Assembly of organosilver coordination frameworks with polycyclic benzenoid aromatic ethynide ligands

Article abstract of DOI:10.1016/j.jorganchem.2015.03.013

Abstract In a series of nine silver(I) complexes synthesized with ethynyl-functionalized condensed-ring benzenoid aromatics, the terminal ethynide group is invariably inserted into an argentophilic Ag_n (n = 4-5) basket, leading to the generation of coordination chains or multinuclear metallocycles via silver-aromatic interaction and strong face-to-face aromatic π-π stacking interaction. The coordination preferences of the ethynide ligand with respect to the size of the aromatic nucleus proved to be dominant factors in directing the construction of multi-dimensional organosilver(I) networks, which are consolidated by weak intermolecular interactions in supramolecular assembly.

Full text of DOI:10.1016/j.jorganchem.2015.03.013

Journal of Organometallic Chemistry 792 (2015) 123e133
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Assembly of organosilver coordination frameworks with polycyclic
benzenoid aromatic ethynide ligands
Sam C.K. Hau b, Thomas C.W. Mak a
a
,
, *
a
Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China
Department of Chemistry, Hong Kong Baptist University, Kowloon, Hong Kong, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 December 2014
Received in revised form
In a series of nine silver(I) complexes synthesized with ethynyl-functionalized condensed-ring benze-
noid aromatics, the terminal ethynide group is invariably inserted into an argentophilic Ag
basket, leading to the generation of coordination chains or multinuclear metallocycles via silverear-
omatic interaction and strong face-to-face aromatic stacking interaction. The coordination prefer-
n
(n ¼ 4e5)
13 March 2015
pep
Accepted 14 March 2015
Available online 24 March 2015
ences of the ethynide ligand with respect to the size of the aromatic nucleus proved to be dominant
factors in directing the construction of multi-dimensional organosilver(I) networks, which are consoli-
dated by weak intermolecular interactions in supramolecular assembly.
Dedicated to Prof. Mike Mingos on the
occasion of his 70th birthday.
© 2015 Elsevier B.V. All rights reserved.
Keywords:
Argentophilicity
Coordination framework
Polycyclic benzenoid aromatic ethynide
Organosilver complex
Introduction
Herein we report the synthesis of a series of six new polymeric
organosilver(I) complexes [AgL1]
n
(8), [AgL2]
n
n
(9), [AgL3] (10),
Over the past decades, our group and others have made use of
[AgL4] (11), [Ag L5] (12) and [Ag
n
2
n
2
L6] (13) AgL1eAg
n
2
L6 con-
the silver(I)eethynide [1] supramolecular synthon [2] ReC^CIAg
n
taining condensed-ring aromatic ethynides, which serve as pre-
cursors for the generation of nine crystalline complexes that
(
R ¼ alkyl, alicyclic [3], phenyl, heteroaryl [4], n ¼ 3e5) as a key
structure building unit (SUB) in the construction of high-nuclearity
clusters [5e7], as well as a wide variety of two- and three-
dimensional metaleorganic frameworks (MOFs) [7,8].
incorporate
AgL1$2.5AgCF
trifluoroacetate:
CO $1.5DMSO (1B), AgL2$3AgCF
CO $1.5DMSO (2B), 2(AgL3)$6AgCF
$4H O$2MeOH (4), 3(Ag L5)$13AgCF
L5$6AgCF $5H (6) and
AgL1$3AgCF
3
CO
2
$3H
2
O
(1A),
3
2
3
CO
2
$2H
2
O$MeCN
(2A), AgL2$2.5AgCF
2(AgL4)$6AgCF CO
CO $7H O$2MeOH
Ag L6$5AgCF CO
3
2
3 2
CO (3),
Recently, we reported new silver(I) trifluoroacetate or nitrate
complexes containing ligands each composed of either a phenyl or
heteroaryl nucleus [4] functionalized with a terminal ethynide
group, which in combination with other substituents like halo- [9],
cyano- [10], isocyano-groups [11] yielded a wide variety of crystal
structures. Besides this, crystallization of silver(I) complexes
generated with phenylethynide ligands and nitrate anions in DMSO
proved to be highly favorable for the assembly of argentophilic
layer-type structures [2d,2e,10]. To continue and extend this line of
investigation, we now focus on the utility of polycyclic benzenoid
ethynide ligands in combination with trifluoroacetate for crystal-
3
2
2
2
3-
2
2
(5),
Ag
2
3
CO
2
2
O
0
2
3
2
$3(2,2 -bipy) (7). On the basis of our previous
experience, dissolution of the crude starting materials in a
concentrated aqueous or mixed solution of water-soluble silver
salts is expected to generate MOFs stabilized by argentophilic and
multinuclear silver(I)eethynide bonding, and the aromatic nucleus
is potentially capable of partaking in silverearomatic and weak
pep stacking interactions.
Experimental
lization in either polar protic (H
DMSO). See Schemes 1 and 2.
2
O, MeOH) or aprotic solvents (THF,
All reagents and solvents used were reagent grade. Further
purification and drying followed the guidelines of Armarego when
necessary [12]. Organic solvents were concentrated under reduced
pressure on a rotary evaporator. Chromatographic purification of
*
Corresponding author. Fax: þ852 26035057.
E-mail address: tcwmak@cuhk.edu.hk (T.C.W. Mak).
http://dx.doi.org/10.1016/j.jorganchem.2015.03.013
022-328X/© 2015 Elsevier B.V. All rights reserved.
0

124
S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
General procedure for crystallization of silver ethynide complexes
1B and 2B) via slow liquid diffusion
(
AgCF
3
CO
2
(0.440 g, 2 mmol) was first dissolved in DMSO (1 mL),
(~30 mg) was then added to the solution.
and polymeric [AgC^CR]
n
After stirring until all solids had dissolved, the solution was filtered
and the filtrate transferred to a test tube. De-ionized water was
layered over the filtrate, which was stored in the dark. Crystals of
good quality were deposited after one week by slow liquid diffusion
of water into the filtrate.
2
Scheme 1. Structures of ligands HL1eH L6 that were designed and synthesized for
this study.
