Organometallic silver(I) coordination polymers and supramolecular complexes based on novel multidentate thiophene- and benzenenitrile-containing symmetric and unsymmetric fulvene ligands

Article abstract of DOI:10.1021/om0507169

Seven new conjugated symmetric and unsymmetric fulvene ligands L1-L7 were synthesized. Thirteen new organometallic coordination polymers and supramolecular complexes were obtained through selfassembly based on these new fulvene ligands in the benzene/toluene mixed solvent system. Compounds 1-13 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can adopt either a cis or a trans conformation to bind Ag(I) ion through not only the terminal -CN and thiophene functional groups but also the fulvene carbon atoms into organometallic coordination polymers or discrete complexes. In addition, the luminescent properties of L1, L3, L5, and L7 and some of their Ag(I) complexes were investigated preliminarily in EtOH and the solid state.

Full text of DOI:10.1021/om0507169

Organometallics 2006, 25, 447-462
447
Organometallic Silver(I) Coordination Polymers and
Supramolecular Complexes Based on Novel Multidentate
Thiophene- and Benzenenitrile-Containing Symmetric and
Unsymmetric Fulvene Ligands
Yu-Bin Dong,* Yan Geng, Jian-Ping Ma, and Ru-Qi Huang
College of Chemistry, Chemical Engineering and Materials Science, and Shandong Key Laboratory of
Functional Chemical Materials, Shandong Normal UniVersity, Jinan 250014, People’s Republic of China
ReceiVed August 18, 2005
Seven new conjugated symmetric and unsymmetric fulvene ligands L1-L7 were synthesized. Thirteen
new organometallic coordination polymers and supramolecular complexes were obtained through self-
assembly based on these new fulvene ligands in the benzene/toluene mixed solvent system. Compounds
1-13 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray
diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They
can adopt either a cis or a trans conformation to bind Ag(I) ion through not only the terminal -CN and
thiophene functional groups but also the fulvene carbon atoms into organometallic coordination polymers
or discrete complexes. In addition, the luminescent properties of L1, L3, L5, and L7 and some of their
Ag(I) complexes were investigated preliminarily in EtOH and the solid state.
could act as a bidentate or multidentate organic spacer to bind
soft metal centers through both carbon-metal and hetero-
atom-metal coordination interactions into novel luminescent
organometallic coordination polymers and supramolecular com-
plexes.7
Introduction
The self-assembly of coordination polymers or supramolecu-
lar complexes with novel structures and properties have attracted
considerable interest by chemists.1,2 It is well-known that the
most efficient approach to prepared polymeric frameworks is
via direct chemical combination of inorganic and organic
components, a method which has proven quite fruitful.3,4
Fulvene,5 as one type of important organic ligand, has been
widely used in the construction of organometallic complexes:
for example, metallocene and related complexes.6 Up to date,
the chemistry of polymeric organic-inorganic architectures
based on fulvene molecules has received considerably less
attention. It is expected that the abundant coordination chemistry
of fulvene could afford us an excellent opportunity to construct
organic-inorganic hybrid materials that might be different from
those based on common organic spacers in topologies and
physical and chemical properties. A continuing project in our
laboratory has been the development of organometallic coor-
dination architectures generated from conjugated symmetric
fulvene ligands (II).7 Our previous study demonstrated that
fulvene (II) with two symmetric substituted benzonitrile arms
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Hashizume, D.; Ohashi, Y. J. Am. Chem. Soc. 1996, 118, 1803. (g) Tamaki,
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* To whom correspondence should be addressed. E-mail: yubindong@
sdnu.edu.cn.
