2)10 (CH3CN)2 (H2O)4 (μ2-H2O)2] (AgBF4) (1),
3
3
3
3
[(Ag2L2) (AgCF3CO2)7 (CH3CN) (H2O)] (2), {[(Ag2L3)
3
3
3
3
(AgCF3CO2)10 (CH3CN)6 (H2O)2 (OH)2] (H2O)} (3), and
3
3
3
3
[(Ag3L4)2 (AgCF3CO2)13 (CH3CN)5 (H2O)] (4), which are
[(Ag2L1)2 (AgCF3CO2)10 (CH3CN)2 (H2O)4 (μ2-H2O)2] (AgBF4)
3
3
3
3
3
3
3
3
expected to be stabilized by silver(I)-ethynide and argentophilic
interactions, and the phenyl ring is potentially capable of partak-
ing in π-π and silver-aromatic interactions.
(1). AgCF3CO2 (0.44 g, 2 mmol) and AgBF4 (0.382 g, 2 mmol) were
dissolved in 1 mL of water and acetonitrile (0.2 mL). Then, [Ag2L1]n
(∼20 mg) solid was added to the solution. After stirring for about 2 h,
the solution was filtered and the filtrate stored at -10 °C in a
refrigerator. After several days, colorless block crystals of 1 were
deposited in about 80% yield. Anal. Calcd (%) for C48H34Ag15BF34-
N2O30: C 16.99; H 1.01. Found: C 17.27; H 0.98. IR: ν 2086 cm-1
(w, νCtC).
’ EXPERIMENTAL SECTION
Reagents. Commercially available o-dihydroxybenzene, m-dihy-
droxybenzene, p-dihydroxybenzene, 1,2,3-benzenetriol, propargyl bro-
mide (80% in toluene), and K2CO3 were used without further
purification. Acetone, dichloromethane, ethyl acetate, n-hexane, acet-
onitrile, and triethylamine were purified according to standard proce-
dures. All synthetic reactions yielding organic ligands and polymeric
starting materials were carried out under a nitrogen atmosphere.
Caution! Silver ethynide complexes are highly potentially explosive in the
dry state when subjected to heating or mechanical shock and should be
handled in small amounts with extreme care.
[(Ag2L2) (AgCF3CO2)7 (CH3CN) (H2O)] (2). AgCF3CO2 (0.44 g,
3
3
3
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL of water
and acetonitrile (0.2 mL). Then, [Ag2L2]n (∼20 mg) solid was added to
the solution. After stirring for about half an hour, the solution was
filtered and left to stand in the dark at room temperature. After several
days, colorless needle crystals of 2 were deposited in about 90% yield.
Anal. Calcd (%) for C28H13Ag9F21NO17: C 16.77; H 0.65. Found:
C 16.73; H 0.69. IR: ν 2075 cm-1 (w, νCtC).
{[(Ag2L3) (AgCF3CO2)10 (CH3CN)6 (H2O)2 (OH)2] (H2O)} (3).
3
3
3
3
3
AgCF3CO2 (0.44 g, 2 mmol) and AgBF4 (0.382 g, 2 mmol) were
dissolved in 1 mL of deionized water and acetonitrile (0.2 mL). Then,
[Ag2L3]n (∼25 mg) solid was added to the solution. After stirring for
about half an hour, the solution was filtered and left to stand in the dark at
room temperature. After several days, colorless block crystals of 3 were
deposited in about 86% yield. Anal. Calcd (%) for C44H34Ag12F30N6O27:
C17.96; H 1.16. Found: C 17.91; H 1.11. IR: ν 2064 cm-1 (w, νCtC).
[(Ag3L4)2 (AgCF3CO2)13 (CH3CN)5 (H2O)] (4). AgCF3CO2 (0.44 g,
2 mmol) and AgBF4 (0.382 g, 2 mmol) were dissolved in 1 mL of
deionized water and acetonitrile (0.2 mL). Then, [Ag3L4]n (∼15 mg)
solid was added to the solution. After stirring for about half an hour, the
solution was filtered and left to stand in the dark at room temperature.
After several days, colorless block crystals of 4 were deposited in about
81% yield. Anal. Calcd (%) for C66H35Ag19F39N5O33: C 18.80; H 0.84.
Found: C 18.77; H 0.86. IR: ν 2047 cm-1 (w, νCtC).