AgL1·3AgCF
Colorless needle crystals in ~90% yield. Anal. Calcd for
: C, 22.16; H,1.34, found C, 22.53; H,1.48. IR spectrum
3 2 2
CO ·3H O (1A)
18 4 9 9
C H13Ag F O
ꢁ1
(
KBr): 2000 cm (w,
n
C^C). Compound 1A decomposes above
ꢂ
220 C.
AgL1·2.5AgCF
Colorless plate-like crystals in ~35% yield. Anal. Calcd for
26: C, 25.87; H, 1.74, found C, 25.99; H, 1.97. IR
3 2
CO ·1.5DMSO (1B)
80 30 6
C H64Ag14F S O
ꢁ1
spectrum (KBr): 2012 cm (w,
n C^C). Compound 1B decomposes
ꢂ
above 220 C.
Scheme 2. General synthetic scheme for preparing polymeric silver salt AgL1.
AgL2·3AgCF
3
2 2
CO ·2H O·MeCN (2A)
Colorless block crystals in ~75% yield. Anal. Calcd for
the products was performed using Macherey Nagel Kieselgel 60M
C
1
20
H
14Ag
4
F
9
NO
8
: C, 24.05; H,1.41; N,1.40, found C, 23.73; H,1.70; N,
(
230e400 mesh). Thin-layer chromatography (TLC) was conducted
ꢁ1
.21. IR spectrum (KBr): 2002 cm (w,
composes above 220 C.
n
C^C). Compound 2A de-
on E. Merck silica gel 60 F254 (0.1 mm thickness) coated on
aluminum plates. Visualization of the developed chromatogram
was performed by a spray of 5% w/v dodecamolybdophosphoric
acid in ethanol and subsequent heating. Melting points (uncor-
rected) were measured with a Reichert apparatus.
ꢂ
AgL2·2.5AgCF
Colorless plate-like crystals in ~50% yield. Anal. Calcd for
: C, 26.07; H, 1.98, found C, 25.98; H, 1.88. IR
3 2
CO ·1.5DMSO (2B)
84 30 28 8
C H76Ag14F O S
ꢁ1
spectrum (KBr): 2018 cm (w,
n C^C). Compound 2B decomposes
ꢂ
above 220 C.
Synthesis of ligands (HL1 e H
2
L6) and preparation of their
polymeric silver salts as synthetic precursors
2
(AgL3)·6AgCF
AgCF CO (0.440 g, 2 mmol) was first dissolved in THF (3 mL),
and polymeric [AgL3] (~10 mg) was then added to the solution.
3 2
CO (3)
HL1eH
2
L6 were synthesized by the literature method [13] via
3
2
the Sonogashira coupling reaction between the corresponding
bromo-substituted aryl compounds and trimethylsilylacetylene
followed by desilylation with K CO in methanol.
2 3
n
After stirring until all solids had dissolved, the solution was filtered
and the filtrate placed in a desiccator filled with de-ionized water,
which was stored in the dark. Red needle crystals of good quality
were deposited in ~30% yield after three days by slow liquid
[
[
AgL1]
Ag L6]
In a 100 mL round bottom flask, silver nitrate (1 mmoL) was
n
(8), [AgL2]
n
(9), [AgL3]
n
(10), [AgL4]
n
(11), [Ag
2
L5]
n
(12),
diffusion of water into the filtrate. Anal. Calcd for C88H36Ag15F36O24
:
2
n
(13)
C, 27.97; H, 0.96, found C, 28.03; H, 1.08. IR spectrum (KBr):
ꢁ
1
ꢂ
n C^C). Compound 3 decomposes above 180 C.
2024 cm (w,
added to a solution of acetonitrile (40 mL) containing an equimolar
amount of the ethynyl-substituted aryl compound, and triethyl-
amine (1 mmoL) was subsequently added with vigorous stirring for
2
(AgL4)·6AgCF
3 2 2
CO ·4H O·2MeOH (4)
Yellow block-like crystals in ~70% yield. Anal. Calcd for
2
h. The resulting yellow precipitate was collected by filtration and
C
50
H32Ag
8
F
18
O
18: C, 28.25; H, 1.52, found C, 28.34; H, 1.48. IR
washed thoroughly with acetonitrile (2 ꢀ 20 mL) and de-ionized
ꢁ1
spectrum (KBr): 2036 cm (w,
above 200 C.
n C^C). Compound 4 decomposes
ꢁ
ꢁ1
1
water (3 ꢀ 10 mL). IR spectrum (KBr,
n
C^C, w): 2006 cm (8);
ꢂ
ꢁ
1
ꢁ1
ꢁ1
1
999 cm (9); 2014 cm (10); 2020 cm (11); 2023 cm (12);
ꢁ1
2
025 cm (13).
3
(Ag
Yellow plate-like crystals in ~65% yield. Anal. Calcd for
34: C, 20.68; H, 1.08, found C, 21.23; H, 1.14. IR
2 3 2 2
L5)·13AgCF CO ·7H O·2MeOH (5)
C
74 39 2
H46Ag19F N O
General procedure for crystallization of silver ethynide complexes
1A, 2A, 4 e 7) via solvent evaporation
ꢁ1
spectrum (KBr): 2020 cm (w,
above 180 C.
n C^C). Compound 5 decomposes
(
ꢂ
AgCF
mixture of deionized water (1 mL) and acetonitrile (0.2 mL) or
methanol (1 mL). Polymeric [AgC^CR] (~30 mg) or [Ag (C^C) R]
~20 mg) was then added to the solution. After stirring until all
solids had dissolved, the solution was filtered and the filtrate stored
in the dark. After a week, crystals of good quality were deposited.
3 2 4
CO (0.440 g, 2 mmol) and AgBF were dissolved in a
Ag
2
L5·6AgCF
Yellow needle crystals in ~45% yield. Anal. Calcd for
26 8 18
C H16Ag F O17: C, 17.30; H, 0.89, found C, 17.66; H, 0.93. IR spec-
3 2 2
CO ·5H O (6)
n
2
2
n
(
ꢁ
1
trum (KBr): 2012 cm (w,
180 C.
n
C^C). Compound 6 decomposes above
ꢂ

S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
125
0
Ag
2
L6·5AgCF
3
CO
2
·3(2,2 -bipy) (7)
respectively, which are necessary for the formation of the
ReC^CIAg supramolecular synthon, where n can be as high as 4
or 5 [16,17].