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10.1021/om0507169 CCC: $33.50 © 2006 American Chemical Society
Publication on Web 12/14/2005

448 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
Scheme 1. Synthesis of Fulvene (II)-(IV) and the New Symmetric and Unsymmetric Pyridazine-Containing Fulvene Ligands
L1-L7
Scheme 2. Synthesis of Ag(I)-Fulvene Complexes
As we know, in addition to the benzonitrile moiety, five-
membered heterocyclic rings are also good candidates for
constructing coordination polymers or supramolecular com-
plexes as either terminal8 or bridging moieties,8 due to their
specific donor orientation and bridging style. For example, the
thiophene unit is widely used to prepare organic and organic-
inorganic functional materials for conductor, sensor, and catalyst
applications.9 The aroylation of cyclopentadienyl or substituted
cyclopentadienyl anions with five-membered 2-thiophenecar-
bonyl chloride and cyanobenzoyl chloride in one pot would
introduce benzonitrile and thiophenecarbonyl moieties into one
molecule in a single step, which is our synthetic approach to
access unsymmetric fulvene ligands of this type (Scheme 1).
In comparison to the well-developed coordination chemistry
based on symmetric organic ligands,1,2 coordination chemistry
based on unsymmetric organic bridging spacers has received
relatively less attention.10 Unsymmetric organic ligands might
generate coordination polymers or supramolecular architectures
not achievable by symmetric ligands, which results from their
more diverse coordination styles around the metal centers.
In this contribution, we present 7 new pyridazine-containing
symmetric and unsymmetric fulvene ligands L1-L7 by reac-
tion of fulvene (II), (III), and (IV) with PhNHNH2, NH2NH2‚
H2O, and NH2OH, respectively (Scheme 1) and 13 new or-
ganometallic Ag(I) polymeric and discrete complexes, namely
[Ag(L1)(SO3CF3)]‚0.5C6H6 (1), [Ag2(L1)2(SO3CF3)]‚2C6H6 (2),
[Ag(L1)(SbF6)(µ-bis-C6H6)0.5]‚H2O (3), [Ag(L1)(ClO4)]‚0.5C6H6
(4), [Ag(L1)(H2PO4)]‚0.5C6H6 (5), [Ag(L2)2]SbF6 (6), [Ag(L3)]-
PF6‚C7H8 (7), [Ag(L3)(SbF6)]‚C7H8 (8), {[Ag(L4)]SbF6}‚C7H8‚
0.5C6H6 (9), [Ag(L5)(C6H6)]PF6 (10), [Ag(L5)SO3CF3] (11),
{[Ag2(L6)(C6H6)(SbF6)]SbF6}‚2.5C6H6 (12), and [Ag(L7)-
(SO3CF3)]‚0.5C6H6 (13), based on them (Scheme 2). In addition,
luminescent properties of L1, L3, L5, and L7 and some of their
Ag(I) complexes were investigated primarily in the solid state
and in solution.
(8) (a) Hoskins, B. F.; Robson, R.; Slizys, D. A. Angew. Chem., Int. Ed.
1997, 36, 2336. (b) Hagrman, D.; Zubieta, J. Chem. Commun. 1998, 2005.
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S.; Harano, K.; Tanaka, T.; Shionoya, M. Angew. Chem., Int. Ed. 2003,
42, 5182. (e) Halper, S. R.; Cohen, S. M. Angew. Chem., Int. Ed. 2004, 43,
2385. (f) Steel, P. J. Coord. Chem. ReV. 1990, 106, 227. (g) Scott, J. D.;
Puddephatt, R. J. Organometallics 1986, 5, 2522. (h) Incarvito, C.;
Rheingold, A. L.; Gavrilova, A. L.; Qin, C. J. Bosnich, B. Inorg. Chem.
2001, 40, 4101. (i) Eillis, W. M.; Schmitz, M.; Arif, A. A.; Stang, P. J.
Inorg. Chem. 2000, 39, 2547. (j) Dong, Y.-B.; Ma, J.-P.; Huang, R.-Q.;
Smith, M. D.; zur Loye, H.-C. Inorg. Chem. 2003, 42, 294. (k) Dong, Y.-
B.; Cheng, J.-Y.; Wang, H.-Y.; Huang, R.-Q.; Tang, B.; Smith, M. D.; zur
Loye, H.-C. Chem. Mater. 2003, 15, 2593. (l) Dong, Y.-B.; Cheng, J.-Y.;
Huang, R.-Q.; Tang, B.; Smith, M. D.; zur Loye, H.-C. Inorg. Chem. 2003,
42, 5699. (m) Dong, Y.-B.; Wang, H.-Y.; Ma, J.-P.; Huang, R.-Q.; Smith,
M. D. Cryst. Growth Des. 2005, 5, 789. (n) Huang, Z.; Song, H.-B.; Du,
M.; Chen, S.-T.; Bu, X.-H.; Ribas, J. Inorg. Chem. 2004, 43, 931.
