Self-assembly of silver(I) coordination polymers from AgX (X = BF 4-, ClO4-, CF3COO -, and SO3CF3-) and a rigid bent 3,6-dicyano-9-phenylcarbazole ligand: The templating effect of anions

Article abstract of DOI:10.1002/ejic.200601259

One rigid bent bridging ligand with highly planar π-conjugated spacers, 3,6-dicyano-9-phenylcarbazole (dcphcz), was designed and synthesized. The coordination reactions of dcphcz with a series of Ag^I salts with different counterions has been investigated. Four coordination polymers were obtained by solution reactions and characterized by IR, elemental analysis, and single-crystal X-ray diffraction. The solid-state structures of {[Ag(dcphcz)]BF₄}_n (1) and {[Ag(dcphcz)]ClO ₄}_n (2), exhibit similar 1D "zigzag" patterns. The complex {[Ag(dcphcz)][Ag₂(dcphcz)(H₂O) ₂](SO₃CF₃)₃·C ₆H₆·(H₂O)₂}_n (3) includes two different one-dimensional (1D) chain units: one forms double-layer two-dimensional (2D) metal-organic frameworks (MOFs) through intermolecular Ag-O-Ag bridging interactions, the other features double-layer 2D supramolecular networks through C-H...O hydrogen-bonding interactions. The complex [Ag₂(dcphcz)-(CF₃COO)₂]n (4) features a bundle of novel nanotubular structures, which contain silver chains formed by carboxylate spacers. Furthermore, all these complexes are connected by face-to-face π...π stacking interactions between carbazolyl planes, affording a series of three-dimensional (3D) architectures with different structural geometries. The structural diversities of these complexes demonstrated that counteranions and bridging ligands play essential roles in the construction of supramolecular frameworks. In addition, the luminescence properties of the free ligand dcphcz and complexes 1-4 were investigated. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200601259

FULL PAPER
DOI: 10.1002/ejic.200601259
–
–
Self-Assembly of Silver(I) Coordination Polymers from AgX (X = BF4 , ClO4 ,
CF3COO–, and SO3CF3 ) and a Rigid Bent 3,6-Dicyano-9-phenylcarbazole
–
Ligand: The Templating Effect of Anions
Kai-Ju Wei,[a] Jia Ni,[b] Jian Gao,[a] Yangzhong Liu,*[a] and Qing-Liang Liu*[a]
Keywords: Silver / N ligands / Supramolecular chemistry / Luminescence / Coordination polymers / Metal-organic frame-
works
One rigid bent bridging ligand with highly planar π-conju-
gated spacers, 3,6-dicyano-9-phenylcarbazole (dcphcz), was
designed and synthesized. The coordination reactions of
dcphcz with a series of AgI salts with different counterions
has been investigated. Four coordination polymers were ob-
tained by solution reactions and characterized by IR,
elemental analysis, and single-crystal X-ray diffraction. The
solid-state structures of {[Ag(dcphcz)]BF4}n (1) and
{[Ag(dcphcz)]ClO4}n (2), exhibit similar 1D “zigzag” patterns.
The complex {[Ag(dcphcz)][Ag2(dcphcz)(H2O)2](SO3CF3)3·
C6H6·(H2O)2}n (3) includes two different one-dimensional
(1D) chain units: one forms double-layer two-dimensional
(2D) metal–organic frameworks (MOFs) through intermo-
lecular Ag–O–Ag bridging interactions, the other features
double-layer 2D supramolecular networks through C–H···O
hydrogen-bonding interactions. The complex [Ag2(dcphcz)-
(CF3COO)2]n (4) features a bundle of novel nanotubular
structures, which contain silver chains formed by carboxylate
spacers. Furthermore, all these complexes are connected by
face-to-face π···π stacking interactions between carbazolyl
planes, affording a series of three-dimensional (3D) architec-
tures with different structural geometries. The structural
diversities of these complexes demonstrated that
counteranions and bridging ligands play essential roles in
the construction of supramolecular frameworks. In addition,
the luminescence properties of the free ligand dcphcz and
complexes 1–4 were investigated.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
the molar ratio of the reagents.[9] On top of these factors, a
bridging ligand as a “building block” is a pivotal point in
manipulating the network structures. Because of configura-
tion, coordination activity, and relative orientation of the
donor groups, the organic spacers take important roles in
determining the structure and geometry of the polymers.
Rigid linear ligands have already been extensively
studied[3n,10] for designing polymers; however, bent ligands
still remain a challenge in self-assembly due to their unpre-
dictable coordination geometry.
