Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group

Article abstract of DOI:10.1016/j.poly.2013.02.020

In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H₂L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H₂L2), each resulting ethynide ligand is invariably inserted into a Ag_n

Full text of DOI:10.1016/j.poly.2013.02.020

Polyhedron 64 (2013) 63–72
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Assembly of organosilver coordination frameworks with aromatic ligands bearing
a terminal enediyne group
⇑
Sam C.K. Hau, Thomas C.W. Mak
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
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 20 February 2013
In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene
(
H
2
L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H
inserted into a Ag (n = 3–4) basket, leading to the generation of coordination chains or multinuclear
metallocycles, but the well shielded ethenyl group does not take part in silver–olefin binding. In
Ag CO CN and (Ag L1) CO O, which can be crystallized in different
2
L2), each resulting ethynide ligand is invariably
n
Dedicated to Prof. George Christou on the
occasion of his 60th birthday.
(
2
L1)ꢀ9AgCF
3
2
ꢀ3H
2
Oꢀ3CH
3
2
2
ꢀ9AgCF
3
2
ꢀ11H
2
polar protic solvent media, an infinite chain composed of metallocycles is favorably generated with the
assistance of silver–aromatic interaction; such chains are further interconnected to form a two- or three-
Keywords:
Argentophilicity
Coordination framework
Enediyne
Ethynide
Organosilver complex
dimensional organosilver network. In (Ag
pate in silver–aromatic interaction; however, its planar skeleton directs the construction of a more
closely packed metal–organic coordination chain.
2
L2)ꢀ5AgCF
3
CO
2
ꢀ5DMSO, the fluorenyl group does not partici-
Ó 2013 Elsevier Ltd. All rights reserved.
1
. Introduction
The designed construction of coordination polymers using tran-
are composed of discrete molecular clusters or coordination net-
works of variable dimensionality [12a]. A subsequent investiga-
tion on silver(I) complexes generated with the flexible 1,5-
2
ꢂ
sition metal–ethynyl complexes has aroused much attention ow-
ing to their structural diversity [1–3] and possible applications as
photoluminescent materials [4], precursors of non-linear optical
materials [5] and rigid-rod molecular wires [6]. In view of its com-
mon occurrence and robustness, the multinuclear silver(I) ethy-
nide supramolecular synthon [7] R–C„CꢁAg
hexadiyne-1,6-diide (C
distinctly different anti ‘‘stretched Z’’ and gauche ‘‘twisted-arch’’
configurations in forming multinuclear Ag ꢁAg (n = 4, 5)
ꢃC
and C supramolecular synthons, respectively [12b]. As
ꢁAg
6
H
4
) ligand showed that it exhibits
4
6
H
4
n
6
H
4
7
a natural extension of this line of study, our attention is turned
to the angular enediyne functional group. Enediynes have been
widely employed as building blocks for the construction of a
wide range of macrocyclic molecular systems and natural prod-
ucts owing to their high rigidity and conjugated properties
[13–15]. Our plan is to study the coordination behavior of li-
1
n
(R = alkyl, phenyl,
heteroaryl, n = 3–5) has been widely employed by our group and
others as a versatile building unit in constructing a wide variety of
high-nuclearity clusters [3a,8,9,10a,10b] and coordination networks
of one to three dimensions [10c,10d,11]. Notably, assembly based on
this synthon can be further diversified through the incorporation of
additional structural components such as carboxylate [11a] and
ancillary ligands/anions [10c,10d], or in cooperation with other sil-
ver-carbon interactions like silver–aromatic and silver–halogen
interactions [10d].
2 2
gands H L1 and H L2, [16] as shown in Scheme 1, each bearing
a terminal enediyne functionality attached to an aromatic skele-
ton. By combining them with different silver(I) salts and sol-
vents, we aim to investigate the construction of new metal–
organic frameworks (MOFs).
In a recent study, we reported new silver(I) complexes con-
Herein we report our synthetic and structural studies of a ser-
2
ꢂ
taining the linear 1,3-butadiyne-1,4-diide (C
4
) ligand that fea-
ies of five new silver–organic complexes: (Ag
(1), (Ag L1) CO
Oꢀ3CH CN (3), (Ag ꢀ9AgCF
2
L1)
L1)ꢀ9AgCF
O (4), (Ag
L2)ꢀ5AgCF
4
ꢀ16AgNO
3
ture a common [Ag Ag ] core, yielding crystal structures that
C
4 4
4
ꢀ2AgBF
4
2
2
ꢀ9AgCF
3
2
ꢀ7DMSO (2), (Ag
CO
ꢀ11H
2
3
CO
2
ꢀ
3
CO
H
2
3
2
L1)
2
3
2
2
2
3
2
ꢀ5DMSO (5). Based on our previous experience, we anticipated
L1]
(7) with water-soluble silver salts would gener-
⇑
Corresponding author. Fax: +86 (852) 26035057.
E-mail address: tcwmak@cuhk.edu.hk (T.C.W. Mak).
The term ‘‘silver-ethynide’’ is preferred to ‘‘silver-ethynyl’’ because the silver–
that the reaction of crude polymeric starting materials [Ag
(6) and [Ag L2]
2
n
2
n
1
ate new MOFs consolidated by argentophilic and multinuclear
silver(I)–ethynide bonding. Furthermore, the ethenyl group and
the phenyl/fluorenyl rings are potentially capable of partaking
carbon bonding interaction is considered to be mainly ionic with minor covalent
r
and components; the negative charge residing mainly on the terminal C atom draws
p
neighboring Ag(I) atoms close to one another to facilitate the onset of argentophilic
Agꢀ ꢀ ꢀAg interactions.
in silver(I)–olefin, silver–aromatic, and
p–p stacking interactions.
0
277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.02.020

6
4
S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
H L1
H L2
2
2
TMS
TMS
Br
Br
O
TMSA,
PdCl (PPh ) , CuI
CBr , PPh
4
3
2
3 2
CH2Cl2
THF
reflux
K2CO3
CHCl , MeOH
3
Scheme 1. Synthetic scheme for ligands H
2
L1–H
2
L2.
2
. Experimental
All reagents and solvents used were reagent grade. Further puri-
through a pad of silica gel and concentrated in vacuo. Column chro-
matography (hexanes as eluent) was used to provide the corre-
sponding pure dibromoolefins.
fication and drying followed the guidelines of Armarego [17] when
necessary. Organic solvents were concentrated under reduced
pressure on a rotary evaporator. Chromatographic purification of
the products was performed on Macherey Nagel Kieselgel 60 M
2.1.2. (2,2-Dibromoethene-1,1-diyl)dibenzene
1
Yield: 88%; R = 0.78 (hexanes); H NMR (CDCl , 400 MHz) d
f
3
1
3
(
230–400 mesh). Thin-layer chromatography (TLC) was conducted
7.27–7.41 (m, 10H); C NMR (CDCl , 100 MHz) d 90.4, 128.4,
3
on E. Merck silica gel 60 F254 (0.1 mm thickness) coated on alumi-
num plates. Visualization of the developed chromatogram was per-
formed by a spray of 5% w/v dodecamolybdophosphoric acid in
ethanol and subsequent heating. Melting points (uncorrected)
were measured with a Reichert apparatus in degrees Celsius. Nu-
clear magnetic resonance (NMR) spectra were recorded with a Bru-
128.5, 128.8, 128.9, 141.4, 147.9.