(9) (a) Kros, N. A.; Sommerdijk, J. M.; Nolte, R. J. M. AdV. Mater.
2002, 14, 1779. (b) Vriezema, M.; Kros, A.; De Gelder, R.; Cornelissen, J.
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(c) Wolf, M. O. AdV. Mater. 2001, 13, 545. (d) Deronizer, A.; Moutet, J.
C. Coord. Chem. ReV. 1996, 147, 339.
Results and Discussion
1. Synthesis and Structural Analysis of ligands L1-L7.
The interesting coordination chemistry exhibited by fulvene (II)
(10) For example, see: (a) Khlobystov, A. N.; Brett, M. T.; Blake, A.
J.; Champness, N. R.; Gill, P. M. W.; O’Neill, D. P.; Teat, S. J.; Wilson,
C.; Schro¨der, M. J. Am. Chem. Soc. 2003, 125, 6753. (b) Uemura, K.;
Kitagawa, S.; Kondo, M.; Fukui, K.; Kitaura, R.; Chang, H.-C.; Mizutani,
T. Chem. Eur. J. 2002, 8, 3586. (c) Lee, I.; Shin, D. M.; Chung, Y. K.
Chem. Eur. J. 2004, 10, 3158. (d) Wang, Y.-T.; Tong, M.-L.; Fan, H.-H.;
Wang, H.-Z.; Chen, X.-M. Dalton Trans. 2005, 424.

Ag(I) Polymers and Complexes with FulVene Ligands
Table 1. Crystallographic Data for 1-4
Organometallics, Vol. 25, No. 2, 2006 449
1
2
3
4
formula
formula wt
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
C19H13AgF3N2O3S3
578.36
triclinic
C44H30Ag2F6N4O6S6
1232.82
triclinic
C18H15AgF6N2OS2Sb
683.06
triclinic
C18H13AgClN2O4S2
528.74
triclinic
P1h
7.228(3)
10.800(4)
13.795(5)
112.361(5)
101.523(5)
93.377(5)
965.0(6)
2
P1h
P1h
P1h
7.2883(12)
12.429(2)
12.539(2)
112.386(2)
102.811(2)
90.246(3)
1019.2(3)
2
10.376(4)
14.152(5)
18.151(7)
75.767(6)
74.094(6)
69.456(6)
2366.7(16)
2
7.262(2)
12.546(3)
13.309(4)
114.817(4)
99.764(4)
92.531(4)
1075.6(5)
2
Z
F
calcd (g/cm3)
1.885
1.349
293(2)
1.730
1.168
293(2)
2.109
2.425
293(2)
1.820
1.427
293(2)
µ (mm-1
)
temp (K)
no. of rflns
3490
12 250
3863
4984
R1; wR2 (I > 2σ(I))
0.0714; 0.1290
0.0706; 0.1616
0.0771; 0.1531
0.0500; 0.1380
Table 2. Crystallographic Data for 5-8
5
6
7
8
formula
formula wt
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
C18H15AgN2O4PS2
578.36
triclinic
P1h
7.228(3)
10.800(4)
13.795(5)
112.361(5)
101.523(5)
93.377(5)
965.0(6)
2
C30H18AgF6N2O2S4Sb
1232.82
monoclinic
C2/c
15.722(11)
26.788(11)
7.388(4)
90
100.455(10)
90
3060(3)
4
C28H22AgF6N2PS2
683.06
orthorhombic
Pbca
18.884(3)
12.9143(18)
22.152(3)
90
C56H44Ag2F12N4S4Sb2
528.74
monoclinic
P21/c
22.412(3)
19.241(3)
13.0265(18)
90
90
90
90
90
5402.4(13)
8
1.730
1.024
293(2)
5617.5(14)
4
1.878
1.870
293(2)
Z
F
calcd (g/cm3)
1.811
1.372
293(2)
1.831
1.866
293(2)
µ (mm-1
)
temp (K)
no. of rflns
4984
8098
26 700
28 972
R1; wR2 (I > 2σ(I))
0.0455; 0.1219
0.0403; 0.1103
0.0914; 0.2247
0.0753; 0.2235
Table 3. Crystallographic Data for 9-13
9
10
11
12
13
formula
C34H26AgF6N3SSb
852.26
monoclinic
P21/c
7.8712(19)
14.214(4)
29.383(7)
90
96.393(4)
90
3266.9(14)
4
1.733
1.553
293(2)
C30H21AgF6N3PS
708.40
triclinic
C25H15AgF3N3O3S2
634.39
monoclinic
C2/c
23.755(2)
13.5252(12)
18.0666(17)
90
108.540(2)
90
5503.4(9)
8
1.531
0.935
293(2)
C48H37Ag2F12N4Sb2
1357.06
triclinic
C50H30Ag2F6N8O6S2
1232.68
triclinic
formula wt
cryst syst