The general preparative procedure was employed with the
addition of 2,2 -bipyridyl (~30 mg). Yellow plate-like crystals in
n
0
~
7 18
60% yield. Anal. Calcd for C110H15Ag F O15: C, 49.42; H, 0.57, found
ꢁ1
C, 48.70; H, 0.64. IR spectrum (KBr): 2018 cm (w,
pound 7 decomposes above 180 C.
n C^C). Com-
Description of crystal structures
ꢂ
AgL1·3AgCF
3 2 2
CO ·3H O (1A)
X-ray crystallography
In the crystal structure of 1A, the ethynide moiety C1^C2 is
bound to a square-pyramidal Ag
mode, and each of three independent aqua ligands is coordinated to
one or two silver atoms (O1WeAg4; O2WeAg4; O3WeAg1;
O3WeAg3) (Fig. 1a). As shown in Fig. 1b, two adjacent baskets are
fused through edge-sharing (Ag2eAg2B) to engender a Ag
aggregate, which is further stabilized by offset face-to-face
stacking interactions (inter-centroid distance: ring I/ring II ,
1
1 1 1 2
5
basket in the
m
5
h ,h ,h ,h ,h
ꢁ
Selected crystals were used for data collection on a Bruker AXS
Kappa ApexII Duo diffractometer at 296K (1Ae2B) and 173K (3e7)
using frames of oscillation range 0.3 , with 2
empirical absorption correction was applied using the SADABS
program [14]. The structures were solved by the direct method and
refined by full-matrix least-squares on F using the SHELXTL pro-
gram package [15]. The crystallographic data are summarized in
Table 1.
ꢂ
ꢂ
ꢂ
< q < 28 . An
8
pe
p
0
2
3.635(2) Å).
Such Ag
8
aggregates are interconnected through silverearomatic
interaction (Ag3A/Ccent of the C8eC9 edge in the naphthyl ring,
2.487(5) Å, under the standard value of 2.9 Å [18e23]) to generate an
infinite coordination silvereorganic chain along the c-axis (Fig. S1 in
the Supporting Information). Adjacent chains are inter-associated
through Hebonding interactions between aqua ligands and coor-
dinated trifluoroacetate groups (O3WA$$$O1B, 2.83(4) Å;
O3WA$$$O3B, 2.87(5) Å) to form a grid-like supramolecular layer
(Fig. 2a) and such layers are linked through additional Hebonding
(O1W/O2WC, 2.85(7) Å; O4/O2WC, 2.90(6) Å) to produce a 3D
supramolecular network (Fig. 2b).
Results and discussion
The polymeric crude materials [AgL1] (8), [AgL2]
n
n n
(9), [AgL3]
(
10), [AgL4] (11), [Ag L5] (12), [Ag L6] (13) were synthesized
n
2
n
2
n
from the reaction between the corresponding condensed-ring ar-
omatic ethynide compounds and silver trifluoroacetate in the
presence of triethylamine. These precursors were then each dis-
solved in a concentrated solution of AgCF
ver(I) ion concentration and provide the auxiliary CF CO ligand,
3
CO
2
to increase the sil-
ꢁ
3
2
Table 1
Crystallography data and structure refinement parameters of complex 1Ae7.
Complex
1A
1B
2A
2B
3
Structural formula
Formula wt.
Crystal system
Space group
a [Å]
C
18
H
13Ag
975.76
Monoclinic
4
F
9
O
9
C
80
H
64Ag14
F
30
S
6
O
26
C
20
H
14Ag
998.80
Monoclinic
4
F
9
NO
8
C
84
H
76Ag14
F
30
O
28
S
8
C
88 36 24
H36Ag15F O
3713.85
Triclinic
3870.11
Monoclinic
P2 /n (No. 14)
1
3779.22
Orthorhombic
Fddd (No. 70)
28.054 (19)
37.705 (3)
39.873 (3)
90.0
90.0
90.0
42175.0 (5)
16
2.381
C2/c (No. 15)
23.713 (15)
14.543 (9)
15.922 (10)
90.0
106.473 (10)
90.0
5265.5 (6)
8
2.462
3.040
0.0316
0.0888
P1 (No. 2)
14.535 (6)
16.662 (7)
24.993 (11)
89.127 (10)
89.695 (10)
65.663 (9)
5515.0 (4)
2
2.237
2.654
0.0872
0.2674
C2/c (No. 15)
22.816 (8)
16.211 (6)
15.502 (6)
90.0
103.499 (10)
90.0
5575.4 (4)
8
2.380
2.873
0.0367
0.0963
16.825 (8)
25.883 (13)
27.026 (14)
90.0
94.339 (10)
90.0
11736.0 (10)
4
2.190
2.535
0.0680
0.2180
1.074
b [Å]
c [Å]
a
b
g
[Å]
[Å]
[Å]
3
V [Å ]
Z
ꢁ
r
c
[g cm 3]
m
[mmꢁ1]
2.848
0.0695
0.1743
1.113
a
R
1
(I > 2
s
)
b
wR
GOF
2
(all data)
1.055
1.029
1.041
Complex
4
5
6
7
Structural formula
Formula wt.
Crystal system
Space group
a [Å]
C
50
H
32Ag
2125.72
Monoclinic
8
F
18
O
18
C
74
H
46Ag19
F
39
2
N O
34
C
26
H
16Ag
8
F
18
O
17
110 7 18 15
C H15Ag F O
4297.66
Triclinic
P1 (No. 2)
1805.35
Triclinic
P1 (No. 2)
13.852 (7)
13.865 (7)
14.160 (7)
68.321 (10)
61.831 (10)
63.282 (10)
2098.4 (18)
2
2673.34
Triclinic
P1 (No. 2)
P2/c (No. 13)
15.654 (11)
16.916 (12)
24.257 (2)
90.0
109.357 (2)
90.0
6060.2 (8)
4
2.330
2.653
0.0405
0.1195
14.012 (11)
14.372 (11)
26.856 (2)
75.347 (2)
82.750 (2)
82.177 (2)
5159.8 (7)
2
2.766
3.662
0.0392
0.1045
12.430 (11)
14.907 (15)
17.988 (17)
92.535 (2)
106.619 (2)
104.284 (2)
3071.4 (5)
1
2.177
2.296
0.0586
0.1591
b [Å]
c [Å]
a
b
g
[Å]
[Å]
[Å]
3
V [Å ]
Z
r
c
[g cmꢁ3]
2.857
3.800
0.0441
0.1206
m
[mmꢁ1]
a
R
1
(I > 2
s
)
b
wR
GOF
2
(all data)
1.147
1.036
1.083
1.081
Space group P2
1
/n is equivalent to standard P2
1
/c by an axial transformation.