2.1.3. 9-(Dibromomethylene)-9H-fluorene
1
f 3
Yield: 90%; R = 0.82 (hexanes); H NMR (CDCl , 400 MHz) d 7.30
(
1
td, J = 0.9, 7.6 Hz, 1H), 7.41 (t, J = 7.3 Hz, 1H), 7.66 (d, J = 7.5 Hz,
H), 8.60 (d, J = 8.0 Hz, 1H); C NMR (CDCl
1
ker ADVANCE-III NMR spectrometer at 400 MHz ( H) and 100 MHz
13
3
, 100 MHz) d 90.7,
1
3
(
C). All NMR measurements were carried out at room tempera-
1
19.6, 126.0, 127.4, 129.4, 138.1, 139.4, 140.5.
ture in deuterated solution and were internally referenced to resid-
1
3
ual proton solvent signals (Note: CDCl referenced at d 7.26 in H,
13
1
and d 77.16 for central line of the triplet in C). Data for H NMR
are reported as follows: chemical shift (d ppm), multiplicity
2
.1.4. General procedure for the palladium cross-coupling reaction
Bis(triphenylphosphine)palladium(II) chloride (42.1 mg,
.06 mmol) and copper(I) iodide (22.8 mg, 0.12 mmol) were added
(
s = singlet, d = doublet, t = triplet, brs = broad singlet, dd = doublet
0
of doublets, m = multiplet), integration, coupling constant (Hz) and
assignment. Mass spectrometry (MS) and high resolution mass
spectrometry (HRMS) measurements were made on a ThermoFinn-
igan MAT 95XL instrument.
to a THF (5 mL) solution mixture of dibromoolefin (1.00 mmol)
with stirring under argon. Triethylamine (0.7 mL) was then in-
jected, and the reaction mixture was kept stirring for 15 min at
2
0 °C. After subsequent addition of trimethylsilylacetylene
(
330 L, 2.30 mmol), the mixture was heated to reflux for 18 h.
l
2
2 2
.1. Synthesis of ligands (H L1 and H L2)
TLC indicated completion of the reaction by showing the disap-
pearance of the starting materials. The mixture was then diluted
with diethyl ether (50 mL), filtered through a pad of silica gel,
and further washed with three portions of hexanes (10 mL). The fil-
trate was concentrated under reduced pressure and purified by
column chromatography (hexanes as eluent) to give the pure
bis(trimethylsilylethynyl)-substituted compounds.
2 2
Ligands H L1 and H L2 were synthesized following the litera-
ture procedure [16] with modification in the use of solvents.
2.1.1. General procedure for dibromoolefination
3
Carbon tetrabromide (662 mg, 2.00 mmol) and PPh (1.05 g,
4
5
.00 mmol) were added to CH
min at 25 °C until the mixture turned bright orange. A solution
Cl (5 mL)
mixture over 1 min, and the
2 2
Cl (50 mL) and allowed to stir for
of benzophenone or fluoren-9-one (1.00 mmol) in CH
was slowly added to the CBr /PPh
2
2
2.1.5. {3-(Diphenylmethylene)penta-1,4-diyne-1,5-
4
3
diyl}bis (trimethylsilane)
1
reaction mixture then developed a darker red/orange color. TLC
analysis indicated completion of the reaction by showing the dis-
appearance of the ketone. The solution mixture was diluted with
hexanes (100 mL), and the heterogeneous mixture was filtered
Yield: 76%; R
f
= 0.65 (hexanes); H NMR (CDCl
3
, 400 MHz) d 0.09
(s, 9H), 7.27–7.31 (m, 3H), 7.41–7.43 (m, 2H); C NMR (CDCl ,
3
100 MHz) d ꢂ0.3, 97.9, 101.9, 103.3, 127.6, 128.6, 130.4, 140.1,
1
3
158.4.

S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
65
2
.1.6. {3-(9H-Fluoren-9-ylidene)penta-1,4-diyne-1,5-
diyl}bis (trimethylsilane)
Yield: 66%; R
= 0.68 (hexanes); 1H NMR (CDCl
.35 (s, 9H), 7.23–7.27 (m, 1H), 7.36 (td, J = 0.9, 7.5 Hz, 1H), 7.64
low plate-like crystals of 2 were obtained after standing in the dark
for one week by slow liquid diffusion of de-ionized water into the
f
3
, 400 MHz) d
filtrate. Yield ca. 55%. Anal. Calc. for C68
H, 1.83. Found: C, 23.81; H, 1.77%. IR:
H
62Ag13
F
27
ꢂ1
O
25
S
7
: C, 23.89;
0
m
2025 cm (w,
m
C„C).
13
(
d, J = 7.4 Hz, 1H), 8.67 (d, J = 7.8 Hz, 1H);
3
C NMR (CDCl ,
1
1
00 MHz) d ꢂ0.1, 100.9, 103.4, 104.6, 119.6, 126.0, 127.3, 129.8,
2
.3.3. Synthesis of (Ag
2
L1)ꢀ9AgCF
3
CO
2
ꢀ3H
2
Oꢀ3CH
3
CN (3)
37.4, 140.3, 146.9.
AgCF CO (440 mg, 2.00 mmol) was dissolved in THF (1 mL) fol-
3
2
lowed by subsequent addition of complex 6 (ꢅ20.0 mg), which was
contaminated with a small amount of acetonitrile. The solution
mixture was kept stirring until all solids were dissolved. After that,
the solution was filtered and left to stand with a beaker of water in
a desiccator in the dark at 20 °C. After several days, yellow blocks
of 3 were deposited through water diffusion in ca. 70% yield. Anal.
2
.1.7. General procedure for the desilylation reaction
The bis(trimethylsilylethynyl)-substituted compound (1.00
mmol) was dissolved in a mixed solution of methanol (5 mL) and
chloroform (5 mL) with stirring. Potassium carbonate (414 mg,
3
for 2–3 h. TLC analysis indicated the disappearance of the starting
materials, and the mixture was filtered through a pad of silica gel.
The filtrate was concentrated and purified through column chro-
matography (hexanes as eluent) to give the pure diethynyl-substi-
tuted compound.
.00 mmol) was then added and the mixture was allowed to stir
Calc. for C42
H
25Ag11
F
27
N
3
O
21: C, 19.35; H, 0.97; N, 1.61. Found: C,
ꢂ1
1
9.21; H, 1.02; N, 1.58%. IR:
m
2029 cm (w,
mC„C).
2
.3.4. Synthesis of (Ag
2
L1)
Complex 6 (ꢅ20.0 mg) was added to a mixed solution of AgCF3-
(440 mg, 2.00 mmol) and AgBF (388 mg, 2.00 mmol) in meth-
2
ꢀ9AgCF
3
CO
2
ꢀ11H
2
O (4)
CO
2
4
2.1.8. (2-Ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H
2
L1)
1
anol (1 mL) and water (1 mL). The preparative procedure for 3 was
repeated to yield yellow block-like crystals of 4 in ca. 65% yield.
Yield: 93%; R
s, 1H), 7.33–7.36 (m, 3H), 7.40–7.44 (m, 2H); C NMR (CDCl
00 MHz) d 80.3, 82.0, 99.8, 127.9, 129.0, 130.2, 139.8, 159.2.
f
= 0.60 (hexanes); H NMR (CDCl , 400 MHz) d 3.03
3
13
(
1
3
,
Anal. Calc. for C54
H
42Ag13
F
27
O
29: C, 21.13; H, 1.38. Found: C,
ꢂ1
2
0.98%. H, 1.26%; IR:
m
2031 cm (w,
mC„C).