space group
a (Å)
b (Å)
c (Å)
P1h
P1h
P1h
7.6547(12)
11.7027(19)
17.768(3)
72.093(3)
77.580(2)
78.561(2)
1464.1(4)
2
12.5677(10)
13.8217(12)
15.4528(13)
80.297(2)
66.647(2)
83.489(2)
2425.9(4)
2
10.410(3)
13.126(4)
19.282(6)
86.692(6)
78.256(6)
76.867(5)
2511.8(14)
2
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F
calcd (g/cm3)
1.607
0.878
293(2)
1.858
1.981
293(2)
1.630
0.943
293(2)
µ (mm-1
)
temp (K)
no. of rflns
16 510
7562
16 250
12 700
13 701
R1; wR2 (I > 2σ(I))
0.0794; 0.1843
0.0769; 0.2034
0.0681; 0.1557
0.0881; 0.1545
0.0585; 0.1164
has encouraged us to undertake further studies on the design
and synthesis of new types of fulvene ligands. Following this
approach, we have expanded the symmetric benzonitrile-
containing fulvene (II) to the symmetric thiophene-containing
fulvene (III) and unsymmetric thiophene- and benzonitrile-
containing fulvene (IV) by the one-pot reaction of 2-thiophen-
ecarbonyl chloride and 4-cyanobenzoyl chloride or 3-cyanoben-
zoyl chloride with cyclopentadiene anion (Scheme 1), respectively.
Symmetric fulvene (II), fulvene (III), and unsymmetric fulvene
(IV) further reacted with hydrazine, benzohydrazine, or hy-
droxylamine to generate the novel target cyclopenta[d]pyridazine
ligands L1-L7. Ligands L1-L7 were isolated as deep yellow
crystalline solids. In comparison to fulvene (II) and (III), ligands
L1-L7 are more soluble in organic solvents, such as CH2Cl2,
CHCl3, THF, benzene, toluene, CH3OH, C2H5OH, and so on.
In the 1H NMR spectra of L1-L7, a single peak related to the
imine group was observed around 14 ppm, which is about 4
ppm shifted to higher field compared to the proton resonance
(∼17-19 ppm) of the hydroxy hydrogen on their precursors of
fulvene (II)-(IV). The IR spectra of ligands L1-L7 showed a
-NH absorption band around 3200 cm-1. The strong absorp-
tion bands around 1600 and 1350 cm-1 are consistent with the
>CdN and fulvene absorptions, respectively, which are com-
parable to those corresponding bands in known compounds.7,11
There are two NS-chelating moieties in L1-L7. These two NS-
chelating coordination moieties and electron-rich cyclopenta-

450 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
Table 4. Interatomic Distances (Å) and Bond Angles (deg)
dienide group cause them to possess two totally different
potential coordination sites: i.e., organometallic vs inorganic
sites. Thus, L1-L7 reported herein could be considered as the
multidentate ligands that could afford not only carbon but also
heteroatom donors. This affords us a good opportunity to
synthesize polymeric organometallic complexes. L4 and L5 are
unsymmetric ligands. As shown in Scheme 1, thiophenecarbonyl
and cyanobenzoyl (4-cyanobenzoyl for L4 and 3-cyanobenzoyl
for L5) moieties are attached to the center five-membered rings,
respectively. Different orientations together with different
coordinative abilities of C , S, and N donors in L4 and L5 would
result in abundant coordination chemistry for this type of ligand.