P
P
a
R
1
¼
jjF
o
j ꢁ jF
c
jj= jF
o
j:P
P
b
2
2
2
2
2
1=2
wR
2
¼ f ½wðF ꢁ F Þ ꢃ= ½wðF Þ ꢃg
:
o
c
o

126
S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
Fig. 1. a) Perspective view of coordination geometry in double salt AgL1 $ 3AgCF
.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of the Ag
stacking interaction. Symmetry code: A: 1 ꢁ x, 1 ꢁ y, 1 ꢁ z, B: 1 ꢁ x, y, 1.5 ꢁ z, C: x, 1 ꢁ y, 0.5 þ z. In this and all other figures, silver atoms coordinated by independent ethynide
ligands are shown in purple, and the hydrogen and fluorine atoms are omitted for clarity.
3
CO
2
$ 3H
2
O (1A). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2
8
aggregate, showing all notable offset face-to-face
pep
AgL1·2.5AgCF CO
3 2
·1.5DMSO (1B)
8
Supporting Information). Such adjacent Ag aggregates are linked
In the crystal structure of 1B, there are four crystallographically
independent L1 anions. The ethynide moieties C1^C2 and C13^C14
to furnish an infinite chain along the c-axis. Silver atom Ag3 is
bound to the center of an edge (C8AꢁC9A) of the naphthyl ring of a
neighboring chain at 2.508(5) Å, which together with their
centrosymmetrically-related moiety constitute a silvereorganic
1
2
2
2
are each inserted to a butterfly-shaped Ag
4
basket in
coordination modes, respectively; while the
remaining two ethynide groups C25^C26 and C37^C38 are both
m
4
ꢁ
h ,h ,h ,h
1
1
2
2
and
m
4
h ,h ,h ,h
ꢁ
cycle. The silvereorganic chains are further consolidated by
1
1
1
2
2
0
bound to a square-pyramidal Ag
coordination mode, as shown in Fig. 3a. The four different Ag
Ag
Ag7) and edge (Ag10eAg11) sharing. Such Ag15 aggregates are
5
basket in the
m
5
ꢁ
h
,
h
,h
,
h
,
h
continuous
pe
p
stacking (inter-centroid distance: ring I/ring I ,
0
4
and
3.905(2) Å, ring II/ring II , 3.966(1) Å) of parallel naphthyl rings
(Fig. 5b).
5
segments coalesce to generate a Ag15 aggregate through vertex
(
Adjacent chains in a pseudo-hexagonal array are interconnected
by additional Hebonds (O4/O2WA, 2.93(7) Å; O1/O1WB, 2.78(4)
Å; O3/O1WB, 2.84(5) Å) to produce a three-dimensional supra-
molecular network (Fig. 6 and Fig. S3b in Supporting Information).
further fused together through argentophilic interaction to form an
infinite silver(I) chain along the a-axis, which is further consoli-
dated by
m
1
ꢁcoordinated (S4 and S6) and
m
2
ꢁcoordinated (S1, S2,
S3 and S5) DMSO ligands (Fig. S2 in Supporting Information).
Such chain is further stabilized with segmented offset face-to-
AgL2·2.5AgCF CO ·1.5DMSO (2B)
3
2
face
p
e
p
stacking (inter-centroid distance: ring I/ring IV,
Similar to 1B, there are four crystallographically independent L2
anions coordinated to a Ag15 aggregate with different coordination
modes. The ethynide moieties C1^C2 and C25^C26 are each capped
3
.760(1) Å, ring III/ring V, 3.697(1) Å, ring IV/ring VI, 3.799(1) Å,
0
0
ring VII/ring I , 3.758(2) Å, ring VIII/ring II , 3.610(2) Å) between
naphthyl rings, which are lying on one side (Fig. 4a).
As shown in Fig. 4b these silver(I) chains are arranged in a
pseudo-hexagonal array and are packed by van der Waals inter-
action in the crystal structure.
1
2
2
2
by
a
butterfly-shaped Ag4 basket in
m
4
ꢁ
h
,
h
,
h
,
h
and
coordination modes, respectively, and the other two
ethynide groups C13^C14 and C37^C38 are each bound to a square-
1
1
2
2
m
4
h ,h ,h ,h
ꢁ
1
1 1 1 2
pyramidal Ag5 basket in
shown in Fig. 7a.
m5ꢁh ,h ,h ,h ,h coordination mode, as
AgL2·3AgCF
3
CO
2
·2H
2
O·MeCN (2A)
Such Ag15 aggregates are fused together through sharing one
silver atom (Ag1) to form an infinite silver(I) chain along the a-axis,
which is further stabilized by discontinuous pairwise offset face-to-
The ethynide moiety (C1^C2) of ligand L2 is encapsulated within
1
1
1
2
2
a Ag
illustrated in Fig. 5a. Two adjacent Ag
edge-sharing (Ag2eAg2B) to generate a Ag
5
basket in the
m
5
ꢁh
,
h
,
h
,
h
,h
coordination mode in 2A, as
baskets are connected by
aggregate (Fig. S3a in
5
face
pep stacking interactions (inter-centroid distances ring
0
8
II/ring VII , 3.666(1) Å; ring III/ring VI, 3.719(1) Å) between
Fig. 2. a) Perspective view of silver(I) layer in 1A along the a-axis. b) Perspective view of the crystal packing in 1A, showing all notable Hebonding and
Symmetry code: A: 1 ꢁ x, 1 ꢁ y, 1 ꢁ z, B: x, ꢁ1 þ y, z, C: 0.5 ꢁ x, 1.5 ꢁ y, 1 ꢁ z.
pep stacking interaction.