1,2-Bis(prop-2-ynyloxy)benzene (H2L1). H2L1 was synthesized ac-
cording to the literature method.17 Propargyl bromide (2.8 mL, 25 mmol)
and K2CO3 (3.46 g, 25 mmol) were added to a solution of o-dihydrox-
ybenzene (1.10 g, 10 mmol) in acetone (30 mL). The solution was heated
under reflux for 24 h under a nitrogen atmosphere. The precipitate was
filtered off, and the filtrate was evaporated to dryness to yield the crude
product as a yellow oil. It was purified by chromatography on silica gel to
afford a pale yellow oil. Yield: 1.58 g, 85%. H NMR (300 MHz, CDCl3):
δ 6.61-6.79 (4H, benzene); 4.68 (4H, OCH2); 2.52 (2H, CtCH). IR: ν
2055 cm-1 (w, νCtC). Anal. Calcd (%) for C12H10O2: C 77.33; H 5.41.
Found: C 77.38; H 5.45.
3
3
3
1,3-Bis(prop-2-ynyloxy)benzene (H2L2). H2L2 was obtained by the
above procedure except that m-dihydroxybenzene replaced o-dihydrox-
ybenzene. Yield: 1.61 g, 87%. H NMR (300 MHz, CDCl3): δ 6.61-7.26
(4H, benzene); 4.68 (4H, OCH2); 2.53 (2H, CtCH). IR: ν 2053 cm-1
1711
dx.doi.org/10.1021/om2000162 |Organometallics 2011, 30, 1710–1718

Organometallics
ARTICLE
X-ray Crystallographic Analysis. Selected crystals were used for
data collection on a Bruker SMART 1000 CCD diffractometer (1-4) at
293Kusingframesofoscillationrange0.3°, with2° <θ<28°. An empirical
absorption correction was applied using the SADABS program.18 The
structures were solved by the direct methods and refined by full-matrix
least-squares on F2 using the SHELXTL program package.19 Most of the
CF3 moieties of CF3CO2- groups in compounds 1-4 were disordered,
and the SADIcommandwasused tofix themin the refinements. In1, silver
atoms Ag1, Ag2, Ag4, Ag7, and Ag8 are located in two disordered positions
with an occupancy ratio of 0.47:0.53. In 4, silver atoms Ag6 and Ag9 are
located in two disordered positions with occupancy ratios of 0.50:0.50 and
0.90:0.10, respectively. The crystallographic data and selectedbond lengths
and angles for 1-4 are listed in Tables 1 and 2. Crystallographic data have
been deposited with the Cambridge Crystallographic Data Center. CCDC
reference numbers: 804457-804460.
are -171.78° and 173.69°, respectively. The ethynide group com-
posed of C1 and C2 is capped by a butterfly-shaped Ag4 basket in
the μ4-η1,η2,η2,η2 coordination mode, and the other one com-
prising C11 and C12 by a different butterfly-shaped Ag4 basket in
the μ4-η1,η1,η2,η2 coordination mode, as shown in Figure 1.
Moreover, the external silver atom Ag8 is attached to the Ag8 unit
by three trifluoroacetate groups (O3-O4, O9-O10, and
O11-O12) via μ3-η1,η2 coordination modes to form a Ag9
aggregate, in which the Ag-Ag distances vary from 2.782 to
3.174 Å, being shorter than twice the van der Waals radius of
silver ions (3.44 Å)20 and suggesting the presence of significant
argentophilic interactions. Such symmetry-related aggregates are
fused by vertex-sharing (Ag4, Ag5, and Ag4#2) to form a Ag15
aggregate (Figure 1 and Figure S1). Additionally, the edge-to-
centroid distance between two proximal phenyl rings in the
aggregate unit is 3.836 Å, indicating the existence of a significant
edge-to-face π-π stacking interaction.21
’ RESULTS AND DISCUSSION
Adjacent Ag15 aggregates are fused by argentophilic interac-
tion Ag1 Ag2#1, Ag2 Ag1#1 (3.174 Å) to yield a thick
Syntheses. The neutral ligands H2L1, H2L2, H2L3, and H3L4
were synthesized from the reaction of o-dihydroxybenzene,
m-dihydroxybenzene, p-dihydroxybenzene, and 1,2,3-benzene-
triol, respectively, with propargyl bromide in acetone in the
presence of K2CO3. Silver(I) double/triple salts 1-4 were
obtained from crystallizationof the correspondingpolymeric crude
compounds [AgL]n (5-8) in a concentrated aqueous or water/
acetonitrile solution of silver(I) trifluorocarboxylate/tetrafluoro-
borate. The tetrafluoroborate ion was employed to provide a high
concentration of silver ions, which enhanced aggregation through
argentophilicity such that the ethynide moiety is embraced within a
butterfly-shaped Ag4 or square-pyramidal Ag5 basket.