It is well recognized that the carbazole moiety not only
possesses highly planar π-conjugated systems, but also can
be easily functionalized at its 3-, 6-, or 9-positions and co-
valently linked to other functional moieties.[11] Further-
more, the thermal stability of organic compounds can be
greatly improved upon incorporation of a carbazole moiety
in the core structure.[12] Therefore, thermally stable mole-
cules possessing dual functions, light-emitting and hole-
transporting, should be achieved by using carbazole as the
central core. Currently, compounds with highly π-conju-
gated systems are of great interest due to their various ap-
plications in chemical sensors, molecular optical and elec-
tronic devices.[13]
Introduction
The design and synthesis of metal–organic coordination
polymers have attracted intensive attention not only be-
cause of their novel topologies and intriguing structural di-
versity,[1] such as nanotubes[2] and various metal–organic
frameworks (MOFs),[3] but also because of their unique
chemical and physical properties and their potential appli-
cations as optoelectronic, magnetic, and porous materials.[4]
In fact, the ultimate aim of supramolecular and coordina-
tion chemistry is to control the structure of the target prod-
ucts and investigate the relationship between the structures
and physicochemical properties. Generally, the topology of
a coordination polymer generated from the self-assembly of
metals and ligands can be controlled by ingenious design
of the organic ligand,[5] selection of proper metal ions and
counterion,[6] solvent system,[7] pH value of solution,[8] and
[a] Department of Chemistry, University of Science & Technology
of China,
Hefei, Anhui 230026, P. R. China
Fax: +86-551-3603388
E-mail: liuyz@ustc.edu.cn
qliu@ustc.edu.cn
[b] Center Lab, Shantou University,
Shantou, Guangdong 515063, P. R. China
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Herein, we report the design and synthesis of a new or-
ganic molecule with large angular and highly planar π-con-
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Self-Assembly of Silver(I) Coordination Polymers
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jugated spacers based on carbazole, 3,6-dicyano-9-phenyl- catalyst. The dcphcz is very soluble in common organic sol-
carbazole (dcphcz). In most cases, the conformation of co- vents, such as CH2Cl2, CHCl3, THF, benzene, toluene, and
ordination polymers from bent bidentate ligands are hardly CH3CN. The slow diffusion of a CH2Cl2 solution of dcphcz
–
–
predictable because of the variation of coordination geome- into a benzene solution of AgX (X = BF4 , ClO4 ,
–
try, such as cis, trans, or intermediary.[7,14] On the other SO3CF3 , and CF3COO–) afforded a 3:2 ratio of AgI salt/
–
hand, these variations also provide more chances for dcphcz ligand adduct for SO3CF3 and 1:1 adducts for
–
–
designing novel polymeric patterns. The ligand dcphcz does BF4 , ClO4 , and CF3COO–, which may result from the
not have a conformational diversity owing to the particular subtle templating effects of the counterions. It was observed
structure of carbazole as the central core, neglecting the ro- that the products do not depend on the ligand/metal ratio;
tationality of the terminal phenyl ring of dcphcz. The coor- however, increasing the metal/ligand ratio resulted in some-
dination reactions of dcphcz and the AgI ion with different what higher yields and better crystal qualities. Complexes
counterions were investigated aiming at expanding dcphcz 1–4 are stable in air at room temperature only for a short
units through the “soft” AgI metal ion and exploring the time. All these complexes are insoluble in CH2Cl2, CHCl3,
templating effects of counterions in the self-assembly pro- THF, benzene, and CH3CN, but moderately soluble in
cess. It has been reported[6b,6c,10c,15] that the –CN functional MeOH, and soluble in DMF.
group on the aromatic ring serves as a good candidate for
The structures of the ligand dcphcz and complexes 1–
coordination bonding in the self-assembly of Ag-supra- 4 were determined by IR and elemental analysis. The IR
molecular architectures. With a d10 electronic configura- spectrum of ligand dcphcz and complexes 1–4 show a –CN
tion, the AgI ion often has irregular coordination geome- absorption band at 2219, 2251, 2251, 2220, and 2219 cm–1,
tries and shows a strong tendency to display versatile coor- respectively. The rigid bidentate or tridentate ligands con-
dinations. Thus, the AgI ion is much more accommodating taining benzonitrile groups, such as 4,4Ј-dicyanobiphen-
towards ligands and is expected to form polymer structures yl,[15n] 2,5-bis{3-[(4-cyanophenyl)ethynyl]phenyl}-1,3,4-oxa-
more readily than other d10 metal ions. At the same time, diazole,[7] 1,3,5-tris[(4-cyanophenyl)ethynyl]benzene,[15n] and
the ancillary ligation by different counterions, such as 1,3,5-tris{4-[(4-cyanophenyl)ethynyl]phenyl}benzene,[15k]
–
–
–
–
–
–
NO3 , BF4 , ClO4 , SO3CF3 , CF3COO–, PF6 , and SbF6 , have shown excellent bridging action to construct porous
may cause a significant structural change of the poly- frameworks and supramolecular polymers. However, to the
mer.[6,10c,14,15] With different polymeric motifs, four new best of our knowledge, no supramolecular architectures
Ag-containing coordination polymers, {[Ag(dcphcz)]BF4}n based on carbazole-containing nitrile groups have been re-
(1), {[Ag(dcphcz)]ClO4}n (2), {[Ag(dcphcz)][Ag2(dcphcz)- ported.
(H2O)2](SO3CF3)3·C6H6·(H2O)2}n (3), and [Ag2(dcphcz)-
(CF3COO)2]n (4), were synthesized based on ligand 3,6-di-
cyano-9-phenylcarbazole and their luminescence properties Crystal Structures
were characterized in this work.
Structural Analysis of Ligand dcphcz
The structure of dcphcz was further confirmed by single-
crystal X-ray diffraction, as shown in Figure 1. The central
Results and Discussion
carbazolyl group is nearly planar (with a dihedral angle of
2.9° between the two benzonitrile groups). The terminal
Synthesis and Characterization
3,6-Dicyano-9-phenylcarbazole (dcphcz) was synthesized (–CN) N···N separation is 9.631 Å, which is close to that of
in high yield by using the modified Ullmann condensation 1,2-bis(4-pyridyl)ethyne (9.685 Å).[16] The terminal phenyl
procedure depicted in Scheme 1, where 3,6-diiodo-9-phenyl- ring is not coplanar with the carbazolyl group, as indicated
carbazole reacts with CuCN in the presence of an HMPA by the dihedral angle of 59.5° between the terminal phenyl
Scheme 1. Preparation of the ligand dcphcz.
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plane and the five-membered ring of the carbazolyl group. tion, face-to-face π···π stacking between terminal phenyl
Evidently, the nonplanarity of the ligand is caused by the rings, constructs 2D networks from the 1D chain (Figure 2).
steric hindrance between C–H groups in two phenyl rings.
At the same time, the C(3)-containing phenyl ring is in-
volved in a moderately strong[18] face-to-face π-stacking in-
teraction with its symmetry-related equivalent, with an in-
terplane distance of 3.47 Å. Thus, the dual interactions of
π-stacking and H-bonding extend the 2D networks into 3D
architectures.