2
.1.9. 9-(Penta-1,4-diyn-3-ylidene)-9H-fluorene (H
Yield: 90%; R
= 0.63 (hexanes); 1H NMR (CDCl
.76 (s, 1H), 7.27–7.30 (m, 1H), 7.38 (td, J = 0.4, 7.2 Hz, 1H), 7.63
2
L2)
f
3
, 400 MHz) d
2.3.5. Synthesis of (Ag L2)ꢀ5AgCF CO ꢀ5DMSO (5)
2
3
2
3
3 2
AgCF CO (440 mg, 2.00 mmol) was first dissolved in DMSO
13
(
d, J = 7.4 Hz, 1H), 8.63 (d, J = 7.8 Hz, 1H);
C NMR (CDCl
3
,
(1 mL), and the polymeric complex 7 (ꢅ20.0 mg) was subsequently
added to the solution. Repeating the preparative procedure for 3
deposited yellow plate-like crystals of 5 in ca. 45% yield. Anal. Calc.
1
1
00 MHz) d 82.3, 86.6, 98.4, 119.6, 125.9, 127.7, 130.3, 137.0,
40.5, 148.3.
for C37
H
32Ag
7
F
15
ꢂ1
S
5
O
15: C, 23.18; H, 1.68. Found: C, 22.96; H, 1.74%.
2.2. Preparation of polymeric silver ethynides as synthetic precursors
IR: 2027 cm (w, mC„C).
m
Caution. Silver ethynides are potentially explosive and should
2
.4. X-ray crystallography
be handled in small amounts with extreme care!
Ligand H L1 (1.00 mmol) was first dissolved in acetonitrile
10 mL). Silver nitrate (170 mg, 1 mmol) and triethylamine
138 L, 1.00 mmol) were added subsequently with vigorous stir-
2
Selected crystals were used for data collection on a Bruker AXS
(
(
Kappa ApexII Duo diffractometer at 100 K (1, 2 and 5), and at 173 K
l
(3 and 4) using frames of oscillation range 0.3°, with 2° < h < 28°.
ring, and the mixture was allowed to stir for 2 h in darkness. The
resulted pale yellow slurry was diluted with methanol (20 mL)
and filtered by suction filtration to collection a pale yellow precip-
An empirical absorption correction was applied using the SADABS
program [18]. The structures were solved by the direct method
and refined by full-matrix least-squares on F using the SHELXTL pro-
gram package [19]. The crystallographic data are summarized in
Table 1.
2
itate of polymeric [Ag
methanol (3 ꢄ 10 mL) and then stored in wet form at ꢂ10 °C in a
refrigerator. Silver complexes of H L2 were prepared in the same
2 n
L1] (6), which was washed thoroughly with
2
manner, the yields and infra-red absorption data are displayed be-
ꢂ1
low: [Ag
2
L1]
n
(6) yield: 95%; IR:
m
2033 cm (w,
m
C„C); [Ag
2
L2]
n
3. Results
ꢂ1
(7) yield: 93%; IR:
m
2042 cm (w,
m
C„C).
3.1. Crystallization
2
2
.3. Synthesis of silver ethynide complexes
2 2
The neutral ligands H L1 and H L2 were synthesized from reac-
.3.1. Synthesis of (Ag
AgNO (680 mg, 4.00 mmol) was first dissolved in a mixed solu-
tion of AgBF (388 mg, 2.00 mmol) in water (1 mL) and methanol
2 4 3
L1) ꢀ16AgNO ꢀ2AgBF
4
(1)
tions using the corresponding benzophenone and fluoren-9-one as
starting materials. Double or triple salts 1–5 were obtained from
room-temperature crystallization of the corresponding crude poly-
3
4
(
1 mL). After the addition of polymeric complex 6 (ꢅ20.0 mg),
meric compounds [Ag
DMSO or water/methanol solution of AgCF
2
L1]
n
(6) and [Ag
2
L2]
n
(7) in a concentrated
CO /AgBF (1:1) or
and AgBF were used to pro-
ligand and increase the sil-
the solution mixture was stirred until it became clear. The solution
was then filtered and left to stand in the dark at 20 °C. After several
days, yellow block-like crystals of 1 were harvested through evap-
3
2
4
AgNO
3
/AgBF
4
(2:1). AgCF
3
CO
2
, AgNO
3
4
ꢂ
ꢂ
vide the auxiliary CF
3
CO
2
and NO
3
oration in ca. 50% yield. Anal. Calc. for C72
H
40Ag26
B
F
2 8
N
16
O
51: C,
ver(I) ion concentration, respectively.
1
2
7.56; H, 0.82; N, 4.55. Found: C, 17.44; H, 0.78; N, 4.46%. IR:
021 cm (w, mC„C).
m
The high concentration of silver ions and their aggregation
through argentophilicity ensure that the ethynide moiety generally
achieves a high ligation number of 4 or 5 within a butterfly-shaped
ꢂ1
2
.3.2. Synthesis of (Ag
2
L1)
2
ꢀ9AgCF
3
CO
2
ꢀ7DMSO (2)
4
Ag or square-pyramidal Ag5 basket [20], as opposed to most tran-
AgCF CO (440 mg, 2.00 mmol) was first dissolved in DMSO
3
2
sition-metal alkyl and aryl ethynide complexes with ligation num-
bers ranging from 1 to 4, and such baskets can be mutually
connected by bridging trifluoroacetate or nitrate ligands to yield
higher-dimensional MOFs.
(
1 mL), and the polymeric complex 6 (ꢅ20.0 mg) was subsequently
added to the solution. After stirring until all solids dissolved, the
solution was filtered and the filtrate transferred to a test tube. Yel-

6
6
S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
Table 1
Crystallography data and structure refinement parameters of complexes 1–5.
Complex
1
2
3
4
5
Structural formula
Formula Wt.
Crystal system
Space group
a (Å)
C
72
H
40Ag26
B
2
F
8
N
16
O
51
C
68
H
62Ag13
F
27
O
25
S
7
C
42
H
25Ag11
F
27
N
3
O
21
C
54
H
42Ag13
F
27
O
29
C
37 7 15 5 15
H32Ag F S O
4923.44
triclinic
P 1ꢀ (No. 2)
3418.91
triclinic
P 1ꢀ (No. 2)
2607.22
monoclinic
3070.19
monoclinic
P2
1917.02
triclinic
P 1ꢀ (No. 2)
C2/c (No. 15)
33.661(18)
14.980(6)
29.601(15)
90.0
114.890(19)
90.0
13539(11)
8
2.558
3.249
0.0562
0.1503
1
/c (No. 14)
15.056(11)
18.836(13)
19.672(14)
73.359(2)
72.540(2)
86.221(2)
5098.0(6)
2
3.207
4.983
0.0414
0.1049
14.205(13)
16.030(14)
22.569(2)
96.267(2)
94.508(2)
108.860(2)
4798.9(8)
2
2.366
2.860
0.0490
0.1342
15.280(8)
32.894(18)
16.986(9)
90.0
115.380(10)
90.0
7713.8(7)
4
2.644
13.557(7)
13.906(7)
16.061(8)
101.026(10)
102.170(10)
100.991(10)
2819.9(2)
2
2.258
2.673
0.0430
0.1166
b (Å)
c (Å)
a
(Å)
b (Å)
(Å)
c
3
V (Å )
Z
q
l
R
ꢂ3
calc (g cm
)
ꢂ1
(mm
)
r
3.363
a
1
(I > 2
)
0.0609
0.1811
1.048
b
wR
2
(all data)
Goodness-of-fit (GOF)
1.061
1.043
1.177
1.033
a
R
wR
1
=
R
= {
||F
R
o
| ꢂ |F
c o
||/R|F |.
b
2
2 2
2)2]}1/2.