3 3 3
3 3 3
silver rod, additional consolidation being provided by a pair of
trifluoroacetate groups (O7-O8 and O7#1-O8#1) through the
μ3-O,O0,O0 mode (Figure 2a and Figure S2). The infinite silver
rods are interconnected by hydrogen bonds (O3W#4 O8
3 3 3
2.780 Å, O1W O11#4 2.810 Å, O1W O10 2.786 Å) to
3 3 3
3 3 3
engender a two-dimensional network parallel to the ac plane
(Figure 2b). There is no obvious intermolecular interaction
between layers.
[(Ag2L2) (AgCF3CO2)7 (CH3CN) (H2O)] (2). The asym-
3
3
3
metric unit of 2 contains nine crystallographically independent
Ag(I) ions, seven trifluoroacetate ions, one coordinated acetoni-
trile molecule, and one coordinated water molecule. In the crystal
structure of 2, the dianionic ligand L2 adopts a nonplanar
conformation, in which the torsion angles C2-C3-O1-C4
and C11-C10-O2-C8 are -69.67° and -68.54°, respec-
tively. As shown in Figure 3, the ethynide groups (C1tC2 and
Description of Crystal Structures. [(Ag2L1)2 (AgCF3CO2)10
(CH3CN)2 (H2O)4 (μ2-H2O)2] (AgBF4) (1). In the crystal structure
3
3
3
3
3
of compound 1, there are two independent phenylethynide (L1)
anions, each adopting a nearly planar conformation, in which
the torsion angles C2-C3-O1-C4 and C11-C10-O2-C9
Table 1. X-ray Crystal Data and Structure Refinement for Compounds 1-4
1
2
3
4
formula
fw
C
48H34Ag15BF34N2O30
C28H13Ag9F21NO17
2005.22
triclinic
C44H34Ag12F30N6O27
2943.21
triclinic
C66H35Ag19F39N5O33
4216.52
triclinic
3393.63
monoclinic
C2/c
cryst syst
space group
a (Å)
P1
P1
P1
12.0752(13)
30.335(3)
24.098(3)
90
11.892(2)
14.616(3)
14.813(3)
107.88(3)
109.19(3)
95.85(3)
2254.5(11)
2
11.504(7)
14.494(8)
15.198(9)
62.249(11)
69.626(11)
73.765(12)
2081(2)
1
17.0118(16)
17.1524(17)
17.9913(16)
89.850(2)
79.799(2)
88.085(2)
5163.8(8)
2
b (Å)
c (Å)
R (deg)
β (deg)
γ (deg)
volume (Å3)
Z
98.459(2)
90
8731.3(16)
4
Dcalc (g cm-3
)
2.582
2.954
2.348
2.712
3
F(000)
R(int)
GOF
6368
1872
1390
3948
0.0635
0.0635
0.0338
0.0431
1.008
1. 021
0.983
1.055
R1[(I > 2σ(I)]
wR2[(I > 2σ(I)]
R1 (all data)
0.0738
0.0661
0.0656
0.0804
0.2130
0.2038
0.1755
0.1720
0.1235
0.0728
0.1106
0.1258
wR2 (all data)
0.2436
0.2112
0.1987
0.1931
residuals (e Å-3
)
1.648, -2.216
1.698,-1.076
1.203, -0.885
1.610, -0.937
1712
dx.doi.org/10.1021/om2000162 |Organometallics 2011, 30, 1710–1718

Organometallics
ARTICLE
Table 2. Selected Bond Lengths (Å) for Complexes 1-4a
1
C1tC2
1.200(2)
C11tC12
Ag3-C1
1.231(17)
2.355(13)