In addition, the >N-H functional group on pyridazine in these
ligands could be potentially linked by other types of organic
spacers into larger multidentate fulvene ligands,12 which might
lead to more new and novel supramolecular systems.
2. Supramolecular Complexes Based on Symmetric
Thiophene-Containing Ligands L1-L3 and Ag(I) Ion. As
we know, coordination chemistry based on symmetric organic
ligands has been the dominating subject in the self-assembly
field. So far, numerous attractive supramolecular complexes
based on symmetric organic spacers, such as symmetric bridged
bipyridine and biphenylcyanide and also related types of ligands,
have been widely used to construct supramolecular complexes.1-4
However, the coordination chemistry based on a fulvene unit
bridging five-membered heterocyclic-ring-containing symmetric
ligands, such as L1 reported herein, is still unprecedented. The
multiple functionalities of L1 and its versatile conformations
have attracted us to test its coordinative ability toward metal
acceptors, especially soft acid Ag(I) ion.9d-f,13
(a) Synthesis and Structural Analysis of 1 and 2. Reaction
of L1 with AgSO3CF3 (1:2 ratio) in the mixed solvent systems
benzene/methylene chloride and benzene/toluene at room tem-
perature afforded compounds 1 (yield, 59%) and 2 (yield, 64%)
as yellow blocklike and platelike crystals, respectively. Crys-
talllographic data for 1 and 2 are given in Table 1, and selected
interatomic distances and bond angles are given in Table 4.
Single-crystal analysis revealed that compound 1 crystallizes
in the triclinic system with the space group P1h. As shown in
Figure 1, the Ag(I) center in 1 lies in a distorted-tetrahedral
organometallic coordination sphere {AgπNSO} consisting of
one pyridazine N atom (dAg(1)-N(2) ) 2.593(7) Å), one thiophene
S atom (dAg(1)-S(2) ) 2.767(3) Å), one triflate oxygen atom
(dAg(1)-O(2) ) 2.347(3) Å), and one π-donor from the cyclo-
pentadienide moiety on the other L1 ligand (C(3) and C(4)).
All AgI-C bond distances lie in the range of normal sil-
ver-carbon bond lengths (2.47-2.80 Å).7,14-16 Two Ag(I)
with Esds in Parentheses for 1-4
Compound 1
Ag(1)-O(3)
Ag(1)-C(3)#1
Ag(1)-S(2)
2.347(7)
2.488(9)
2.767(3)
Ag(1)-C(4)#1
Ag(1)-N(2)
2.396(8)
2.593(7)
O(3)-Ag(1)-C(4)#1
C(4)#1-Ag(1)-C(3)#1
C(4)#1-Ag(1)-N(2)
O(3)-Ag(1)-S(2)
146.0(3)
31.6(3)
104.3(2)
99.78(17)
144.4(2)
O(3)-Ag(1)-C(3)#1
O(3)-Ag(1)-N(2)
C(3)#1-Ag(1)-N(2)
C(4)#1-Ag(1)-S(2)