2
[w(F
o
ꢂ F ) ]/R[w(F
c o
3.2. Description of crystal structures
a bond distance of 2.766(8) Å (Fig. 1a), while silver atom Ag20 is
1
g
-coordinated by carbon atom C44 of the phenyl ring
As listed in Table S1 in the Supporting Information, the mea-
sured and mixed ( ) Ag–C bond distances in complexes
–5 lie in the range 2.151(2)–2.268(8), 2.278(6)–2.570(10) and
.120(8)–2.576(14) Å, respectively.
(2.769(8) Å) (Fig. 1b), which are indicative of significant silver–aro-
matic interaction (under 2.9 Å) [21–26].
r
,
p
r,p
1
2
The Type 2 Ag
fragment through two
designated by naming their nitrogen atoms N11A and N14) and
one -bridged aqua ligand (O2W) (Fig. 2a). Besides this, the Type
2 segment is linked with a Type 3 Ag fragment through another
three nitrate groups (N7, N9 and N10) by
6
segment is associated with an adjacent Type 4
1
2
2
Ag
7
4
l -g ,g ,g -coordinated nitrate groups
(
3
.2.1. (Ag
Complex 1 contains four crystallographic independent ligands
L1 with eight ethynide moieties that exhibit different coordination
2
L1)
4
ꢀ16AgNO
3
ꢀ2AgBF
4
(1)
l
2
7
3
3
1
1
1
1
5 3
l -g ,g ,g , l -g ,g ,g
1
1
2
1
1
2
modes: C1„C2 and C53„C54 taking the
remaining ethynide moieties are each bound to a butterfly-shaped
Ag basket but in different ways (C17„C18, C19„C20, C35„C36,
C37„C38 and C71„C72 in
l
3
-
g
,g
,g
mode and the
and
4
l -g ,g ,g modes, respectively. Through two bridging nitrate
2
2
2
3
3
1
groups (N6 in
5 5
l -g ,g ,g and N7 in l -g ,g ,g ), the Type 3 seg-
ment is further interconnected with a symmetry-related Type 2
aggregate (Fig. 2b).
4
1
1
1
2
l
4
-g
,g
,g
,
g
, and C55„C56 in
) (Fig. 1). Furthermore, such silver-ethynide aggregates
coalesce to yield two types of Ag fragment (Type 1: C1„C2 and
C71„C72 share Ag14; Type 2: C35„C36 and C53„C54 share
Ag11) and two types of Ag segment (Type 3: C17„C18 and
1
1
2
2
l -g
4
,g
,g
,g
The interconnection between two symmetry-related Type 1 Ag
6
aggregates and one Type 3 aggregate is formed by two tetrafluoro-
borate groups (B1 and B2) as depicted in Fig. 2c. The Type 3 frag-
6
1
3
3
5
ment is linked with the Type 2 segment through a l -g ,g ,g -
7
C19„C20 share Ag6; Type 4: C37„C38 and C55„C56 share
coordinated nitrate group (N7), while the latter is interconnected
Ag21). Phenyl carbon atom C14 is attached to silver atom Ag7 with
with the adjacent Type 1 aggregate through two bridging nitrate
Fig. 1. (a) Coordination modes of two independent L1 ligands in triple salt (Ag
2
L1)
4
ꢀ16AgNO
3
ꢀ2AgBF (1). Symmetry code: A: ꢂx, 1 ꢂ y, 2 ꢂ z. (b) Coordination modes of
4
remaining independent L1 ligands in 1. Symmetry code: A: 2 ꢂ x, 1 ꢂ y, 1 ꢂ z. The argentophilic Agꢀ ꢀ ꢀAg distances shown as thick rods lie in the range 2.70–3.40 Å. Silver
atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. The hydrogen atoms, nitrate and tetrafluoroborate ligands are omitted for clarity (Color
scheme: purple, silver atoms; black ball and stick, C„C bonds; broken line, Ag–C bonds; the same color scheme for atoms and bonds applies to all other figures). (Color
online.)

S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
67
Fig. 2. (a) Perspective view of coordination environment of nitrate groups between Type 2 and Type 4 aggregates. Symmetry code: A: 1 ꢂ x, 1 ꢂ y, 1 ꢂ z; B: 2 ꢂ x, 1 ꢂ y, 1 ꢂ z;
C: 1 ꢂ x, 1 ꢂ y, 2 ꢂ z. (b) Perspective view of coordination environment of nitrate groups between Type 2 and Type 3 aggregates. Symmetry code: A: 2 ꢂ x, 1 ꢂ y, 1 ꢂ z; B: 1 + x,
y, z. (c) Perspective view of coordination environment of nitrate groups between Type 1, Type 2 and Type 3 aggregates. Symmetry code: A: 2 ꢂ x, 1 ꢂ y, 1 ꢂ z; B: 1 + x, y, z; C:
1
ꢂ x, 1 ꢂ y, 2 ꢂ z. (d) Perspective view of coordination environment of nitrate groups between Type 2, Type 3 and Type 4 aggregates. Symmetry code: A: 1 ꢂ x, 1 ꢂ y, 1 ꢂ z; B:
ꢂ1 + x, y, z. The ligands L1 and hydrogen atoms are omitted for clarity. (Color scheme: orange, oxygen atoms; blue, nitrogen atoms; green, fluorine atoms; plum, boron atoms;
henceforth the same representation will apply to other figures.) (Color online.)
1,
g
2,
g
2,
l
3
-g
1,
g
2
modes, respec-
bond distance of 2.623(9) Å, while silver atom Ag9 is
nated by C36 at 2.736(9) Å.
g
1-coordi-
groups (N1B and N9) by the
4
l -
g
tively. The Type 4 fragment is associated with symmetry related
Type 2 and Type 3 aggregates through three coordinated nitrate
Besides this, each pair of adjacent Ag
4
baskets coalesce to yield a
1
2
2
1
2
2
groups (N12, N13 and N15B) via different
l
4
-
g
,
g
,
g
,
l
4
-
g
,
g
,
g
Ag
7
segment and a Ag aggregate, respectively, through atoms
6
1
1
2
and
l
2
-g
,g
,g
modes (Fig. 2d), respectively. As a result, a com-
sharing (Ag1–Ag7 shares Ag1; Ag8–Ag13 shares Ag9 and Ag11).
The two silver segments are further fused together to generate a
Ag13 aggregate through argentophilic interactions between Ag2
and Ag8 (Fig. 3b).
plex, closely knitted three-dimensional silver(I)–organic coordina-
tion network structure is constructed.
Two adjacent Ag13 aggregates are linked through three DMSO
1
1
3
.2.2. (Ag
Complex 2 contains two crystallographically independent L1
ligands in which the ethynide moieties exhibit different coordina-
2
L1)
2
ꢀ9AgCF
3
CO
2
ꢀ7DMSO (2)
2
molecules (S5A, S4A and S6) by the l -g ,g mode to generate an
infinite silver–organic coordination chain along the b-axis
(Fig. 4a). Neighboring adjacent chains are interconnected through
1
1
1
2
tion modes: C1„C2, C4„C5 and C19„C20 take the
coordination mode, and the remaining ethynide moiety is also
bound to a butterfly-shape Ag basket but in a different way
). The Agꢀ ꢀ ꢀAg distances lie in a range
l
4
-g
,g
,g
,g
weak C–Hꢀ ꢀ ꢀ
p
[C15–Hꢀ ꢀ ꢀCcent of C32B and C33B, 2.807(2) Å] and
C–Hꢀ ꢀ ꢀF interactions [C57–Hꢀ ꢀ ꢀF12A, 2.498(11) Å] to yield a
three-dimensional supramolecular network (Fig. 4b).