Structural Analysis of {[Ag(dcphcz)]BF4}n (1) and
{[Ag(dcphcz)]ClO4}n (2)
Crystallization of dcphcz with AgBF4 in a dichlorometh-
ane/benzene mixed solvent afforded 1 as an infinite 1D
chain structure. As shown in Figure 3a, single-crystal analy-
sis reveals, that there is only one AgI center in complex 1.
Each AgI ion is coordinated by two nitrogen atoms from
two different dcphcz ligands and two fluorine atoms from
–
the BF4 anion. The bond lengths of Ag(1)–N(1) and
Ag(1)–N(3) are 2.116 and 2.119 Å, respectively. The Ag(1)–
F(1) and Ag(1)–F(2) bonds (2.654 and 2.910 Å) are signifi-
cantly shorter than the sum of the van der Waals radii for
Ag and F (3.19 Å),[17] which indicates the coordination be-
Figure 1. ORTEP diagram showing the structure of dcphcz with
30% thermal ellipsoid probability and the atom-labeling scheme.
Hydrogen atoms have been omitted for clarity in this and the fol-
lowing figures.
–
tween AgI and anion BF4 .
Figure 2 shows several intermolecular noncovalent inter-
As shown in Figure 4a, the intrapolymer chain Ag···Ag
actions in the dcphcz crystal that extends the packing in distance is 13.378 Å. Furthermore, the 1D polymeric chain
the solid-state structure. There are two kinds of C–H···N of 1 is linked into a 2D double-layer network through inter-
hydrogen-bond interactions between the –CN groups and polymer C–H···F hydrogen-bonding interactions (Figure 5).
carbazolyl groups on adjacent molecules of dcphcz, which The hydrogen-bonding system involves F(3) of the coordi-
–
results in the formation of 1D double chains. The distances nated BF4 counterion and H(7) and H(13) on the dcphcz
of N(1)···H(9) and N(3)···H(3) (2.620 and 2.75 Å, respec- ligand of the neighboring chain. The F(1)···H(7) and F(1)···
tively) are significantly shorter than the sum of the H(13) contacts are 2.398 and 2.563 Å, respectively. The cor-
van der Waals radii for nitrogen and hydrogen (ca. 1.2 Å for responding C(7)–H(7)···F(1) and C(13)–H(13)···F(1) angles
H, and 1.70 Å for N).[17] The other intermolecular interac- are 158.36° and 155.18°, respectively.
Figure 2. 2D network of dcphcz, showing the π-stacking interactions between the phenyl rings and weak C–H···N hydrogen-bond interac-
tions.
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Self-Assembly of Silver(I) Coordination Polymers
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Figure 3. ORTEP diagram showing the structures of 1 (a) and 2 (b), respectively, with 30% thermal ellipsoid probability and the atom-
labeling scheme.
Figure 4. View of one-dimensional “zigzag” chain of 1 (a) and 2 (b).
The existence of weak C–H···X (X = F, Cl, Br, I, O, S,
The other 1D zigzag chain 2 was obtained in a similar
and N) hydrogen-bonding interactions are observed in way to 1 by using AgClO4 in place of AgBF4. The two
many compounds and the structural importance is well es- complexes have very similar coordination features with two
tablished.[11b,11c,15d–15j,19] These weak hydrogen bonds often dcphcz chelating ligands (Figure 3b and Figure 4b), while
contribute significantly to the alignment of the supramolec- the ClO4– anion takes the place of BF4– with two coordinat-
ular structures in the crystalline state. In complex 1, the ing O atoms. The Ag–N bond lengths are close to those in
–
BF4 anion contributes to the packing of the complex by complex 1, whereas the two Ag–O bonds are somewhat
coordinating the AgI center in one chain and hydrogen- longer (2.636 and 2.847 Å) than Ag–F and within the typi-
bonding to the F atoms in the neighboring chain. These 2D cal Ag–O bond lengths as reported previously.[11c] The
double-layer networks stack in the ac plane through π···π N(1)–Ag(1)–N(3) bond angle (154.02°) and the intrapo-
interactions between the lateral carbazolyl planes with an lymer Ag···Ag distance (13.257 Å) are similar to those in
interplane distance of 3.391 Å. Of course, there is also a complex 1. Obviously, the structural similarity of 1 and 2 is
–
face-to-face π···π stacking in 2D double-layer networks with generated by the similar nature of the anions (BF4 and
–
an interplane distance of 3.357 Å. Undoubtedly, these π- ClO4 ).
stacking interactions serve as important driving forces to
Recently, Ag-supramolecular complexes have been re-
cross-link the 2D double-layer networks into a 3D architec- ported[6,10c,14,15,21] based on bent organic ligands with pyr-
ture. Some examples have shown that the organic ligands idyl, cyano, aminophenyl, and acetylenylphenyl groups as
involved in the nucleation process use both coordination the terminal coordination sites. However, these bent organic
and π···π interactions to construct the framework.[6b,20]
ligands exhibit potentially diverse conformations on coordi-
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Figure 5. Top (top) and side (bottom) views of two-dimensional double-layer supramolecular networks of 1 stacked together through
multiple C–H···F hydrogen-bonding interactions and face-to-face π···π stacking interactions (dπ–π = 3.357 Å).
nation; while dcphcz has a conformation suitable for coor- weakly coordinates to an anionic oxygen atom [Ag(1)–O(2)
dinating to metal centers retaining the bending geometry, 2.803 Å], and a water oxygen atom [Ag(1)–O(11) 2.738 Å],
making it easy to control and predict the structure and showing tetrahedral coordination geometry with an N(3)–
geometry of the resulting polymers.