2.487(13)
2.438(11)
2.782(6)
2.928(18)
2.967(4)
3.023(5)
Ag1-C1
2.104(12)
2.500(13)
2.133(13)
3.118(8)
3.180(16)
2.981(8)
2.848(5)
Ag2-C1#1
Ag5-C12
Ag7-C12#2
2.553(14)
2.487(13)
2.347(11)
3.174(9)
Ag4-C1
Ag5-C12#2
Ag7-C11#2
Ag6-C12#2
Ag1 Ag2
3 3 3
Ag1 Ag2#1
Ag1 Ag3
Ag1 Ag4
3 3 3
3 3 3
3 3 3
Ag1 Ag6
3.191(14)
2.958(10)
2.958(10)
Ag2 Ag1#1
Ag2 Ag3
3 3 3
3 3 3
3 3 3
Ag5 Ag6#2
Ag4 Ag5
Ag4 Ag6
3 3 3
3 3 3
3 3 3
Ag5 Ag6
Ag6 Ag7
3 3 3
3 3 3
2
C1tC2
1.216(15)
2.451(10)
2.427(10)
2.345(10)
2.374(10)
2.988(14)
2.925(15)
2.895(16)
3.239(2)
C11tC12
Ag2-C2
1.228(15)
2.536(10)
2.585(10)
2.412(10)
2.297(10)
2.751(13)
3.315(17)
2.734(14)
3.128(2)
Ag1-C12
Ag2-C12
Ag4-C1
Ag7-C11
Ag8-C2
2.080 (11)
2.498 (10)
2.095(11)
2.959(12)
3.090(10)
2.919(16)
3.247(2)
Ag2-C1
Ag3-C1
Ag6#1-C11
Ag7-C12
Ag9-C11
Ag3-C2
Ag6#1-C12
Ag8-C1
Ag9-C12
Ag1 Ag2
3 3 3
Ag1 Ag7
Ag1 Ag9
Ag2 Ag3
3 3 3
3 3 3
3 3 3
Ag3 Ag4
Ag4 Ag8
Ag6#1 Ag1
3.342(19)
3 3 3
3 3 3
3 3 3
Ag6#1 Ag6
Ag7 Ag8
3 3 3
3 3 3
3
C1tC2
Ag2-C1
Ag3-C2
1.201(14)
2.511(10)
3.028(1)
Ag1-C1
Ag2-C2
Ag4-C1
2.401(11)
2.526(11)
2.150(10)
3.036(18)
2.860(19)
Ag1-C2
Ag3-C1
Ag5-C1
2.747(16)
2.315(11)
2.312(10)
2.985(19)
2.918(2)
Ag1 Ag4
2.947(18)
3.059(19)
Ag1 Ag5
Ag2 Ag3
3 3 3
3 3 3
3 3 3
Ag2 Ag4
Ag3 Ag5
Ag4 Ag5
3 3 3
3 3 3
3 3 3
4
C8tC9
1.223(17)
1.198 (9)
2.733(14)
2.168(17)
2.097(12)
2.270(13)
2.467(13)
2.227(13)
2.288(13)
2.923(12)
2.258(12)
2.299(12)
3.081(12)
2.783(11)
3.193(17)
2.862(18)
3.377(4)
C14tC15
Ag1-C9
1.198(17)
2.207(14)
2.217(12)
2.346(13)
2.359(13)
2.19 (2)
C23tC24
Ag2-C9
1.219(17)
2.272(13)
2.537(13)
2.089(12)
2.139(13)
2.633(13)
2.15(2)
C29tC30
Ag2-C8
Ag3-C9
Ag4-C8
Ag4-N1
Ag4-C9
Ag5-C12
Ag7-C15
Ag9-C14#2
Ag10-N4
Ag12-C24
Ag14-C24
Ag11#3-C27
Ag16-C26
Ag16-C30
Ag18-C30
Ag19#4-C30
Ag5-N2
Ag6-C15
Ag8-N5
Ag8-C15
Ag9-C15#2
Ag11-C24
Ag13-C24
Ag15-C24
Ag12-C27
Ag16-C27
Ag17-C29
Ag19-C29
Ag10-N3
Ag12-C23
Ag14-C23
Ag11#3-C26
Ag15#3-C27
Ag16-C29
Ag17-C30
Ag19-C30
2.19(2)
2.725(14)
2.711(14)
2.594(12)
2.175(12)
2.886(13)
2.260(12)
2.625(12)
2.835(15)
3.270(17)
3.073(4)
2.375(13)
2.308(12)
2.501(12)
2.794(1)
2.428(11)
2.184(10)
2.495(12)
2.987(16)
3.028(16)
3.249(18)
2.896(3)
Ag1 Ag4
Ag1 Ag3
Ag1 Ag5#1
3 3 3
3 3 3
3 3 3
Ag2 Ag5
Ag2 Ag3
Ag1 Ag2
3 3 3
3 3 3
3 3 3
Ag6 Ag8
Ag5 Ag6
Ag3 Ag4
3 3 3
3 3 3
3 3 3
Ag7 Ag9#2
3.090(18)
3.094(3)
Ag7 Ag9
2.999(2)
Ag6 Ag7
3 3 3
3 3 3
3 3 3
Ag9 Ag9#2
Ag9 Ag7#2
3.090(18)
2.820(15)
2.786(17)
3.067(2)
Ag7 Ag8
2.997(2)
3 3 3
3 3 3
3 3 3
Ag11 Ag12
3.053(15)