4
1
1
1
1
(
4
C22„C23 in l -g ,g ,g ,g
of 2.815(11) and 3.335(6) Å (Fig. 3a), which are comparable to
those observed in a wide variety of silver double and multiple salts
reported by our group and attributable to argentophilic interac-
tions [27]. Phenyl carbon C9 is attached to silver atom Ag7 at a
3.2.3. (Ag
2 3 2 2
L1)ꢀ9AgCF CO ꢀ3H Oꢀ3CH
3
CN (3)
In silver double salt 3, a crystallographic mirror plane bisects
the enediyne groups (C3@C4 and C13@C14) of two independent
L1 ligands (Fig. 5a). The pair of symmetry-related ethynide groups

6
8
S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
Fig. 3. (a) Coordination modes of two independent L1 ligands in double salt (Ag
2
L1)
2
ꢀ9AgCF
3
CO
2
ꢀ7DMSO (2). The argentophilic Agꢀ ꢀ ꢀAg distances shown as thick rods lie in
the range 2.70–3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. Symmetry code: A: x, ꢂ1 + y, z. The hydrogen atoms, DMSO
molecules and trifluoroacetate groups are omitted for clarity. (b) Coordination environment of independent L1 ligands in a metal–organic chain. Symmetry code: A: x, ꢂ1 + y,
z; B: x, 1 + y, z. The hydrogen atoms, DMSO molecules and trifluoroacetate groups are omitted for clarity.
Fig. 4. (a) Perspective view of a portion of the silver–organic coordination chain in 2 along the b-axis, showing the connection between the two adjacent silver segments by
DMSO molecules. Symmetry code: A: x, 1 + y, z. The L1 ligands, hydrogen and fluorine atoms are omitted for clarity. (b) Perspective view of the interconnection between
adjacent coordination chains in 2, showing notable weak C–Hꢀ ꢀ ꢀp and C–Hꢀ ꢀ ꢀF interactions. Symmetry code: A: 1 ꢂ x, 1 ꢂ y, ꢂz; B: ꢂx, ꢂy, 1 ꢂ z. (Color scheme: yellow, sulfur
atoms; turquoise broken line, C–Hꢀ ꢀ ꢀ
p
interactions; dark red broken line, C–Hꢀ ꢀ ꢀF interactions, henceforth the same representation will apply to other figures.) (Color online.)
2
(
C1„C2 and C1A„C2A) acting in the
mode is each clasped by a butterfly-shaped Ag
other pair (C11„C12 and C11A„C12A) taking the
coordination mode are inserted into two Ag baskets. Through
edge sharing involving Ag1, Ag2 and Ag5, the four symmetry-re-
lated Ag segments are fused into a large Ag14 metallocyclic aggre-
gate with Agꢀ ꢀ ꢀAg distances ranging from 2.881(14) to 3.362(19) Å
Fig. 5b).
As shown in Fig. 6a, peripheral silver atom Ag8 is attached to
the Ag14 metallocyclic aggregate through trifluoroacetate groups
l
4
-
g
1,
g
1,
g
2,
g
coordination
trile (N1, N2 and N3) ligands are attached to different silver(I)
atoms by the mode.
Cross-linkage of adjacent silver(I) metallocycles by a dinuclear
bridging unit [(Ag10–Ag10B)(O15^O16) ] produce an infinite zig-
4
basket, while the
l
1
1
1
1
2
4
l -g ,g ,g ,g
4
2
zag silver–organic chain along the c-axis, which is further consoli-
4
dated by additional H-bonding with aqua liagnds [O2Wꢀ ꢀ ꢀO3W,
2.776(11) Å;
O2Wꢀ ꢀ ꢀO11A,
2.764(11) Å;
O18ꢀ ꢀ ꢀO1WA,
(
2.705(11) Å; O1WAꢀ ꢀ ꢀO15A, 2.773(9) Å] (Figs. 6b and 7a).
Further connection between adjacent infinite chains through H-
bonds between aqua ligands and trifluoroacetate groups
1
2
2
2
O7^O8 and O13^O14 by the
l
3
-g
,g
and
l
4
-
g
,
g
modes, respec-
[O2Aꢀ ꢀ ꢀO3WB,
2.796(11) Å;
O2WAꢀ ꢀ ꢀO3WA,
2.776(11) Å;
tively. Phenyl carbon atom C7 is attached to Ag8 at a bond distance
of 2.652(17) Å. Silver atom Ag9 is linked to the Ag14 metallocycle
O2WAꢀ ꢀ ꢀO3WB, 2.854(10) Å] then generates a three-dimensional
supramolecular network (Fig. 7b).
1
2
through two
and O5^O6) and a
3
l -
g
,g
-coordinated trifluoroacetate groups (O3^O4
-bridged aqua ligand (O1W). Two other
peripheral silver(I) atoms (Ag10 and Ag11) are hitched to the
Ag14 aggregate through pairs of trifluoroacetate groups (O11^O12
and O13^O14 for Ag10; O9^O10 and O17^O18 for Ag11) in the
l
2
3
.2.4. (Ag
In the crystal structure of 4, two independent L1 ligands are sur-
rounded by a Ag13 metallocyclic aggregate. The ethynide group
2
L1)
2
ꢀ9AgCF
3
CO
2
ꢀ11H
2
O (4)
1
1
2
2
composed of C1 and C2 acting in the
4
l -g ,g ,g ,g coordination
1
2
3
l -g ,g mode. The remaining aqua (O2W and O3 W) and acetoni-
mode is capped by a butterfly-shaped Ag4 aggregate, while the

S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
69
Fig. 5. (a) Coordination modes of independent L1 ligands in double salt (Ag
the range 2.70–3.40 Å. The hydrogen atoms, acetonitrile and trifluoroacetate ligands are omitted for clarity. Symmetry code: A: 1 ꢂ x, y, 0.5 ꢂ z. (b) Perspective view of a Ag14
metallocycle in 3, silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. Symmetry code: A: 1 ꢂ x, y, 0.5 ꢂ z.
2
L1)ꢀ9AgCF
3
CO
2
ꢀ3H
2
Oꢀ3CH CN (3). The argentophilic Agꢀ ꢀ ꢀAg distances shown as thick rods lie in
3
Fig. 6. (a) Coordination environment of the silver(I) atoms in 3. The hydrogen and fluorine atoms are omitted for clarity. (b) Perspective view of a portion of the coordination
chain consists of metallocycles in 3, indicating all notable H-bond interactions. Symmetry code: A: 1 ꢂ x, y, 0.5 ꢂ z; B: 1.5 ꢂ x, ꢂ1.5 ꢂ y, 1 ꢂ z. The ligands L1, hydrogen and
fluorine atoms are omitted for clarity. (The color scheme used for atoms and bonds are the same as those in Fig. 1; in addition, green broken lines indicate H-bond
interactions.) (Color online.)
Fig. 7. (a) Perspective view of a silver coordination chain in the crystal packing of 3, viewing from the direction of a-axis. Symmetry code: A: 1 ꢂ x, y, 0.5 ꢂ z; B: 1.5 ꢂ x,
ꢂ1.5 ꢂ y, 1 ꢂ z. The ligands L1 and hydrogen atoms are omitted for clarity. (b) Perspective view of the crystal packing of 3 approximately along the b-axis, indicating all
significant H-bond interactions between metal–organic chains. Symmetry code: A: 1 ꢂ x, y, 0.5 ꢂ z; B: x, ꢂ1 ꢂ y, 0.5 + z. The ligands L1, hydrogen and fluorine atoms are
omitted for clarity.

7
0
S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
Fig. 8. Coordination environment of the silver(I) atoms in double salt (Ag
.70–3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. The trifluoroacetate groups, water molecules and hydrogen atoms are
omitted for clarity.