Ag(1)–N(4) bond angle of 174.4°. While Ag(2) in the chain
Similar to complex 1, a double-layer architecture is b center only weakly coordinates to an anionic oxygen atom
formed through multiple C–H···O hydrogen bonding [O(2)··· [Ag(2)–O(9) 2.660 Å], showing T-shaped coordination ge-
H(5) 2.594 Å, C(5)–H(5)···O(2) 155.75°; O(2)···H(8) ometry with an N(1)–Ag(2)–N(2) bond angle of 166.3°. Al-
2.395 Å, C(8)–H(8)···O(2) 159.68°]. The parallel carbazole though these Ag–O distances are relatively long, they are
rings from adjacent chains are paired to furnish face-to-face all significantly shorter than the sum of the van der Waals
π···π stacking with an interplane distance of 3.349 Å, which radii for silver and oxygen (3.24 Å).[17] The intrapolymer
extends the 2D network into 3D supramolecular architec- Ag···Ag distances are 12.559 and 12.308 Å for chains a and
tures along the ac plane.
b, respectively, which are shorter than those of complexes 1
and 2. Interestingly, a solvent benzene molecule is located
in chain b through weak Ag···C interactions with the near-
est Ag···C distance of 2.959 Å.
Structural Analysis of {[Ag(dcphcz)][Ag2(dcphcz)-
(H2O)2](SO3CF3)3·C6H6·(H2O)2}n (3)
Sitting on the flank of chain a, Ag(3) has a coordination
environment different to those of atoms Ag(1) and Ag(2).
In addition to the coordination of two water molecules,
Ag(3) has a strong interaction with a terminal phenyl ring
from chain a. The Ag(3) atom sits above the phenyl rings
and slightly off the center, resulting in a shortest Ag–
Cbenzene distance of Ag(3)–C(17) (2.523 Å) which is still
within the normal range for Ag–C bond lengths (2.47–
2.76 Å), while the remaining Ag–C distances [Ag(3)···C(16)
2.852 Å; Ag(3)···C(18) 2.889 Å] are beyond the limits com-
monly observed in AgI-aromatic complexes.[14,15f–15j,22]
Thus, it is concluded that the benzene ring coordinates to
the Ag(3) ion with an η1-bonding mode. The η1-type inter-
action between the AgI ion with a phenyl ring has already
been observed in many complexes,[14,15j] although it is less
Bright yellow single crystals of 3 were obtained by slow
diffusion of a benzene solution of AgSO3CF3 into a CH2Cl2
solution of dcphcz. Single-crystal analysis reveals that there
are three independent AgI centers in 3. The ligand dcphcz
has a similar coordination mode in this complex relative to
1 and 2, however, the different property of the anion alters
the molecular architectures in 3. Atoms Ag(1) and Ag(2)
expand the dcphcz units into two independent zigzag chains
a and b, respectively, whereas atom Ag(3) is locked in the
chain b through a peculiar Ag–C interaction to the phenyl
ring (Figure 6). The Ag–N bond lengths in the two chains
are all within the range typical for Ag–N bond lengths,[15]
though it is slightly longer in chain a [Ag(1)–N(3) 2.134 Å;
Ag(1)–N(4) 2.148 Å] than in chain b [Ag(2)–N(1) 2.098 Å;
Ag(2)–N(2) 2.119 Å]. The Ag(1) center in chain a also
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Self-Assembly of Silver(I) Coordination Polymers
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Figure 6. Views of the “zigzag” chains a (top) and b (bottom) in complex 3.
common than the η2-type interaction in which the metal O interactions [O(7)···H(30) 2.436 Å, C(30)–H(30)–O(7)
ion interacts with one edge of the phenyl ring. 138.23°; O(9)···H(34) 2.656 Å, C(34)–H(34)–O(9) 125.35°]
As shown in Figure 7, the packing style of 3 from chains and face-to-face π···π stacking between adjacent b chains
a and b is different from 1 and 2. Chains a extend along with an interplane distance of 3.485 Å (Figure 8). Conse-
the crystallographic b axis and generate a 2D double-layer quently, chains a and b stack in an ...ABC... sequence along
metal–organic framework containing irregular channels the a axis in complex 3. The parallel carbazole rings from
through Ag–(µ-Owater)–Ag and Ag–(µ-SO3CF3)–Ag bridg- adjacent chains a and b are also paired to furnish π···π
ing and face-to-face π···π stacking with an interplane dis- stacking with a centroid–centroid distance of 3.879 Å and
tance of 3.552 Å. Chains b link together into a 2D double- a dihedral angle of 8.4°, which extend two 2D networks
layer supramolecular network through interpolymer C–H··· into a 3D architecture along the ac plane (Figure 9). In ad-
Figure 7. Top (top) and side (bottom) views of 2D double-layer metal–organic frameworks (MOFs) of chain a stacked together through
µ-O and µ-SO3CF3 bridging and face-to-face π···π stacking interactions (dπ–π = 3.552 Å).
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–
dition, the chains a and b are also linked through interpoly- polymer, the more strongly coordinating CF3CO2
–
mer O···H hydrogen-bonding interactions. The O(8)··· anion was used instead of the weakly coordinating BF4 ,
–
–
H(10A) distance of 1.945 Å and the O(8)···H(10A)–O(10) ClO4 , and SO3CF3 anions. Yellowish crystals of 4 were
angle of 162.67° indicate a very strong hydrogen-bonding obtained.
interaction. To the best of our knowledge, it is the first ex-
ample that independent 2D + 1D polymers coexist in one
crystal without mutual interpenetration. The shortest in-
terchain Ag(1)···Ag(2) separation is 3.593 Å between chains
a and b, which is slightly longer than the sum of the
van der Waals radii of two silver atoms, 3.44 Å. It can be
concluded from the architecture of the three complexes that
Single-crystal X-ray analysis of 4 reveals a novel two-
dimensional nanotube from two different crystallographic
silver(I) centers. As shown in Figure 10, each Ag(1) center
is coordinated by two nitrogen atoms of –CN groups and
–
two oxygen atoms from two different CO2CF3 anions, re-
sulting in a severely distorted tetrahedral environment, with
the angles around the Ag(1) center ranging from 98.1 to
150.05°. The Ag(1)–N(1) and Ag(1)–O(1) bond lengths are
2.371 and 2.263 Å, respectively, while the coordination
sphere around each Ag(2) center is composed of four oxy-
–
–
the counterions (polar SO3CF3 vs. nonpolar ClO4 and
–
BF4 ) play a key role in determining the polymeric struc-
tures of complex 3.