2.848(15)
3.344(16)
3.121(18)
3.122(17)
3.035(2)
Ag11 Ag13
Ag11 Ag14
2.978(15)
3.056(16)
2.848(15)
2.823(15)
2.959(15)
3 3 3
3 3 3
3 3 3
Ag11 Ag15
Ag12 Ag15#3
Ag12 Ag16
3 3 3
3 3 3
3 3 3
Ag13 Ag14
Ag15#3 Ag16
Ag15#3 Ag11#3
3 3 3
3 3 3
3 3 3
Ag16 Ag17
Ag16 Ag18
3.015(16)
3.213(16)
Ag17 Ag18
3 3 3
3 3 3
3 3 3
Ag17 Ag19#4
Ag18 Ag19#4
Ag18 Ag19
3 3 3
3 3 3
3 3 3
Ag19 Ag19#4
3 3 3
a Symmetry transformations used to generate equivalent atoms: #1 -x þ 1/2, -y þ 1/2, -z þ 1; #2 -x, y, -z þ 1/2 for 1; #1 -x, -y, -z for 2; #1 -x,
1 - y, 1 - z; #2 1 - x, 1 - y, 1 - z; #3 -x, 2 - y, 2 - z; #4 1 - x, 2 - y, 2 - z for 4.
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Figure 1. Atom labeling and coordination mode of L1 in 1 (50% thermal
ellipsoids are drawn for silver atoms). All hydrogen atoms, acetonitrile
molecules, BF4- anions, and CF3 moieties of CF3CO2- are omitted for
clarity. Symmetry code: #1 -x þ 1/2, -y þ 1/2, -z þ 1; #2 -x, y, -zþ
1/2; #3 x - 1/2, -y þ 1/2, z - 1/2. Atom color codes: Ag purple,
C gray, O orange.
Figure 3. Atom labeling and coordination mode of L2 in 2 (50% thermal
ellipsoids are drawn for silver atoms). All hydrogen atoms and
-
CF3 moieties of CF3CO2 are omitted for clarity. Symmetry codes:
#1 - x, -y, -z; #2 -x þ 1, -y þ 1, -z þ 1. Atom color codes:
Ag purple, C gray, N blue, O orange.
trifluoroacetate groups (O15-O16 and O15#2-O16#2) with
the assistance of argentophilic interactions Ag3 Ag4#2, Ag4
3 3 3
3
Ag3#2 (3.226 Å) to produce a Ag8-(μ3-η1,η2-CF3CO2)2-
3 3
Ag8 building unit. Such units are connected by a pair of inversion-
related trifluoroacetate groups (O9-O10 and O9#1-O10#1)
acting in the μ4-η2,η2 mode, which together with argentophilic
interactions (Ag1 Ag6#1 3.342 Å, Ag6 Ag1#1 3.342 Å,
3 3 3
3 3 3
Ag6 Ag6#1 3.239 Å) generate a silver column (Figure 4 and
3 3 3
Figure S3). As shown in Figure 5a, adjacent silver columns are
associated by the external Ag5 atom, a pair of trifluoroacetate
groups (O11#1-O12#1 and O11#3-O12#3), and argentophi-
lic interaction Ag9#1 Ag9#3 (3.092 Å), resulting in a two-
3 3 3
dimensional (2D) network, and further consolidation is provided
by hydrogen bonding (O1W#2 O4#3 2.800 Å, O1W#2
3 3 3
3 3 3
O7 2.932 Å, and O1W#2 F7#3 2.968 Å).22 Finally, associa-
3 3 3
tion of layers through face-to-face π-π stacking interactions
between adjacent phenyl rings (centroid-centroid distance
3.638 Å) leads to a 3D supramolecular framework (Figure 5b).