2 2
L1) ꢀ9AgCF
3
CO
2
ꢀ11H
2
O (4). The argentophilic Agꢀ ꢀ ꢀAg distances shown as thick rods lie in the range
2
other ethynide (C4„C5) of the same ligand is inserted to a Ag4
2.477(8) Å;
C29C–Hꢀ ꢀ ꢀF5B,
2.657(15) Å;
C30C–Hꢀ ꢀ ꢀF6B,
1
2
2
2
basket via the
independent L1, the ethynide moieties are capsulated by separate
Ag baskets in different coordination modes (C19„C20 in
l
4
-g
,g
,g
,g
mode, as shown in Fig. 8. For the other
2.654(12) Å] to yield a three-dimensional supramolecular network
(Fig. 11b).
4
4
l -
1
1
2
2
1
1
1
2
g
,g
,g
,g
; C22„C23 in
l
4
-g
,g
,g
,g
). Through sharing silver(I)
atoms Ag4, Ag7, Ag10 and Ag13, the four Ag
4
segments are coa-
4. Discussion
lesced to form a Ag12 metallocycle. Silver atom Ag2 is attached to
the Ag12 fragment by argentophilic interaction to engender a larger
4.1. Influence of aromatic substituent, ancillary anion and solvent
2
Ag13 aggregate. Notably, silver atom Ag1 is
g
-coordinated by C8
and C9 of the phenyl ring at a Ag–Ccent bond distance of
Systematic investigation of the present series of silver com-
plexes (1–5) demonstrates the general utility of the silver–ethy-
nide supramolecular synthon R–C„CꢁAgn (n = 3, 4) in
coordination network assembly. Among the five complexes re-
ported herein, the ethenyl group in either L1 or L2 does not take
part in silver–olefin binding as it is well shielded by the silver
aggregates around the two conjugated ethynide groups. It is noted
that the pair of phenyl groups in L1 allows for higher flexibility
than the rigid fluorenyl skeleton in L2, and this facilitates the onset
of silver(I)–aromatic interaction during the assembly of MOFs.
In triple salt 1, nitrate and tetrafluoroborate groups serve as
ancillary anions instead of the trifluoroacetate ion. Their low
1
2
.611(12) Å, and phenyl carbon atom C26 is
g -coordinated to sil-
ver atom Ag6 at 2.677(11) Å.
Adjacent metallocycles are associated through linkage by two
2
-bridging aqua ligands (O4W and O6WA) to generate an infinite
l
metal–organic coordination chain along the b-axis (Fig. 9a). Such
structure is further stabilized by additional H-bonds involving the
aqua ligands [O11ꢀ ꢀ ꢀO7W, 2.740(15) Å; O12ꢀ ꢀ ꢀO3WA, 2.685(9) Å;
O3WAꢀ ꢀ ꢀO4W, 2.707(8) Å; O4Wꢀ ꢀ ꢀO8W, 2.649(14) Å; O6Aꢀ ꢀ ꢀO8W,
2
.854(19) Å;
O15ꢀ ꢀ ꢀO5WA,
2.699(13) Å;
O5WAꢀ ꢀ ꢀO10W,
2.838(15) Å; O16AꢀꢀꢀO10W, 2.806(14) Å; O16AꢀꢀꢀO6WA, 2.753(14) Å].
Neighboring coordination chains are interconnected by a pair of
inversion-related trifluoroacetate groups (O1^O2 and O1A^O2A) to
yield a three-dimensional coordination network (Fig. 9b), which is
consolidated by additional H-bonds [O18ꢀ ꢀ ꢀO1W, 2.708(9) Å;
O3Aꢀ ꢀ ꢀO1W, 2.799(8) Å].
3
.2.5. (Ag
In the crystal structure of 5, the ethynide groups (C1„C2 and
C4„C5) of ligand L2 are each capsulated within a Ag basket in
coordination mode with Agꢀ ꢀ ꢀAg bond distances
in a range of 2.742(8) and 3.088(8) Å (Fig. 10a). With an inversion
center located between Ag4 and Ag4A, each Ag segment is further
expanded into a Ag aggregate by sharing a common vertex.
Around a crystallographic inversion center, two symmetry-re-
lated Ag aggregates are bridged by pairs of trifluoroacetate groups
O5^O6 and O5A^O6A) and DMSO molecules (S5 and S5A) by
2
L2)ꢀ5AgCF
3
CO
2
ꢀ5DMSO (5)
4
1
1
1
2
the
4
l -g ,g ,g ,g
4
7
7
(
l
1
2
1
1
3
-g
,g
and
2
l -
g
,g
coordination modes, respectively (Fig. 10b).
Neighboring Ag
7
aggregates are connected through a positionally
0
0
Fig. 9. (a) Perspective view of a portion of the infinite silver–organic chains in the
crystal packing of 4, showing all significant H-bonds. Symmetry code: A: x, 1.5 ꢂ y,
disordered DMSO ligand (S3A/S3A or S3B/S3B , which exhibits an
occupancy ratio of 6:4), to generate an infinite anti-parallel double
silver–organic chains along the b-axis (Fig. 11a). Adjacent chains
are interconnected by weak C–Hꢀ ꢀ ꢀF interactions [C35–Hꢀ ꢀ ꢀF7A,
0
.5 + z. (b) Perspective view of a portion of the three-dimensional silver–organic
network structure in 4, showing all notable H-bonds. Symmetry code: A: ꢂ1 ꢂ x,
1 ꢂ y, ꢂ1 ꢂ z. The ligands L1, hydrogen and fluorine atoms are omitted for clarity.

S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
71
Fig. 10. (a) Coordination environment of the silver(I) atoms in double salt (Ag
2
L2)ꢀ5AgCF
3
CO
2
ꢀ5DMSO (5). The argentophilic Agꢀ ꢀ ꢀAg distances shown as thick rods lie in the
range 2.70–3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. Symmetry code: A: 1 ꢂ x, 1 ꢂ y, 1 ꢂ z. The hydrogen and fluorine
atoms are omitted for clarity. (b) Perspective view of the crystal packing in 5, showing an inversion center located between Ag4 and Ag4A. Symmetry code: A: 1 ꢂ x, 1 ꢂ y,
1
ꢂ z. The hydrogen and fluorine atoms are omitted for clarity.
0
0
Fig. 11. (a) Perspective view of a portion of the infinite metal–organic chains in 5 along the b-axis, showing the DMSO molecules (S3A/S3A and S3B/S3B ), which exhibit a
positional disorder. Symmetry code: A: 1 ꢂ x, 1 ꢂ y, 1 ꢂ z; B: x, 1 + y, z. (b) Perspective view of the interconnection between adjacent chains in 5, showing weak C–Hꢀ ꢀ ꢀF
interaction. Symmetry code: A: 1 + x, y, z; B: 2 ꢂ x, 2 ꢂ y, 1 ꢂ z; C: 2 + x, 1 + y, 1 + z. The ligands L2, hydrogen and fluorine atoms are omitted for clarity.
hydrophobicity and diverse coordination modes account for the
formation of a complex silver–organic coordination network struc-
ture. In complex 2, construction of the silver–organic framework
involves the ligation of DMSO molecules, which direct all L1 li-
gands to be positioned on the same side, resulting in an infinite sil-
ver–organic coordination chain. When the crystallization process is
carried out in polar protic solvents using silver(I) trifluoroacetate
using p–p stacking interaction for consolidation of their coordina-
tion network structure.