–
gen atoms from four CO2CF3 anions with two different
Structural Analysis of [Ag2(dcphcz)(CF3COO)2]n (4)
Ag–O distances (2.235 and 2.570 Å). Thus, the final coordi-
In order to further investigate the effect of the counterion nation geometry around the Ag(2) center is irregular with
on the long-range order of the AgI-dcphcz coordination bond angles ranging from 75.30 to 163.84°. The Ag(1) and
Figure 8. Top (top) and side (bottom) views of two-dimensional double-layer supramolecular networks of chain b stacked together
through multiple C–H···O hydrogen-bonding interactions and face-to-face π···π stacking interactions (dπ–π = 3.485 Å).
Figure 9. View of the packed structure (parallel to ac plane) in complex 3, showing ...ABC... packing sequence of chains a and b in the
–
crystal lattice. Some of the SO3CF3 anions, water, and benzene molecules have been omitted for clarity in this figure.
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Figure 10. Perspective view of 4, showing a one-dimensional macrocycle-containing chain.
Ag(2) atoms are bridged by two carboxyl groups with an between the carbazolyl planes of dcphcz ligands with an
Ag–Ag distance of 2.992 Å, which is slightly longer than interplane distance of 3.355 Å for 4. However, the open
for metallic silver (ranging from 2.803 to 2.987 Å) and channels are fully filled with the terminal phenyl group of
shorter than for other reported ligand-unsupported Ag–Ag dcphcz from adjacent 2D units. These noncovalent interac-
distances (ranging from 3.011 to 3.655 Å).[14,23] To form the tions serve again as important driving forces for cross-link-
–
nanotube, each carboxyl group of CF3CO2 connects to ing the 2D structure into a 3D architecture.
three Ag atoms through its two oxygen atoms: one oxygen
The different polymeric motifs from the four complexes
atom bridges two Ag atoms, while another oxygen atom indicate that the counteranions and bridging ligands are
–
attaches to the third Ag atom. Therefore, CF3CO2 acts as two crucial factors in designing the structure and geometry
a µ2-bridge and links two Ag(2) units, resulting in linear of the self-assemblies. The properties of the bridging li-
distorted ladder-like Ag chains. The ligand dcphcz is there- gands, such as π-conjugated spacers and relative orientation
fore bridged by Ag(1) atoms, producing a condensed nano- of the donor groups, take important roles in controlling the
tubular structure with dimensions of about 12ϫ13 Å. The structural topologies of their metal–organic supramolecular
adjacent nanotubes are in line through multiple Ag– architectures. In this system, the coordination conformation
Ocarbonyl bonding (Figure 11). Of course, the whole struc- of dcphcz is special because of the conformational irrot-
ture can also be regarded as parallel Ag chains linked by ationality around the central five-membered ring of the car-
dcphcz spacers.
bazolyl group. Thus, the architecture of the complexes de-
Analogously, adjacent 2D architectures containing 1D pends greatly on the counterions. Furthermore, π···π stack-
open channels along the c axis direction stack in the ab ing between carbazole rings is the basis of the 3D architec-
plane through noncovalent face-to-face π···π interactions tures in the complexes 1–4.
Figure 11. (a) View of two-dimensional nanotubal structure in 4 along the ac plane. (b) Space-filling representation of the 2D nanotubal
polymer along the c axis. (c) View of supramolecular networks of 4 stacked together through face-to-face π···π stacking interactions
(dπ–π = 3.355 Å).
Eur. J. Inorg. Chem. 2007, 3868–3880
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3875

K.-J. Wei, J. Ni, J. Gao, Y. Liu, Q.-L. Liu
FULL PAPER
Thermogravimetric Analysis
show broad emission bands at 499 (1), 515 (2), and 492 nm
(3), respectively, upon 330 nm excitation, whereas 4 has also
a very broad emission band (bandwidth at half-height =
110 nm) with λmax = 425 nm, which is in the blue region
and yields visible blue luminescence. Thus, complex 4 may
have potential applications as a luminescent material in or-
ganic light-emitting devices. Generally, the intraligand fluo-
rescence emission wavelength is determined by the energy
gap between π and π* molecular orbitals of the free ligand,
which is related to the extent of π conjugation in the sys-
tem.[28] Since the emission peak positions of complex 4 al-
most corresponded to that of the ligand dcphcz, they
should be due to neither ligand-to-metal nor metal-to-li-
gand charge transfer and can be ascribed to the intraligand
π-π* charge transfer of dcphcz. All these complexes exhib-
Thermogravimetric analysis of compound 3 was per-
formed by heating the complex from 20 to 600 °C under
N2. The TGA curve for complex 3 showed that the first
major weight loss of the lattice benzene occurred between
40 and 100 °C by 5.10% weight (calcd. 7.38%), which indi-
cates that benzene molecules could easily escape from the
crystal lattice of 3. As shown in Figure S14, further thermo-
gravimetric data shows the second major weight loss of the
four water molecules between 110 and 145 °C by 4.11%
weight (calcd. 4.78%).