Moreover, two phenyl carbon atoms (C4 and C9) coordinate to
the silver atom Ag2 by the μ-η2 mode with bond lengths of 3.054
and 2.668 Å, respectively, implying the presence of significant
Ag(I)-π interaction.23
Figure 2. (a) In the crystal structure of 1, Ag15 aggregates are fused by
argentophilic interaction Ag1 Ag2#1, Ag2 Ag1#1 (2.928 Å) and
3 3 3
3 3 3
{[(Ag2L3) (AgCF3CO2)10 (CH3CN)6 (H2O)2 (OH)2] (H2O)}
3
3
3
3
3
bridging trifluoroacetate groups to yield a thick silver rod. (b) The silver
(3). In the crystal structure of 3, dianionic ligand L3 located at a
center of symmetry takes an anti conformation with a C2-C3-
O1-C4 torsion angle of 55.19°. As shown in Figure 6, the
ethynide group (C1tC2) is bound to the square-pyramidal Ag5
basket inthe μ5-η1,η1,η2,η2,η2 coordinationmode. TheAg6 atom
is hitched to the Ag5 basket through two trifluoroacetate groups
(O2-O3 and O4-O5) in the μ3-η1,η2 mode to give an Ag6
cluster, within which the argentophilic Ag-Ag distances vary
from 2.860 to 3.059 Å. As shown in Figure 7a, a novel Ag6-
phenyl ring-Ag6 structural unit is formed. Such units are con-
nected by a pair of μ4-η2,η2 trifluoroacetate groups (O2-O3 and
O2#2-O3#2) to yield an infinite column along the a axis, and
such columns are further united through hydrogen bonds
rods are further interconnected through interchain hydrogen bonds to
give a 2D network. All hydrogen atoms and CF3 moieties of CF3CO2
are omitted for clarity. Symmetry code: #1 -x þ 1/2, -y þ 1/2, -z þ 1;
#2 -x, y, -z þ 1/2; #3 x - 1/2, -y þ 1/2, z - 1/2; #4 x þ 1, y, z.
Color codes: Ag purple, C gray, O orange.
-
C11tC12) are enveloped by a butterfly-shaped Ag4 basket in
the μ4-η1,η2,η2,η2 coordination mode and a square-pyramidal
Ag5 basket in the μ5-η1,η1,η2,η2,η2 mode, respectively. The
peripheral Ag5 atom is hitched to the Ag4 basket by a pair of
μ3-O,O0,O0 and μ4-O,O,O0,O0 trifluoroacetate groups (O13, O13,
O14, O14 and O15, O15, O16), while atom Ag6 is attached to
the Ag5 basket by trifluoroacetate groups in μ3-O,O0,O0 (O7, O8,
O8) and μ4-O,O,O0,O0 (O9, O9, O10, O10) modes and argentophilic
interaction (Ag6-Ag6#1 3.239 Å). Adjacent Ag4 and Ag5 baskets
coalesce by sharing one vertex (Ag2) to yield a Ag8 aggregate.
The acetonitrile molecule is attached to silver atom Ag1. The Ag8
aggregates are further connected by a pair of inversion-related
(O2W O7#3 2.748 Å) to give a metal-organic layer in the
3 3 3
ab plane (Figure 7a). Adjacent layers are also associated through
hydrogen bonds (C22 O9#4 3.435 Å, C22 O10#4 3.611 Å,
3 3 3
3 3 3
C20#1 O9#4 3.441 Å, and C20#1 O10 3.489 Å)24 to
3 3 3
3 3 3
produce a 3D supramolecular network (Figure 7b).
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Figure 4. Ag7-(μ3-η1,η2-CF3CO2)2-Ag7 building units in 2 are connected by a pair of inversion-related trifluoroacetate groups (O9-O10 and
O9#1-O10#1) acting in the μ3-η1,η2 mode, together with argentophilic interactions (Ag1 Ag6#1 3.342 Å; Ag6 Ag1#1 3.342 Å; Ag6 Ag6#1
3 3 3
3 3 3
3 3 3
3.239 Å) to generate a thick silver rod. CF3 moieties of CF3CO2- are omitted for clarity. Symmetry codes: #1 - x, -y, -z; #2 -x þ 1, -y þ 1, -z þ 1;
#3 x - 1, y, z. Color codes: Ag purple, C gray, O orange.