As solvated water molecules are found in complexes 1 and 4,
weak H-bonds are employed to enhance the stability of the silver(I)
coordination chains and connect them into a three-dimensional
supramolecular structure. In complex 2 and 5, three-dimensional
networks are constructed by weak C–Hꢀ ꢀ ꢀ
p
and C–Hꢀ ꢀ ꢀF
(
complexes 3 and 4), an infinite chain composed of multinuclear
interactions.
metallocycles is favorably generated with the assistance of sil-
ver–aromatic interaction. In complex 5, the rigid fluorenyl skeleton
prohibits L2 from engagement in silver–aromatic interaction with
nearby silver atoms. However, its planar structure directs the con-
struction of a more closely packed metal–organic coordination
chain.
5. Conclusion
In summary, the present work reports the synthesis and struc-
tural characterization of a series of five organosilver(I) complexes
containing aromatic ligands each bearing a terminal enediyne
group, from which each ligand is invariably inserted into a Ag
n
4
.2. Role of weak intermolecular interactions
(n = 3–4) basket, leading to the generation of coordination chains
or multinuclear metallocycles. It is notable that the well shielded
ethenyl group does not take part in silver–olefin binding. In com-
plexes 3 and 4, which can be crystallized in different polar protic
solvent media, an infinite chain composed of metallocycles is
favorably generated with the assistance of silver–aromatic interac-
tion; such chains are further interconnected to form a two- or
Among the five complexes reported herein, none exhibits offset
face-to-face p–p stacking interaction in their metal–organic frame-
work structures. It is observed that the aromatic skeletons of the
ligands, especially that of L1, have a higher preference to form sil-
ver–aromatic interaction with nearby silver atoms rather than

7
2
S.C.K. Hau, T.C.W. Mak / Polyhedron 64 (2013) 63–72
three-dimensional organosilver network. In 5, the fluorenyl group
does not participate in silver–aromatic interaction; however, its
planar skeleton directs the construction of a more closely packed
metal–organic coordination chain.
(d) G.A. Koutsantonis, G.I. Jenkins, P.A. Schauer, B. Szczepaniak, B.W. Skelton,
C. Tan, A.H. White, Organometallics 28 (2009) 2195;
(
e) K.J. Kilpin, M.L. Gower, S.G. Telfer, G.B. Jameson, J.D. Crowley, Inorg. Chem.
0 (2011) 1123.
[7] (a) G.R. Desiraju, Angew. Chem., Int. Ed. 34 (1995) 2311;
5
(
(
(
b) A. Nangia, G.R. Desiraju, Top. Curr. Chem. 198 (1998) 57;
c) G.R. Desiraju, Angew. Chem., Int. Ed. 46 (2007) 8342;
d) P.-S. Cheng, S. Marivel, S.-Q. Zang, G.-G. Gao, T.C.W. Mak, Cryst. Growth
Acknowledgments
Des. 12 (2012) 4519.
[
8] (a) P. Pyykkö, Chem. Rev. 88 (1988) 563;
We gratefully acknowledge financial support by the Hong Kong
Research Grants Council (GRF CUHK 402710) and the Wei Lun
Foundation, and the award of a Postdoctoral Research Fellowship
to S.C.K. Hau by The Chinese University of Hong Kong.
(
(
b) P. Pyykkö, Chem. Rev. 97 (1997) 597;
c) P. Pyykkö, Chem. Soc. Rev. 37 (2008) 1967;
(d) S. Grimme, J.-P. Djukic, Inorg. Chem. 49 (2010) 2911;
e) J. Muñiz, C. Wang, P. Pyykkö, Chem. Eur. J. 17 (2011) 368.
9] V.W.W. Yam, W.K.M. Fung, K.K. Cheung, Angew. Chem., Int. Ed. 35 (1996) 1100.
(
[
[
[
10] (a) S.C.K. Hau, P.-S. Cheng, T.C.W. Mak, J. Am. Chem. Soc. 134 (2012) 2922;
(b) Y.-P. Xie, T.C.W. Mak, Angew. Chem., Int. Ed. 51 (2012) 8783;
Appendix A. Supplementary data
(
(
(
c) T.C.W. Mak, L. Zhao, Chem. Asian J. 2 (2007) 456;
d) T.C.W. Mak, L. Zhao, X.-L. Zhao, in: E.R.T. Tiekink, J. Zukerman-Schpector
Eds.), The Importance of Pi-Interactions in Crystal Engineering, Wiley,
CCDC 917554–917558 contains the supplementary crystallo-
graphic data for compounds 1–5. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: de-
posit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
Chichester, 2012, pp. 323–366 (Chapter 13).
11] (a) T. Zhang, J. Kong, Y. Hu, X. Meng, H. Yin, D. Hu, C. Ji, Inorg. Chem. 47 (2008)
3
(
144;
b) T. Zhang, H. Song, X. Dai, X. Meng, Dalton Trans. 38 (2009) 7688;
(c) T. Zhang, Y. Hu, J. Kong, X. Meng, X. Dai, H. Song, CrystEngComm 12 (2010)
027;
d) Y. Zhao, P. Zhang, B. Li, X. Meng, T. Zhang, Inorg. Chem. 50 (2011) 9097.
3
(
[
[
12] (a) T. Hu, T.C.W. Mak, Organometallics 31 (2012) 7539–7547;
(b) T. Hu, T.C.W. Mak, Organometallics, in press. http://dx.doi.org/10.1021/
om300988r.
13] (a) K. Campbell, C.J. Kuehl, M.J. Ferguson, P.J. Stang, R.R. Tykwinski, J. Am.
Chem. Soc. 124 (2002) 7266;
1
0.1016/j.poly.2013.02.020.
References
(
b) K. Campbell, C.A. Johnson II, R. McDonald, M.J. Ferguson, M.M. Haley, R.R.
[
1] (a) P. Braunstein, C. Frison, N. Oberbeckmann-Winter, X. Morise, A. Messaoudi,
M. Bénard, M.-M. Rohmer, R. Welter, Angew. Chem., Int. Ed. 43 (2004) 6120;
Tykwinski, Angew. Chem., Int. Ed. 43 (2004) 5967;
(c) M. Gholami, F. Melin, R. McDonald, M.J. Ferguson, L. Echegoyen, R.R.
Tykwinski, Angew. Chem., Int. Ed. 46 (2007) 9081;
(d) M. Gholami, M.N. Chaur, M. Wilde, M.J. Ferguson, R. McDonald, L.
Echegoyen, R.R. Tykwinski, Chem. Commun. (2009) 3038.
(
b) T.K. Ronson, T. Lazarides, H. Adams, S.J.A. Pope, D. Sykes, S. Faulkner, S.J.
Coles, M.B. Hursthouse, W. Clegg, R.W. Harrington, M.D. Ward, Chem. Eur. J. 12
(
(
2006) 9299;
c) D. Salazar-Mendoza, S.A. Baudron, M.W. Hosseini, Chem. Commun. (2007)
[14] K.C. Nicolaou, H. Zhang, J.S. Chen, J.J. Crawford, L. Pasunoori, Angew. Chem., Int.
Ed. 46 (2007) 4704.
[15] (a) N.N.P. Moonen, C. Boudon, J.-P. Gisselbrecht, P. Seiler, M. Gross, F.
Diederich, Angew. Chem., Int. Ed. 41 (2002) 3044;
2
252;
(
d) C. Fernádez-Cortabitarte, F. García, J.V. Morey, M. McPartlin, S. Singh, A.E.H.
Wheatley, D.S. Wright, Angew. Chem., Int. Ed. 46 (2007) 5425.