Luminescent Properties
For potential applications as luminescent materials,[24] ited relatively weak emissions, which may be a result of the
fluorescence properties have been investigated in metal–or- heavy-atom effect of silver.[29]
ganic coordination polymers. Because of their ability to af-
It is clear that significantly different emission in 1–4 is
fect the emission wavelength of organic materials, syntheses due to the variation of anions and coordination environ-
of inorganic–organic coordination polymers have employed ments, because photoluminescence behaviors closely associ-
the ingenious design of conjugated organic ligands and ju- ate with the local environments around metal ions.[20a,30] In
–
–
dicious choice of proper metal centers in order to obtain 1 and 2, the anions BF4 and ClO4 are similar in nature
new types of luminescent materials,[25] especially for d10 and also display similar weak coordination to AgI. Com-
metal systems[13c,13d,26] and highly conjugated ligand-con- plex 3 has two 1D chain units, which are similar to those
taining complexes.[11,13c,27] We have explored the lumines- in 1 and 2, and the anion CF3SO3– also weakly coordinates
cent properties of 3,6-bis(2,2Ј-dipyridylamino)-9-phenyl- to AgI although it has properties different from those of
–
–
carbazole and its AgI coordination polymer.[11c] The results BF4 and ClO4 . In contrast, each AgI ion in complex 4 is
–
indicated that the emission color of organic spacers strongly coordinated by O atoms of CF3CO2 and provides
ddpapcz was remarkably affected by Ag coordination com- a coordination geometry different from those of 1–3.
pounds. Herein, the luminescent properties of 3,6-dicyano-
9-phenylcarbazole and its metal complexes 1–4 were investi-
gated.
Conclusions
The UV/Vis spectra of ligand dcphcz and complexes 1–4
display two intense absorption bands from πǞπ* electronic
Four AgI-dcphcz coordination polymers with one-, two-,
transitions (from 230 to 290 nm), which originate from the and three-dimensional supramolecular structures have been
carbazolyl groups (Figure S15). No difference in emission successfully prepared by the reaction of dcphcz and AgI
colors has been observed between free ligand and com- salts with different counterions in solution. The roles of the
plexes in methanol, which has a broad fluorescent emission counteranions in determining the molecular structures of
band (from 340 to 420 m), with λmax = 367 nm (Fig- the coordination polymers have been exhibited. The nature
ure S16). This probably implies that the polymeric com- of the anions is the underlying reason behind the differences
plexes disaggregate in methanol solution. The dissociation in the structures of this series of AgI complexes. In com-
–
–
of Ag-supramolecules in solvent has been reported in many plexes 1 and 2, the weakly coordinated BF4 and ClO4
other samples.[11c,14]
anions not only act as the counteranions to balance the
Despite the similarity of emission bands in solution, the charge but have a spatial templating effect in building up
emission bands of five compounds in the solid state are sig- the coordination frameworks. For 3 and 4, the bulkier
–
–
nificantly different (Figure S17). A very strong emission of CF3SO3 and CF3CO2 anions possess stronger coordina-
–
–
the free ligand dcphcz with a wavelength from 375 to tion ability than BF4 and ClO4 and serve as linkages to
575 nm (λmax = 404 nm) upon excitation at 330 nm is ob- bridge the 1D chains to 2D MOFs with Ag–O contacts.
–
–
served, which has a redshift relative to the solution state. Moreover, the coordinated CF3SO3 and CF3CO2 ions
This can be explained by the extensive π···π stacking in the also possess weak interactions with ligand units, probably
solid state, which is between the carbazolyl planes of one act as templates for the formation of the network, and con-
dcphcz and the neighboring molecules with an interplane sequently maintain the structural stability. In addition, for
distance of 3.47 Å. This π···π stacking lowers the excited the AgI-dcphcz system in this work, the conformation of
energy of dcphcz in the solid state and causes the redshift dcphcz does not depend on the counterion and solvent sys-
of emission energy relative to the solution, in which the tem used in the formation of the complexes.
carbazolyl stacking could not exist.
The self-assembly of the bent organic ligands with highly
Blue/green luminescence is observed with the coordina- planar π-conjugated spacers provides a new approach for
tion to the silver center. In the solid state, complexes 1–3 building metal–organic frameworks consisting of a 1D open
3876
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3868–3880

Self-Assembly of Silver(I) Coordination Polymers
FULL PAPER
C20H11AgClN3O4 (500.6): calcd. C 47.98, H 2.215, N 8.393; found
C 48.09, H 2.209, N 8.401.
channel. We are also intrigued by the question whether the
variation of the terminal group of dicyanocarbazole will
lead to MOF assemblies with open channels by introducing
small groups to the 9-position of the carbazole on coordi-
nation. Further work is currently ongoing in this labora-
tory.
Synthesis of {[Ag(dcphcz)][Ag2(dcphcz)(H2O)2](SO3CF3)3·C6H6·
(H2O)2}n (3): Upon a solution of dcphcz (0.0586 g, 0.2 mmol) in
5 mL of dichloromethane was successively layered a solution of
AgSO3CF3 (0.0514 g, 0.2 mmol) in benzene (5 mL). The vial was
covered with aluminum foil and the solvents were allowed to diffuse
slowly. Bright yellow single crystals suitable for X-ray structure
analysis were obtained several days later. Yield: 0.0573 g, 57%. IR
Experimental Section
(KBr): ν = 2220 (vs), 1632 (m), 1596 (s), 1503 (s), 1481 (s), 1456
˜
(m) 1369 (m), 1245 (vs), 1176 (vs), 1034 (vs) cm–1.
C49H36Ag3F9N6O13S3 (1507.6): calcd. C 39.04, H 2.407, N 5.574;
found C 39.01, H 2.402, N 5.583.