S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
127
Fig. 3. a) Perspective view of coordination geometry in double salt AgL1$2.5AgCF
.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver chain along the c-axis. Symmetry code:
A: 1 þ x, ꢁ1 þ y, z.
3 2
CO $1.5DMSO (1B). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2
Fig. 4. a) Perspective view of silver(I) layer in 1B, showing all notable
pep stacking interaction. b) Perspective view of the crystal packing in 1B.
Fig. 5. a) Perspective view of coordination geometry in double salt AgL2$3AgCF
CO
3 2
$2H
2
O$MeCN (2A). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver chain along the c-axis. Symmetry code:
A: 1 þ x, ꢁ1 þ y, z; B: 1 ꢁ x, y, 1.5 ꢁ z.
naphthyl rings lying on one side (Fig. 7b). Further stability is pro-
vided by ecoordinated (S2, S6 and S7) and ecoordinated (S1,
mode, as shown in Fig. 9a. Through sharing vertex silver atom Ag4,
two Ag segments coalesces to generate a Ag aggregate. Peripheral
4 7
m
1
m
2
S3, S4, S5 and S8) DMSO ligands (Fig. S4 in Supporting Information).
Adjacent infinite silver(I) chains are interconnected by weak
CeH/F interaction between DMSO ligands and nearby tri-
fluoroacetate groups (C81AeH/F10B, 2.52(1) Å; C82AeH/F14B,
silver atoms Ag8 and Ag9 are attached to this Ag7 segment by
1
2
2
different pairs of trifluoroacetate groups (Ag8 by O1^O2 in
and O7^O8 in coordination modes; Ag9 by O9^O10 in
and O11^O12 in
m
3
ꢁ
h
,
,
h
1
m
1
m
3
ꢁ
h
h
2
m
2
h coordination modes).
ꢁ
2
(
.57(2) Å) (Fig. 8a), and also between trifluoroacetate and L2
C8eH/F10C, 2.64(1) Å) (Fig. 8b) to yield a three-dimensional
supramolecular network.
With successive two-fold axes located at the Ag1 and Ag6,
adjacent Ag segments are linked together to yield an infinite silver
7
ribbon (Fig. S5a in Supporting Information), which is further
consolidated by significant silverearomatic interaction (Ag2A/C-
cent of C5eC6, 2.490(1) Å; Ag7B/Ccent of C30eC31, 2.525(1) Å),
2
(AgL3)·6AgCF
In 3, there are two crystallographically independent L3 anions.
The ethynide moieties C1^C2 and C17^C18 are each encapsulated by
3 2
CO (3)
along with off-set face-to-face
pep stacking interaction (ring
II/ring V, 3.562(2) Å) between phenyl rings of adjacent ligands
(Fig. 9b).
1
1
2
2
a butterfly-shaped Ag
4
basket in the
m
4
ꢁ
h
,h
,h
,h
coordination

128
S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
Fig. 6. a) Perspective view of silver(I) layer in 2A, showing all notable hydrogen bonds. b) Perspective view of the crystal packing in 2A, showing all notable hydrogen bonds.
Symmetry code: A: 0.5 ꢁ x, 1.5 ꢁ y, 1 ꢁ z; B: 1 ꢁ x, 2 ꢁ y, 1 ꢁ z; C: 1 ꢁ x, y, 1.5 ꢁ z; D: x, 2 ꢁ y, ꢁ0.5 þ z.
Fig. 7. a) Perspective view of coordination geometry in double salt AgL2$2.5AgCF
.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver chain along the a-axis. Symmetry code:
A: ꢁ1 þ x, y, z.
3 2
CO $1.5DMSO (2B). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2
Fig. 8. a) Perspective view of silver(I) layer in 2B, showing all notable weak CeF/H bond. b) Perspective view of the crystal packing in 2B, showing all notable weak CeF/H bond.
Symmetry code: A: 1 þ x, y, z; B: 1.5 ꢁ x, ꢁ0.5 þ y, 0.5 ꢁ z; C: 0.5 þ x, 1.5 ꢁ y, 0.5 þ z.
Fig. 9. a) Perspective view of coordination geometry in double salt 2(AgL3)$6AgCF
Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver chain along the a-axis. Symmetry code: A: 0.75 ꢁ x, y,
.75 ꢁ z; B: 1.25 ꢁ x, 1.25 ꢁ y, z; C: ꢁ0.5 þ x, 1.25 ꢁ y, 0.75 ꢁ z.
3 2
CO (3). The argentophilic Ag/Ag distances shown as thick rods lie in the range 2.70e3.40 Å.
0

S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
129
Fig. 10. a) Perspective view of the centrosymmetric silvereorganic cyclic structure in 3. b) Perspective view of the crystal packing in 3, showing all notable CeH/F bonding
between coordination layers. Symmetry code: A: 1.25 ꢁ x, 1.25 ꢁ y, z; B: 1.25 ꢁ x, ꢁ0.5 þ y, 0.75 ꢁ z; C: 0.5 þ x, 1.25 ꢁ y, 0.75 ꢁ z; D: 0.5 þ x, ꢁ0.5 þ y, z; E: 0.75 ꢁ x, y, 0.75 ꢁ z;
F: ꢁ0.25 þ x, ꢁ0.25 þ y, 1 ꢁ z; G: 0.25 þ x, 1 ꢁ y, 0.25 þ z; H: 1 ꢁ x, 1 ꢁ y, 1 ꢁ z.
Two neighboring ribbons are interconnected by a pair of
inversion-related [Ag (CF CO ] units to yield a centrosymmetric
silvereorganic cycle (Fig. 10a and Fig. S5b in Supporting
Information). Such cyclic structures are interconnected to pro-
duce a coordination layer along the ab plane (Fig. S6a in Supporting
offset face-to-face
p
e
p
stacking interaction between pyrene rings
0
4
3
2
)
4
(inter-centroid distance: ring I/ring VI , 3.717(2) Å, ring II/ring
0
0
III , 3.613(2) Å, ring IV/ring VIII, 3.845(3) Å, ring V/ring VIII ,
0
3.925(2) Å, ring VI/ring VII , 3.622(2) Å).