Figure 6. Atom labeling and coordination mode of L3 in 3 (50%
thermal ellipsoids are drawn for silver atoms). All hydrogen atoms, free
water molecule, and CF3 moieties of CF3CO2- are omitted for clarity.
Symmetry code: #1 -x þ 1, -y þ 2, -z þ 1. Atom color codes: Ag
purple, C gray, N blue, O orange.
μ5-η1,η1,η1,η2,η2, μ4-η1,η1,η2,η2, and μ5-η1,η1,η2,η2,η2 man-
ner (Figure 8). Adjacent Ag11 aggregates are connected by
vertex-sharing to yield a novel Ag20 aggregate (Figure 9a), and
such aggregates are fused by edge-sharing (Ag9
Ag9#2,
3 3 3
3.094 Å) to form a type A thick silver rod (Figure 9c and
Figure S5). Similarly, edge-sharing between symmetry-related
Ag12 aggregates yields a similar Ag20 aggregate (Figure 9b),
and such aggregates are further associated through sharing
Figure 5. (a) 2D metal-organic network of 2. (b) 3D network of 2
linked by face-to-face π-π stacking interactions. All hydrogen atoms
and CF3 moieties of CF3CO2- are omitted for clarity. Symmetry codes:
#1 -x, -y, -z; #2 -x þ 1, -y þ 1, -z þ 1; #3 x - 1, y, z. Color codes:
Ag purple, C gray, N blue, O orange.
of another edge (Ag19
Ag19#4, 3.035 Å) to give a type B
3 3 3
silver rod (Figure 9d and Figure S6). The two kinds of
silver rods in parallel orientation are bridged by three μ3-η1,
η2 and one μ4-η2,η2 trifluoroacetate group to generate a
two-dimensional metal-organic network parallel to the ac
plane (Figure 9e and f). The remaining nine trifluoroacetate
groups span edges of the Agn baskets to stabilize each
[AgnCtC](n-1)þ moiety.
Supramolecular Synthons. In contrast to reported silver
ethynediide (Ag2C2), silver(I) 1,3-butadiynediide (Ag2C4),
R-CtC⊃Agn (R = aryl or alkyl; n = 4, 5), and Agn⊂CtC-
R-CtC⊃Agn (R = o-, m-, p-C6H4; n = 4, 5) supramolecular
synthons, the new Agn⊂CtCCH2OC6H4OCH2CtC⊃Agn syn-
thon has much longer flexible arms. Although the invariable μ4- and
[(Ag3L4)2 (AgCF3CO2)13 (CH3CN)5 (H2O)] (4). The asym-
3
3
3
metric unit of 4 contains 19 crystallographically independent
Ag(I) ions, two L4 ligands bearing bunched ethynide groups that
exhibit different ligation modes A and B (Figure 8), 13 trifluor-
oacetate groups, one aqua ligand, and five acetonitrile ligands
(Figure S4). As expected, each ethynide species in L4 is inserted
into a Agn (n = 4, 5) basket. The ethynide groups acting in mode
A are attached to a Ag11 aggregate in the μ4-η1,η1,η2,η2, μ4-
η1,η2,η2,η2. and μ5-η1,η1,η1,η2,η2 fashion, whereas those func-
tioning in mode B coordinate to a Ag12 aggregate in the
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Figure 7. (a) Layer structure of 3. All hydrogen atoms, acetonitrile
-
molecules, and CF3 moieties of CF3CO2 are omitted for clarity.
(b) 3D network of 3. All hydrogen atoms and CF3 moieties
-
of CF3CO2 are omitted for clarity. Symmetry codes: #1 -x þ 1,
-y þ 2, -z þ 1; #2 -x þ 2, -y þ 2, -z þ 1; #3 -x þ 2, -y þ 1,
-z þ 1; #4 -x þ 2, -y þ 2, -z.