Materials and Methods: All starting chemicals were of reagent-
grade quality, obtained from commercial sources and used without
further purification. Bromobenzene was freshly distilled. Benzene
was freshly distilled from sodium/benzophenone; dichloromethane
was dried and distilled from P2O5 under nitrogen; dmf was dried
Synthesis of [Ag2(dcphcz)(CF3COO)2]n (4): Upon a solution of
dcphcz (0.0586 g, 0.2 mmol) in 4 mL of dichloromethane was suc-
cessively layered a solution of CF3COOAg (0.0442 g, 0.2 mmol) in
benzene (5 mL). The vial was covered with aluminum foil and the
solvents were allowed to diffuse slowly. Bright yellow single crystals
suitable for X-ray structure analysis were obtained several days
1
and distilled from MgSO4. H NMR spectra were recorded with a
Bruker 300 Ultrashield spectrometer operating at 300 MHz. The
FT-IR spectra were recorded in the region 400–4000 cm–1 with a
Bruker EQUINOX 55 VECTOR22 spectrophotometer and the
samples were prepared using KBr pellets. Elemental analyses were
carried out with an Elmentar Vario EL-III analyzer. Fluorescence
measurements were carried out with a JOBIN YVON Analytical
Instrument FLUOROLOG-3-TAU at room temperature. Thermo-
gravimetric analyses (TGA) were performed with a TGA-50H
thermoanalyzer under N2 (in the temperature range 20–600 °C) at
a heating rate of 10 °C/min. 9-Phenylcarbazole and 3,6-diiodo-9-
phenylcarbazole were synthesized according to procedures reported
earlier.[11c,31]
later. Yield: 0.0471 g, 64%. IR (KBr): ν = 2219 (vs), 1682 (vs),
˜
1595 (m), 1501 (m), 1480 (m), 1292 (m), 1209 (vs), 1132 (vs) cm–1.
Table 1. Selected interatomic distances [Å] and angles [°] for com-
plexes 1–4.
Complex 1
Ag(1)–N(1)
Ag(1)–F(1)
2.116(3)
2.654
Ag(1)–N(3)
N(3)–Ag(1)–F(1)
2.119(3)
82.77
Caution! One of the crystallization procedures involves AgClO4,
which is a strong oxidizer.
N(1)–Ag(1)–N(3)
156.89(15) F(1)–Ag(1)–N(1)
119.75
Synthesis of 3,6-Dicyano-9-phenylcarbazole (dcphcz): A mixture of
3,6-diiodo-9-phenylcarbazole (0.99 g, 0.002 mol) and CuCN pow-
der (0.448 g, 0.005 mol) in HMPA (10 mL) was stirred under the
protection of dry nitrogen at 160 °C for 6 h. The reaction mixture
was cooled to ambient temperature, poured into aqueous NaHCO3
(10%) and extracted with dichloromethane. The aqueous phase was
discarded, the organic layer was washed with distilled water to neu-
tral pH, dried with MgSO4 and concentrated in vacuo. The residue
was filtered to give the desired compound as a primrose solid.
Complex 2
Ag(1)–N(2)
Ag(1)–O(1)
N(2)–Ag(1)–N(3)
N(3)–Ag(1)–O(4)
N(2)–Ag(1)–O(4)
2.112(3)
2.636
154.02(11) O(1)–Ag(1)–N(3)
86.06
115.07
Ag(1)–N(3)
Ag(1)–O(4)
2.122(3)
2.847
84.46
49.10
120.51
O(1)–Ag(1)–O(4)
N(2)–Ag(1)–O(1)
Complex 3
Ag(1)–N(3)
Ag(2)–N(1)
Ag(3)–O(11)
Ag(3)–C(17)
Ag(1)–O(1)
Ag(3)–O(1)
N(3)–Ag(1)–N(4)
O(11)–Ag(3)–C(17)
O(10)–Ag(3)–C(17)
O(9)–Ag(2)–N(1)
O(11)–Ag(1)–O(2)
O(11)–Ag(1)–N(4)
Ag(1)–O(11)–Ag(3)
O(1)–Ag(3)–C(17)
O(10)–Ag(3)–O(1)
2.134(5)
2.098(5)
2.327(6)
2.523(7)
3.031
Ag(1)–N(4)
Ag(2)–N(2)
Ag(3)–O(10)
Ag(1)–O(2)
Ag(1)–O(11)
Ag(2)–O(9)
N(1)–Ag(2)–N(2)
O(11)–Ag(3)–O(10)
O(9)–Ag(2)–N(2)
O(2)–Ag(1)–N(4)
O(2)–Ag(1)–N(3)
O(11)–Ag(1)–N(3)
O(10)–Ag(3)–C(17)
O(11)–Ag(3)–O(1)
2.148(5)
2.119(5)
2.344(6)
2.803
2.738
2.660
166.3(2)
100.56(19)
87.04
86.86
94.99
Yield: 0.55 g, 93%. IR (KBr): ν = 2219 (vs), 1631 (m), 1595 (s),
˜
1502 (s), 1480 (s), 1455 (m) 1369 (m), 1292 (s), 1243 (s), 1185 (m)
cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.48 (d, 2 H), 7.75–7.71
(d, 4 H), 7.68–7.60 (d, 1 H), 7.49–7.52 (d, 2 H), 7.42–7.44 (d, 2 H)
ppm.
2.704
174.4(2)
123.5(2)
119.9(2)
98.67
100.47
84.00
118.66
80.44
106.88
Synthesis of {[Ag(dcphcz)]BF4}n (1): Upon a solution of dcphcz
(0.0586 g, 0.2 mmol) in 5 mL of dichloromethane was successively
layered a solution of AgBF4 (0.0390 g, 0.2 mmol) in benzene
(4 mL). The vial was covered with aluminum foil and the solvents
were allowed to diffuse slowly. Bright yellow crystals suitable for
X-ray structure analysis were obtained several days later. Yield:
90.51
119.91
125.53
0.0517 g, 53%. IR (KBr): ν = 2251 (vs), 1631 (m), 1591 (s), 1492
˜
(s), 1362 (m), 1294 (s), 1244 (s), 1187 (m), 1063 (vs), 821 (m) cm–1.
C20H11AgBN3F4 (488.00): calcd. C 49.23, H 2.273, N 8.611; found
C 49.31, H 2.274, N 8.620.