Such silvereorganic chains are interconnected through addi-
tional Hebonding between aqua ligands and trifluoroacetate
groups (O2W/O7A, 2.77(1) Å; O2W/O9A, 2.78(9) Å; O3WA/O1,
2.79(1) Å; O3WA/O3, 2.80(7) Å) (Fig. S7 in Supporting
Information), and also between methanol and aqua ligands
(O4WA/O14B, 2.76(1) Å), to yield a three-dimensional supramo-
lecular network (Fig. 12b).
Information), which is further consolidated by continuous
pep
stacking interaction between phenyl rings of L3 (Fig. S6b in
Supporting Information). Inter-association of neighboring layers
through weak CeH/F bonding between L3 ligands and tri-
fluoroacetate groups (C8GeH/F17A, 2.58(2) Å; C13HeH/F17A,
2
.70(2) Å; C28GeH/F18A, 2.67(1) Å) generates a supramolecular
network (Fig. 10b).
3
(Ag
Complex 5 contains three crystallographic independent ligands
L5 with six ethynide moieties that exhibit different coordination
2 3 2 2
L5)·13AgCF CO ·7H O·2MeOH (5)
2
(AgL4)·6AgCF
As shown in Fig. 11a, the ethynide moieties C1^C2 and C19^C20
of two crystallographically independent ligand L4 are each capped
by a butterfly-shaped Ag segment, which includes symmetry-
3 2 2
CO ·4H O·2MeOH (4)
1
1
2
2
modes (Fig.13a): C1^C2 and C12^C13 taking the
and the remaining ethynide moieties are each bound to either a
m
4
ꢁh ,h ,h ,h mode
5
related silver atoms Ag2A and Ag6B. Silver atom Ag4 is bonded to
the edge of an adjacent pyrene ring (C28eC29) with a bond dis-
tance of 2.486(8) Å, while Ag7 is similarly involved in silver-
earomatic interaction (Ag7/Ccent of C10eC11, 2.537(8) Å). As a
result, a silvereorganic cycle is generated with a pseudo inversion
center between Ag4 and Ag7.
pyramidal Ag
5
basket or butterfly-shaped Ag
4
basket but in
1
1
1
2,
2
different ways (C15^C16, C40^C41 in
m
5
ꢁ
h
,
h
,
h
,
h
h
, C29^C30 in
1
1
1
1
1 1 1 1 2
m
4
ꢁh
,
h
,
h
,
h
, and C26^C27 in
m
5
h ,h ,h ,h ,h ). Furthermore, such
ꢁ
silvereethynide aggregates coalesce to yield a Ag18 segment
through sharing silver atoms Ag5, Ag6, Ag7, Ag10, Ag12 and Ag15
via argentophilic interaction, and further stabilization is provided
With successive two-fold axes located at the center between
Ag2 and Ag2A, and also between Ag6 and Ag6B, two adjacent
by offset face-to-face pep stacking between phenyl rings (inter-
centroid distance: ring II/ring III, 3.609(2) Å). Adjacent Ag18 ag-
gregates are interlinked through argentophilic interaction to
generate an infinite silver ribbon along the a-axis (Fig. 13b).
Adjacent ribbons are interconnected through symmetry-related
symmetry-related Ag
sharing to engender a Ag
5
aggregates coalesce together through edge-
segment (Fig. 11b). Such Ag segments
8
8
are inter-associated through silverearomatic interaction to
generate an infinite silvereorganic coordination double chain along
the a-axis (Fig. 12a), which is further consolidated by continuous
pairs of
2
m ecoordinated aqua ligands (O6W and O6WB) with an
inversion center located between Ag18A and Ag18B to yield a
Fig. 11. a) Perspective view of coordination geometry in double salt 2(AgL4)$6AgCF
.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver chain along the a-axis. Symmetry code:
A: 1 ꢁ x, y, 1.5 ꢁ z; B: 2 ꢁ x, y, 1.5 ꢁ z.
3 2 2
CO $4H O$2MeOH (4). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2

130
S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
Fig. 12. a) Perspective view of the infinite double silvereorganic coordination chain in 4. b) Perspective view of the crystal packing in 4, showing all notable hydrogen bonds.
Symmetry code: A: 2 ꢁ x, y, 1.5 ꢁ z; B: 1 ꢁ x, y, 1.5 ꢁ z; C: ꢁ1 þ x, y, z; D: x, 1 ꢁ y, ꢁ0.5 þ z; E: ꢁ1 þ x, 1 ꢁ y, ꢁ0.5 þ z.
coordination layer (Fig. 14a), which is consolidated by additional
Hebonds with aqua and methanol ligands (O3W/O7, 2.79(1) Å;
O3W/O23, 2.71(1) Å; O4W/O9, 2.80(1) Å; O4W/O25, 2.75(1) Å;
O6W/O24, 2.75(1) Å; O6W/O27, 2.72(1) Å; O7W/O8B, 2.75(1)
Å; O27/O10B, 2.76(1) Å; O27/O28C, 2.82(2) Å; O20/O5W,
AgCF
3 2 8
CO . The two ethynide groups of L5 are attached to a Ag
aggregate including one symmetry-related Ag7A in the
1
1
1
2
2
1 1 1 1 2
m
5
ꢁ
h
,
h
,
h
,
h
,h
(C1^C2) and
respectively (Fig. 15a). A peripheral silver atom Ag8 is connected to
the Ag segment through a pair of trifluoroacetate groups (O1^O2
m
5
ꢁ
h
,
h
,
h
,
h
,
h
(C13^C14) modes,
8
2
.84(1) Å; O5W/O11A, 2.82(2) Å; O1W/O19, 2.87(1) Å) (Fig. S8 in
and O5^O6) and also coordinated by two aqua ligands (O4W and
Supporting Information). Weak hydrogen bonding between aqua
ligands and trifluoroacetate groups (O2WC/O21, 2.73(1) Å;
O2W/O2WC, 2.72(1) Å) then generates a three-dimensional su-
pramolecular network (Fig. 14b).