N(2)-Ag(1)-S(2)
115.5(3)
93.1(2)
106.5(3)
114.0(2)
65.06(16)
C(3)#1-Ag(1)-S(2)
Compound 2
Ag(1)-O(4)
Ag(1)-C(24)#1
Ag(1)-S(2)
Ag(2)-N(3)
Ag(2)-C(8)
2.337(6)
2.410(8)
2.827(3)
2.397(6)
2.592(9)
Ag(1)-N(2)
Ag(1)-C(23)#1
Ag(2)-O(1)
Ag(2)-C(9)
Ag(2)-S(4)
2.369(5)
2.590(8)
2.378(6)
2.420(8)
2.795(2)
O(4)-Ag(1)-N(2)
111.5(3)
O(4)-Ag(1)-C(24)#1
O(4)-Ag(1)-C(23)#1
147.4(3)
115.7(3)
N(2)-Ag(1)-C(24)#1 101.1(2)
N(2)-Ag(1)-C(23)#1 132.0(2)
C(24)#1-Ag(1)-C(23)#1 32.8(2)
N(2)-Ag(1)-S(2) 70.78(14)
C(24)#1-Ag(1)-S(2) 108.53(18) C(23)#1-Ag(1)-S(2)
O(4)-Ag(1)-S(2)
84.62(17)
104.96(19)
147.7(3)
116.1(3)
32.1(3)
70.52(15)
104.8(2)
O(1)-Ag(2)-N(3)
N(3)-Ag(2)-C(9)
N(3)-Ag(2)-C(8)
O(1)-Ag(2)-S(4)
C(9)-Ag(2)-S(4)
113.0(3)
99.2(3)
129.2(2)
81.33(17)
O(1)-Ag(2)-C(9)
O(1)-Ag(2)-C(8)
C(9)-Ag(2)-C(8)
N(3)-Ag(2)-S(4)
108.09(18) C(8)-Ag(2)-S(4)
Compound 3
Ag(1)-N(2)
Ag(1)-C(9)
Ag(1)-S(2)
2.337(9)
2.53(2)
2.927(4)
Ag(1)-C(12)
Ag(1)-C(1)#1
2.469(14)
2.636(13)
N(2)-Ag(1)-C(12)
C(12)-Ag(1)-C(9)
C(12)-Ag(1)-C(1)#1
N(2)-Ag(1)-S(2)
C(9)-Ag(1)-S(2)
104.7(4)
N(2)-Ag(1)-C(9)
N(2)-Ag(1)-C(1)#1
C(9)-Ag(1)-C(1)#1
C(12)-Ag(1)-S(2)
C(1)#1-Ag(1)-S(2)
156.1(5)
109.4(4)
93.9(6)
113.2(3)
143.5(3)
98.2(6)
30.6(4)
66.3(2)
98.3(5)
Compound 4
Ag(1)-O(4)
Ag(1)-O(4)#2
Ag(1)-C(23)#1
2.379(5)
2.463(4)
2.613(6)
Ag(1)-C(24)#1
Ag(1)-N(2)
Ag(1)-S(1)
2.449(5)
2.477(4)
2.8546(18)
O(4)-Ag(1)-C(24)#1
131.9(2)
O(4)-Ag(1)-O(4)#2
75.67(17)
104.49(15)
151.04(18)
C(24)#1-Ag(1)-O(4)#2 96.56(17) O(4)-Ag(1)-N(2)
C(24)#1-Ag(1)-N(2)
O(4)-Ag(1)-C(23)#1
O(4)#2-Ag(1)-C(23)#1 102.43(19) N(2)-Ag(1)-C(23)#1
O(4)-Ag(1)-S(1)
O(4)#2-Ag(1)-S(1)
C(23)#1-Ag(1)-S(1)
103.63(14) O(4)#2-Ag(1)-N(2)
102.5(2)
C(24)#1-Ag(1)-C(23)#1 31.84(19)
105.69(15)
115.37(14)
65.46(10)
111.61(15) C(24)#1-Ag(1)-S(1)
87.25(14) N(2)-Ag(1)-S(1)
145.91(13)
centers are linked together by two trans-L1 species into a
{Ag2(trans-L1)2} cationic dinuclear boxlike unit (Figure 2). The
Ag(I)‚‚‚Ag(I) separation in the {Ag2(trans-L1)2} moiety is
7.087(3) Å. These boxlike units are connected to each other
by three sets of weak F‚‚‚H-C17 (F(1)‚‚‚H(14) ) 2.6 Å,
F(2)‚‚‚H(13) ) 2.5 Å, F(2)‚‚‚H(2) ) 2.7 Å) hydrogen-bonding
systems into one-dimensional chains extended along the crystal-
lographic b axis. Benzene solvent molecules are located between
these chains. As shown in Figure 3, the benzene molecules are
close to Ag(I) centers, and the closest Ag‚‚‚C distance is 3.0
Å, which is beyond of the normal range of Ag-C bond lengths.