Complex 4
Ag(1)–O(1)
Ag(1)–Ag(2)
Ag(2A)–O(2)
O(1)–Ag(1)–O(1A)
O(1)–Ag(1)–N(1)
O(1)–Ag(1)–Ag(2)
O(2)–Ag(2)–O(2A)
O(2A)–Ag(2)–O(2AЈ)
2.263(3)
2.9924(7)
2.570(3)
Ag(1)–N(1)
Ag(2)–O(2)
2.371(4)
2.235(3)
Synthesis of {[Ag(dcphcz)]ClO4}n (2): Upon a solution of dcphcz
(0.0586 g, 0.2 mmol) in 5 mL of dichloromethane was successively
layered a solution of AgClO4 (0.0414 g, 0.2 mmol) in benzene
(5 mL). The vial was covered with aluminum foil and the solvents
were allowed to diffuse slowly. Bright yellow crystals suitable for
X-ray structure analysis were obtained several days later. Yield:
150.05(16) O(1A)–Ag(1)–N(1A) 94.84(15)
104.74(13) N(1)–Ag(1)–N(1A)
75.02(8) N(1)–Ag(1)–Ag(2)
163.84(17) O(2)–Ag(2)–O(2AЈ)
75.30(12)
98.1(2)
130.97(11)
115.94(15)
O(2AЈ)–Ag(2)–Ag(1) 130.76(8)
O(2)–Ag(2)–Ag(1)
O(2AЈ)–Ag(2)–O(2AЈЈ) 98.48(17)
Ag(2)–O(2A)–Ag(2A) 104.70
81.92(9)
0.0651 g, 65%. IR (KBr): ν = 2251 (vs), 1628 (m), 1592 (s), 1501
˜
(s), 1479 (s), 1367 (m), 1295 (s), 1245 (vs), 1188 (m), 1092 (vs) cm–1.
Eur. J. Inorg. Chem. 2007, 3868–3880
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3877

K.-J. Wei, J. Ni, J. Gao, Y. Liu, Q.-L. Liu
Table 2. Crystallographic data and structure refinement summary for the ligand dcphcz and complexes 1–4.
FULL PAPER
dcphcz
1
2
3
4
CCDC
286976
C20H11N3
293.32
608217
C20H11AgBF4N3
488.00
286975
C20H11AgClN3O4
500.64
monoclinic
0.27ϫ0.08ϫ0.07
P21/c
10.600(17)
11.076(18)
15.23(2)
90.00
90.26(3)
90.00
1788(5)
1.860
4
286973
286974
Empirical formula
Formula mass
Crystal system
Crystal size [mm]
Space group
A [Å]
b [Å]
c [Å]
α [°]
β [°]
C49H36Ag3F9N6O13S3 C24H11Ag2F6N3O4
1507.63
monoclinic
0.28ϫ0.20ϫ0.15
P21/c
14.343(7)
15.873(7)
24.558(11)
90.00
93.095(8)
90.00
5583(4)
1.794
4
735.1
triclinic
monoclinic
monoclinic
0.32ϫ0.30ϫ0.15
P2/c
11.2145(8)
15.2776(11)
7.1139(5)
90.00
94.5540(10)
90.00
1214.98(15)
2.009
0.35ϫ0.33ϫ0.30 0.41ϫ0.30ϫ0.28
¯
P1
P21/c
8.802(5)
9.011(5)
10.104(6)
74.672(11)
81.129(13)
74.356(11)
741.2(8)
1.314
10.6840(11)
11.0728(12)
15.3809(18)
90.00
90.134(3)
90.00
1819.6(3)
1.781
4
γ [°]
V [Å3]
Dcalcd. [Mgm–3]
Z
2
4
F(000)
304
0.080
960
1.158
992
1.312
2984
1.251
712
1.696
µ [mm–1]
Reflections collected
Reflections unique
R(int)
3714
2535
0.0297
13720
3209
0.0295
3209/0/262
R1 = 0.0472
wR2 = 0.1169
R1 = 0.0578
wR2 = 0.1233
1.050
18998
4071
0.0329
4071/0/262
R1 = 0.0457
wR2 = 0.1213
R1 = 0.0560
wR2 = 0.1283
1.035
26453
9825
0.0402
9825/0/748
R1 = 0.0633
wR1 = 0.1492
R1 = 0.0958
wR1 = 0.1710
1.035
7439
2776
0.0197
2776/0/179
R1 = 0.0390,
wR1 = 0.1067
R1 = 0.0467
wR1 = 0.1219
1.021
Data/restraints/parameters 2535/0/208
Final R indices [IϾ2σ(I)]
R indices (all data)
GOF on F2
R1 = 0.0620
wR2 = 0.1106
R1 = 0.1057
wR2 = 0.1251
1.005
Dyson, S. Antonijevic, G. Bodenhausen, Angew. Chem. Int. Ed.
2005, 44, 5720–5725; d) S. U. Son, K. H. Park, B. Y. Kim, Y. K.
Chung, Cryst. Growth Des. 2003, 3, 507–512.
C24H11Ag2F6N3O4 (735.1): calcd. C 39.21, H 1.509, N 5.716; found
C 39.22, H 1.509, N 5.721.
X-ray Crystallography: X-ray diffraction data were collected with a
Bruker-AXS SMART CCD area detector diffractometer at 293 K
using ω-rotation scans with a scan width of 0.3° and Mo-Kα radia-
tion (λ = 0.71073 Å). The structures were solved by direct methods
and refined with the full-matrix least-squares technique using
SHELXTL.[32] Anisotropic thermal parameters were applied to all
non-hydrogen atoms. All of the hydrogen atoms in these structures
are located from the differential electron density map and con-
strained to the ideal positions in the refinement procedure. The
crystallographic calculations were conducted using the SHELXL-
97 program. Crystal data and experimental details for the crystals
of the ligand dcphcz and complexes 1–4 are summarized in Tables 1
and 2. CCDC-286976, -608217, -286975, -286973, and -286974 con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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this article): TGA, UV/Vis absorption spectra, emission spectra in
MeOH solution and solid state.
Acknowledgments
This work was support by the National Natural Science Founda-
tion of China and the China Postdoctoral Science Foundation.
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3868–3880

Self-Assembly of Silver(I) Coordination Polymers
FULL PAPER
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