O5W). With a two-fold axis located at the inversion center between
Ag7 and Ag7A, two symmetry-related Ag
to form a Ag14 segment (Fig. 15b).
8
aggregates are coalesced
Such Ag14 segments are interconnected through pairs of
inversion-related trifluoroacetate groups (O1^O2 and O1A^O2A;
O3^O4 and O3A^O4A) and aqua ligands (O1W and O1WB) to form a
closely knitted coordination layer (Fig. 16a), which is further sta-
bilized by weak Hebonding between trifluoroacetate and aqua
ligand (O1W/O9, 2.73(1) Å; O1W/O5W, 2.87(1) Å; O7/O3WA,
Ag
2
L5·6AgCF
Unlike 5, which is crystallized from slow evaporation of a
saturated methanol solution, complex 6 is obtained from slow
evaporation of a saturated aqueous solution of Ag L5 with
3 2 2
CO ·5H O (6)
2
2 3 2 2
Fig. 13. a) Perspective view of coordination geometry in double salt 3(Ag L5)$13AgCF CO $7H O$2MeOH (5). The argentophilic Ag/Ag distances shown as thick rods lie in the
range 2.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of an infinite silver ribbon along the a-axis.
Symmetry code: A: 1 þ x, y, z; B: ꢁ1 þ x, y, z.
Fig. 14. a) Perspective view of the coordination layer in 5. b) Perspective view of the crystal packing in 5, showing all notable hydrogen bonds. Symmetry code: A: 1 þ x, y, z; B: ꢁx,
2
ꢁ y, ꢁz; C: 1 ꢁ x, 1 ꢁ y, 1 ꢁ z; D: ꢁ1 þ x, y, z.

S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
131
2 3 2 2
Fig. 15. a) Perspective view of coordination geometry in double salt 3(Ag L5)$13AgCF CO $7H O$2MeOH (5). The argentophilic Ag/Ag distances shown as thick rods lie in the
range 2.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of the Ag14 segment in 5. Symmetry code: A: ꢁx,
3
ꢁ y, ꢁz.
2
.71(1) Å; O2W/O8A, 2.87(1) Å; O5W/O3WA, 2.76(1) Å;
C
cent of C53eC54/Ccent of C43eC44, 3.828(3) Å;
N2eC30/Ccent of C36AeC35A, 3.486(3) Å; Ccent of N1eC29/Ccent
of C39AeN3A, 3.363(2) Å; cent of C35AeC36A/Ccent of
Ccent of
O3W/O12, 2.71(1) Å) (Fig. S9a in Supporting Information). Sub-
sequently, neighboring layers are linked by hydrogen bonding be-
tween the trifluoroacetate and aqua ligands (O3/O4WC, 2.83(1) Å;
O11B/O4WC, 2.64(1) Å; O7A/O3WB, 2.71(1) Å; O5WA/O3WB,
C
C49AeN5A, 3.615(2) Å; Ccent of C35AeC36A/Ccent of C49AeC48A,
3.600(2) Å) yields a three dimensional supramolecular network
(Fig. S10 in Supporting Information).
2
.76(1) Å) to construct a 3D supramolecular network (Fig. 16b and
Fig. S9b in Supporting Information).
Structure-correlation relationship
0
Ag
2
L6·5AgCF CO
3 2
·3(2,2 -bipy) (7)
In the crystal structure of 7, the two ethynide moieties of a
The series of nine crystalline complexes reported herein reaf-
disordered L6 ligand are each capsulated by a butterfly-shaped Ag
4
firms the general utility of the silvereethynide supramolecular
1
1 1 2
basket via the same coordination mode (
m
4
ꢁ
h
,
h
,
h
,
h
) (Fig. 17a).
synthon ReC^CIAg
n
(n ¼ 4, 5) in coordination network assembly.
Two adjacent Ag segments are joined to yield a Ag
4
7
aggregate
Except for 1B, which exists as an infinite coordination chain, all
complexes form three-dimensional supramolecular network
structures. Silver(I)echain formation is facilitated by multinuclear
AgeC and argentophilic interaction in 1A, 1B, 2A and 2B, and such
through sharing the same vertex Ag4 silver atom. With an inversion
center located at the center between Ag2 and Ag2A, and between
Ag7 and Ag7A, a centrosymmetric metaleorganic cycle is gener-
ated containing two independent L6 ligands, which are held tightly
chain structures are further consolidated by aromatic
pep stacking
to each other through offset face-to-face
p
e
p
stacking interaction
interaction. In complex 3, continuous offset face-to-face pep
stacking between anthracenyl rings was found to be a dominant
factor of layer-structure construction. Upon switching to the steri-
cally bulkier pyrene nucleus in 4, enhanced pep stacking leads to
dimeric units in a loosely packed coordination chain via silver-
earomatic interaction.
In addition, formation of a coordination layer structure through
silvereethynide bonding in complexes 5 and 6 is favored by ligand
L5, which has two proximal and parallel ethynide groups attached
to the 1,8-positions of its napthylene nucleus. On the other hand,
when the two terminal ethynide groups of L6 bear an anti rela-
0
(
inter-centroid distances ring I/ring II , 3.566(3) Å) (Fig. 17b). In
0
addition, the structure is stabilized by chelation of 2,2 -bipyridyl
ligands to silver atoms (N1^N2 to Ag2; N3^N4 to Ag5; N5^N6 to
Ag7).
Such silvereorganic cycles are inter-associated through weak
Hebonding between trifluoroacetate groups and methanol mole-
cules (O1W/O11A, 2.76(1) Å; O2/O11, 2.74(1) Å) to generate a
supramolecular layer structure (Fig. 18a). Interconnection between
0
neighboring layers by edge-to-edge
pe
p
stacking between 2,2 -
bipyridyl ligands (Ccent of N3eC35/Ccent of N5eC45, 3.787(3) Å;
cent of C37eC38/Ccent of N1eC25, 3.751(3) Å;
C
Ccent of
tionship, face-to-face pep stacking interaction occurs in 7. Conse-
C38eC39/Ccent of C25eC26, 3.749(3) Å; Ccent of N6eC50/Ccent of
N4eC40, 3.785(3) Å; Ccent of N6eC54/Ccent of N4eC44, 3.567(3) Å;
quently, a centrosymmetric silvereorganic cycle is generated with
protection from the attached 2,2 -bipyridyl ligands. Furthermore,
0
Fig. 16. a) Perspective view of a closely-knitted coordination layer structure in 6. b) Perspective view of the crystal packing in 6, showing all notable hydrogen bonds. Symmetry
code: A: ꢁx, 3 ꢁ y, ꢁz; B: 1 ꢁ x, 3 ꢁ y, ꢁ1 ꢁ z; C: ꢁx, 4 ꢁ y, ꢁ1 ꢁ z; D: x, 1 þ y, ꢁ1 þ z.