2] (a) M.I. Bruce, Chem. Rev. 91 (1991) 197;
[
[
(b) F. Mitzel, C. Boudon, J.-P. Gisselbrecht, P. Seiler, M. Gross, F. Diederich,
Chem. Commun. (2003) 1634;
(
1
b) H. Lang, D.S.A. George, G. Rheinwald, Coord. Chem. Rev. 206–207 (2000)
01;
(c) N.N.P. Moonen, W.C. Pomerantz, R. Gist, C. Boudon, J.-P. Gisselbrecht, T.
Kawai, A. Kishioka, M. Gross, M. Irie, F. Diederich, Chem. Eur. J. 11 (2005) 3325;
(d) Y.-L. Wu, F. Bureš, P.D. Jarowski, W.B. Schweizer, C. Boudon, J.-P.
Gisselbrecht, F. Diederich, Chem. Eur. J. 16 (2010) 9592.
[16] P.M. Donovan, L.T. Scott, J. Am. Chem. Soc. 126 (2004) 3108.
[17] W.L.F. Armarego, Purification of Laboratory Chemicals, Butterworth-
Heinemann, Oxford, 2003.
[18] G.M. Sheldrick, SADABS: Program for Empirical Absorption Correction of Area
Detector Data, University of Göttingen, Göttingen, Germany, 1996.
[19] G.M. Sheldrick, SHELXTL 5.10 for Windows Structure Determination Software
Programs, Bruker Analytical X-ray Systems, Inc., Madison, WI, 1997.
[20] G.-C. Guo, T.C.W. Mak, Chem. Commun. (1999) 813.
[21] (a) M. Munakata, L.P. Wu, T. Kuroda-Sowa, M. Maekawa, Y. Suenaga, G.L. Ning,
T. Kojima, J. Am. Chem. Soc. 120 (1998) 8610;
(
(
(
(
c) N.J. Long, C.K. Williams, Angew. Chem., Int. Ed. 42 (2003) 2586;
d) V.W.-W. Yam, J. Organomet. Chem. 689 (2004) 1393;
e) S.S.Y. Chui, M.F.Y. Ng, C.-M. Che, Chem. Eur. J. 11 (2005) 1739;
f) W.-Y. Wong, Coord. Chem. Rev. 251 (2007) 2400.
3] (a) C.P. McArdle, J.J. Vittal, R.J. Puddephatt, Angew. Chem., Int. Ed. 39 (2000)
819;
3
(
(
(
b) C.P. McArdle, M.C. Jennings, J.J. Vittal, R.J. Puddephatt, Chem. Eur. J. 7
2001) 3572;
c) C.P. McArdle, M.J. Irwin, M.C. Jennings, J.J. Vittal, R.J. Puddephatt, Chem.
Eur. J. 8 (2002) 723;
(
(
(
(
d) C.P. McArdle, S. Van, M.C. Jennings, R.J. Puddephatt, J. Am. Chem. Soc. 124
2002) 3959;
e) F. Mohr, M.C. Jennings, R.J. Puddephatt, Eur. J. Inorg. (2003) 217;
f) T.J. Burchell, M.C. Jennings, R.J. Puddephatt, Inorg. Chim. Acta 359 (2006)
(b) M. Munakata, L.P. Wu, G.L. Ning, T. Kuroda-Sowa, M. Maekawa, Y. Suenaga,
N. Maeno, J. Am. Chem. Soc. 121 (1999) 4968;
(c) M. Munakata, L.P. Wu, K. Sugimoto, T. Kuroda-Sowa, M. Maekawa, Y.
Suenaga, N. Maeno, M. Fujita, Inorg. Chem. 38 (1999) 5674;
(d) M. Munakata, G.L. Ning, Y. Suenaga, T. Kuroda-Sowa, M. Maekawa, T. Ohta,
Angew. Chem., Int. Ed. 39 (2000) 4555.
2
812;
(
g) N.C. Habermehl, D.J. Eisler, C.K. Kirby, N.L.-S. Yue, R.J. Puddephatt,
Organometallics 25 (2006) 2921.
4] (a) S. Barlow, D. O’Hare, Chem. Rev. 97 (1997) 637;
[
[
(
(
(
b) I.R. Whittal, A.M. McDonagh, M.G. Humphrey, Adv. Organomet. Chem. 42
1998) 291;
c) M.P. Cifuentes, M.G. Humphrey, J. Organomet. Chem. 689 (2004) 3968.
[22] S.-L. Zheng, M.-L. Tong, S.-D. Tan, Y. Yu Wang, J.-X. Shi, Y.-X. Tong, H.K. Lee, X.-
M. Chen, Organometallics 20 (2001) 5319.
[23] A.P. Côté, G.K.H. Shimizu, Inorg. Chem. 43 (2004) 6663.
[24] E.L. Elliott, G.A. Hernández, A. Lindenc, J.S. Siegel, Org. Biomol. Chem. 3 (2005)
407.
5] (a) M. Younus, A. Kohler, S. Cron, N. Chawdhury, M.R.A. Al-Madani, M.S. Khan,
N.J. Long, R.H. Friend, P.R. Raithby, Angew. Chem., Int. Ed. 37 (1998) 3036;
(
(
(
(
b) V.W.-W. Yam, Acc. Chem. Res. 35 (2002) 555;
c) Q.-H. Wei, L.-Y. Zhang, G.-Q. Yin, L.-X. Shi, Z.-N. Chen, J. Am. Chem. Soc. 126
2004) 9940;
[25] R. Cacciapaglia, S.D. Stefano, L. Mandolini, P. Mencarelli, F. Ugozzoli, Eur. J. Org.
Chem. (2008) 186.
d) H.-B. Xu, L.-X. Shi, E. Ma, L.-Y. Zhang, Q.-H. Wei, Z.-N. Chen, Chem.
[26] (a) Q.-M. Wang, T.C.W. Mak, Chem. Commun. (2002) 2682;
(b) L. Zhao, W.-Y. Wong, T.C.W. Mak, Chem. Eur. J. 13 (2007) 5927.
[27] (a) G.-C. Guo, G.-D. Zhou, T.C.W. Mak, J. Am. Chem. Soc. 121 (1999) 3136;
(b) G.-C. Guo, G.-D. Zhou, Q.-G. Wang, T.C.W. Mak, Angew. Chem. 110 (1998)
652;
Commun. (2006) 1601;
e) H.-B. Xu, J. Ni, K.-J. Chen, L.-Y. Zhang, Z.-N. Chen, Organometallics 27 (2008)
665;
f) H.-B. Xu, L.-Y. Zhang, J. Ni, H.-Y. Chao, Z.-N. Chen, Inorg. Chem. 47 (2008)
0744;
(
5
(
1
(c) G.-C. Guo, G.-D. Zhou, Q.-G. Wang, T.C.W. Mak, Angew. Chem., Int. Ed. 37
(1998) 630;
(d) Q.-G. Wang, T.C.W. Mak, J. Am. Chem. Soc. 123 (2001) 1501;
(e) Q.-M. Wang, T.C.W. Mak, Angew. Chem., Int. Ed. 40 (2001) 1130;
(f) Q.-M. Wang, T.C.W. Mak, Chem. Commun. (2001) 807.
(
(
g) H.-B. Xu, L.-Y. Zhang, X.-M. Chen, X.-L. Li, Z.-N. Chen, Cryst. Growth Des. 9
2009) 569.
[
6] (a) F. Paul, C. Lapinte, Coord. Chem. Rev. 178–180 (1998) 431;
(
(
b) V.W.-W. Yam, K.M.-C. Wong, Top. Curr. Chem. 257 (2005) 1;
c) S. Rigaut, C. Olivier, K. Costuas, S. Choua, O. Fadhel, J. Massue, P. Turek, J.Y.
Saillard, P.H. Dixneuf, D. Touchard, J. Am. Chem. Soc. 128 (2006) 5859;