Compound 2 crystallizes in the triclinic system with the space
group P1h. As shown in Figure 4, the asymmetric unit contains
two different Ag(I) centers, two L1 ligands, two triflate
(11) William, J. L.; William, H. S. J. Am. Chem. Soc. 1957, 79, 4970.
(12) Su, C.-Y.; Cai, Y.-P.; Chen, C.-L.; Lissner, F.; Kang, B.-S.; Kaim,
W. Angew. Chem., Int. Ed. 2002, 41, 3371.
(13) (a) Khlobystov. A. N.; Blake, A. J.; Champness, N. R.; Lemenovskii,
D. A.; Majouga, A. G.; Zyk, N. V.; Schro¨der, M. Coord. Chem. ReV. 2001,
222, 155. (b) Dong, Y.-B.; Zhao, X.; Huang, R.-Q.; Smith, M. D.; zur Loye,
H.-C. Inorg. Chem. 2004, 43, 5603. (c) Dong, Y.-B.; Zhao, X.; Tang, B.;
Huang, R.-Q.; Wang, H.-Y.; Smith, M. D.; zur Loye, H.-C. Chem. Commun.
2004, 220. (d) Chen, C.-L.; Su, C.-Y.; Cai, Y.-P.; Zhang, H.-X.; Xu, A.-
W.; Kang, B.-S.; zur Loye, H.-C. Inorg. Chem. 2003, 42, 3738. (e) Hong,
M.; Su, W.; Cao, R.; Fujita, M.; Lu, J. Chem. Eur. J. 2003, 6, 427. (f)
Hirsch, K. A.; Wilson, S. R.; Moore, J. S. Chem. Eur. J. 1997, 3, 765. (g)
Venkataraman, D.; Lee, S.; Moore, J. S.; Zhang, P.; Hirsch, K. A.; Gender,
G. B.; Covey, A. C.; Prentice, C. L. Chem. Mater. 1996, 8, 2030. (h) Hirsch,
K. A.; Wilson, S. R.; Moore, J. S. Inorg. Chem. 1997, 36, 2960. Xu, Z. T.;
Kiang, Y.-H.; Lee, S.; Lobkovsky, E. B.; Emmott, N. J. Am. Chem. Soc.
2000, 122, 8376. (i) Min, K. S.; Suh, M. P. J. Am. Chem. Soc. 2000, 122,
6834. (j) Zhang, S.-L.; Tong, M.-L.; Chen, X.-M. Coord. Chem. ReV. 2003,
246, 185.
(15) Munakata, M.; Wu, L. P.; Ning, G. L. Coord. Chem. ReV. 2000,
198, 171.
(16) Rundle, R. E.; Goring, J. H. J. Am. Chem. Soc. 1950, 72, 5337. (b)
Smith, H. G. Rundle, R. E. J. Am. Chem. Soc. 1958, 80, 5075.
(17) (a) Hobza, P.; Havlas, Z. Chem. ReV. 2000, 100, 4253 and references
therein. (b) Dong, Y.-B.; Smith, M. D.; Layland, R. C.; zur Loye, H.-C.
Inorg. Chem. 1999, 38, 5027. (c) Cai, Y.-P.; Zhang, H.-X.; Xu, A.-W.; Su,
C.-Y.; Chen, C.-L.; Liu, H.-Q.; Zheng, L.; Kang, B.-S. Dalton Trans. 2001,
2429.
(14) (a) Griffith, E. A. H.; Amma, E. L. J. Am. Chem. Soc. 1974, 96,
5407. (b) Rodesiler, P. F.; Amma, E. L. Inorg. Chem. 1972, 11, 388.