132
S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
0
Fig. 17. a) Perspective view of coordination geometry in double salt Ag
2
L6$5AgCF
3
CO
2
$3(2,2 -bipy) (7). The argentophilic Ag/Ag distances shown as thick rods lie in the range
2.70e3.40 Å. Silver atoms are drawn as thermal ellipsoids (50% probability level) with atom labeling. b) Perspective view of a centrosymmetric metaleorganic cycle in 7. Symmetry
code: A: 1 ꢁ x, 1 ꢁ y, 1 ꢁ z.
Fig. 18. a) Perspective view of the crystal packing in 7, showing all notable hydrogen bonds. b) Perspective view of the crystal packing in 7, showing all notable edge-to-edge
stacking interaction. Symmetry code: A: 1 ꢁ x, 2 ꢁ y, 1 ꢁ z; B: ꢁx, 1 ꢁ y, 1 ꢁ z.
pep
the face-to-face aromatic
pe
p
stacking interactions observed in the
crystalline lattices. In those complexes that contain co-crystallized
reported complexes lie in the range 3.56e3.79 Å, which are much
stronger than those reported in our previous studies (3.71e3.90 Å)
solvent molecules, hydrogen bonding between the trifluoroacetate
group and the methanol or aqua ligand (1A, 2A, 4e6), or weak
CeH/F interaction (2B) with the phenyl ring, confers enhanced
stability to the silver(I) coordination chains or layers to connect
them into a two- or three-dimensional supramolecular network.
[7e10].
Weak intermolecular interactions and formation of supramolecular
frameworks
Conclusion
The coordination modes of the trifluoroacetate groups vary from
The present work reports the structural characterization of a
series of nine silver(I) trifluoroacetate complexes containing
carbon-rich ligands each composed of a condensed-ring benzenoid
aromatic nucleus bearing one or two terminal ethynyl groups at
variable positions. Single-crystal X-ray analysis of the complexes
provided detailed information on the influence of aromatic-ring
size and orientation, coordination preferences, and co-existence
of different kinds of silver(I)eethynide and silver(I)earomatic in-
teractions in coordination network construction, as well as the
roles played by weak interactions in supramolecular assembly.
2
1
1
1 2
the common
trifluoroacetate ligand generally plays two important roles: one
type spans an edge of the Ag basket to consolidate the
cationic moiety, whereas the other bridges adjacent
baskets or Ag atoms to generate an infinite chain or a layer-type
structure.
Among the nine complexes reported herein, silvereorganic cy-
m
2
ꢁ
h
kind to the
2
m ꢁ
h
,
h
and
m
3
ꢁh ,h varieties. The
n
(
nꢁ1)þ
[
Ag
Ag
n
C^C]
n
cles are constructed in 1A and 2A from aqueous concentrated silver
salt solution, while formation of an infinite silver chain in 1B and 2B
is more favorable when crystallized from the polar aprotic solvent
DMSO. Similarly, an infinite multinuclear silver ribbon is assembled
in 3 from crystallization in THF. In 1A, 2A, 3 and 4, the offset face-to-
Acknowledgments
face
pep stacking interactions and silverearomatic interactions
We gratefully acknowledge financial support by the Hong Kong
Research Grants Council (GRF CUHK 402710), the Wei Lun Foun-
dation and a Postdoctoral Research Fellowship to S. C. K. Hau,
respectively, by The Chinese University of Hong Kong.
play significant roles in stabilizing the argentophilic silver(I) chains.
In complex 7, edge-to-edge
attached 2,2 -bipyridyl ligands leads to the generation of a three-
dimensional supramolecular network. When the complex is crys-
tallized from aqueous solution in 6, stronger Hebonding in-
teractions dominate formation of the assembled structure at the
pep stacking interaction between
0
Appendix A. Supplementary material
expense of weak pep stacking interactions.
With the exception of 3 and 7, all other complexes incorporate
CCDC 1040752e1040760 for compounds 1Ae7 contain the
solvated DMSO, water, MeCN or MeOH molecules in their
supplementary crystallographic data for this paper. These data can

S.C.K. Hau, T.C.W. Mak / Journal of Organometallic Chemistry 792 (2015) 123e133
133
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[8] (a) T. Zhang, J. Kong, Y. Hu, X. Meng, H. Yin, D. Hu, C. Ji, Inorg. Chem. 47 (2008)
144e3149;
3
(
(
b) T. Zhang, H. Song, X. Dai, X. Meng, Dalton Trans. 38 (2009) 7688e7694;
c) T. Zhang, Y. Hu, J. Kong, X. Meng, X. Dai, H. Song, CrystEngComm 12 (2010)
3
(
027e3032;
d) Y. Zhao, P. Zhang, B. Li, X. Meng, T. Zhang, Inorg. Chem. 50 (2011)
097e9105;
e) Z. Zhang, B. Li, X. Meng, X. Yin, T. Zhang, Dalton Trans. 42 (2013)
306e4312.
9] P.-S. Cheng, S.C.K. Hau, T.C.W. Mak, Aust. J. Chem. 67 (2014) 1849e1859.
Appendix B. Supplementary data
9
(
4
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2015.03.013.
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10] P.-S. Cheng, S.C.K. Hau, T.C.W. Mak, Inorg. Chim. Acta 403 (2013) 110e119.
11] S.C.K. Hau, T.C.W. Mak, J. Chin. Chem. Soc. 60 (2013) 877e886.
12] W.L.F. Armarego, Purification of Laboratory Chemicals, Butterworth-Heine-
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