Figure 9. (a) Centrosymmetric Ag20 aggregate in 4 built from inver-
sion-related L4 ligands acting in mode A sharing vertex silver atoms
(Ag1 and Ag1#1) and stabilized by argentophilic interaction
(Ag1 Ag5#1, 2.987 Å). (b) Similar Ag20 aggregate acting in mode
3 3 3
B (Ag11 Ag15, 2.848 Å). (c) Ag20 aggregates are united through
3 3 3
sharing one edge (Ag9 Ag9#2, 3.094 Å) to give a thick silver rod. (d)
Ag20 aggregates are united through sharing one edge (Ag19 Ag19#4,
3 3 3
3 3 3
3.035 Å) to give a silver rod. (e) Two kinds of silver rods in parallel
orientation are bridged by three μ3-η1,η2 and one μ4-η2,η2 trifluoroa-
cetate group to generate a two-dimensional metal-organic network
parallel to the ac plane. (f) Enlargement to show the interchain linkage
through three μ3-η1,η2 (O7-O8, O15-O16, and O21-O22) and one
μ4-η2,η2 (O11-O12) trifluoroacetate group. Acetonitrile molecules and
other CF3CO2- groups are omitted for clarity. Symmetry codes: #1 -x,
1 - y, 1 - z; #2 1 - x, 1 - y, 1 - z; #3 - x, 2 - y, 2 - z; #4 1 - x, 2 - y,
2 - z. Atom color codes: Ag purple, C gray, O orange.
present Agn⊂CtCCH2OC6H4OCH2CtC⊃Agn (n = 4, 5) multi-
nuclear supramolecular synthons in coordination network assembly,
they give rise to very different crystal structures. No silver(I)-
aromatic interaction was found in silver complexes constructed with
the Agn⊂C2-C6H4-C2⊃Agn (n = 4, 5) supramolecular synthon,
whereas the propargyl-functionalized di- and trihydroxybenzenes
employed in the present work offer a good opportunity to introduce
silver(I)-aromatic interactions in the construction of coordination
networks of variable dimensions. In the crystal structure of 4, the
fully deprotonated 1,2,3-tris(prop-2-ynyloxy)benzene ligand exhi-
bits the highest Ag20 aggregation reported to date for a silver(I)-
ethynide metal-organic framework, which may be attributed to the
presence of three neighboring pendant arms bearing terminal
ethynide groups.
Figure 8. Coordination modes A (top) and B (bottom) of anionic L4 in
Ag11 and Ag12 aggregates, respectively (50% thermal ellipsoids are
drawn for silver atoms). Symmetry codes: #1 -x, 1 - y, 1 - z; #2
1 - x, 1 - y, 1 - z; #3 -x, 2 - y, 2 - z; #4 1 - x, 2 - y, 2 - z. Atom
color codes: Ag purple, C gray, O orange.
μ5-ligation modes of the ethynide moiety appear in both the
previously studied Agn⊂C2-C6H4-C2⊃Agn (n = 4, 5)14 and
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ARTICLE
Scheme 2. Coordination Modes Observed for L1 (in 1), L2
(in 2), L3 (in 3), and L4 (in 4)
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’ CONCLUSION
In summary, the present study has established that ethynide
moieties of the flexible multifunctional ligands L1-L4 can adopt
μ4- and μ5-ligation modes upon bonding to silver(I) centers, and
the new metallo-ligand supramolecular synthon Agn-L-Agn
(n = 4, 5) may be utilized for the construction of metal-organic
networks (Scheme 2). In addition, a thick silver rod has been
shown to exist in silver(I)-ethynide compounds 1, 2, and 4. The
interplay of silver-ethynide bonding, argentophilicity, and weak
intermolecular interactions such as hydrogen bonding, silver-
aromatic, and π-π interactions in these complexes has been
shown to play a vital role in the formation and stabilization of
supramolecular aggregates.
’ ASSOCIATED CONTENT
S
Supporting Information. X-ray crystallographic files
b
(CIF) and diagrams of the structures of complexes 1-4. This
material is available free of charge via the Internet at http://pubs.
acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: (S.-Q.Z.) zangsqzg@zzu.edu.cn; (T.C. W.M.) tcwmak@
cuhk.edu.hk.
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’ ACKNOWLEDGMENT
We gratefully acknowledge financial support by the National
Natural Science Foundation of China (No. 20901070), the
China Postdoctoral Science Foundation (Grant 20090460859
and 201003399), Zhengzhou University (No. 000001307015),
and the Hong Kong Research Grants Council (ref. No. CUHK
402408).
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