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 451
Figure 4. ORTEP drawing of 2.
Figure 1. ORTEP drawing of 1.
Figure 2. Organometallic dinuclear boxlike unit in 1.
Figure 5. (a) View of twin chain formed by linking a single chain
through the Ag-(SO3CF3)2-Ag linkage. (b) Twin chains arranged
one by one along the b axis, with benzene molecules filling in the
clearance.
bond lengths range from 2.478 to 2.481 Å) and two triflate O
donors (O(1), dAg(1)-O(1) ) 2.378(6) Å; O(3), dAg(1)-O(3) ) 2.828-
(6) Å) surround the Ag(2) atom into a five-coordinated sphere.
In the solid state, trans-L1 binds the Ag(1) and Ag(2) cen-
ters through the η2-cyclopentadienide group and NS-chelating
interactions into one-dimensional chains along the crystal-
lographic [100] direction. Every two of these chains are further
linked together by interchain Ag-(SO3CF3)2-Ag linkages into
a twin-chain motif (Figure 5a). The shortest intrachain and
interchain Ag‚‚‚Ag distances are 7.6 and 5.6 Å. These twin
chains arrange in the crystallographic bc plane in parallel, and
the uncoordinated benzene molecules are located between them
(Figure 5b).
Figure 3. Crystal packing of 1. Benzene guest molecules are
located between chains.
counterions, and two benzene solvent molecules. The first silver
atom lies in a {AgNOSπ} coordination sphere, being made of
one N donor (N(2), dAg(1)-N(2) ) 2.369(5) Å), one O donor
(O(4), dAg(1)-O(4) ) 2.337(6) Å), one S donor (dAg(1)-S(2)
)
2.827(3) Å), one π donor from one L1 ligand and one
coordinated SO3CF3- counterion, and two π donors (Ag(1)-C
bond distances range from 2.410(8) to 2.592(9) Å) from the
cyclopentadienide groups on the other L1 ligand, respectively.
The second Ag(I) center adopts a {AgNO2Sπ} coordination
environment. One set of NS-chelating moiety (Ag(2)-N(3) and
Ag(2)-S(4) bond lengths are 2.397(6) and 2.795(6) Å, respec-
tively) and one π donor from the other L1 ligand (Ag(2)-C
(b) Synthesis and Structural Analysis of 3. Compound 3
was obtained by combination of L1 with AgSbF6 in a benzene/
toulene mixed solvent system as yellow platelike crystals in
41% yield. Compound 3 crystallizes in the triclinic system with
the space group P1h. Crystalllographic data for 3 are given in
Table 1, and selected interatomic distances and bond angles are
given in Table 4. As shown in Figure 6, there is one kind of
crystallographically independent Ag(I) atom in the asymmetric

452 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
Figure 6. Molecular structure of 3.
Figure 8. Coordination environment of Ag(I) in 4.
Figure 7. µ2-η2-benzene molecules bridging {Ag2(trans-L1)2} units
into a one-dimensional chain.
Figure 9. Boxlike moiety in compound 4.
unit. It adopts a {AgNSπ2} distorted coordination sphere which
consists of an NS chelating moiety (dAg(1)-N(2) ) 2.337(9)Å)
and dAg(1)-S(2) ) 2.927(4) Å), two π donors (AgI-C bond
distances range from 2.469(14) to 2.636(13) Å) from the
cyclopentadienide group on the other L1 ligand, and one solvent
benzene molecule, respectively.
-
Figure 10. Bidentate ClO4 anions linking boxlike moieties into
As shown in Figure 7, two silver atoms are bound together
by two trans-L1 ligands into boxlike {Ag2(trans-L1)2} units,
which are further bridged together by µ2-η2 solvent benzene
molecules through Ag-π interactions into a one-dimensional
chain along the crystallographic b axis.
a one-dimensional chain.
(c) Synthesis and Structural Analysis of 4 and 5. Ligand
L1 together with AgClO4 in a benzene/toluene mixed solvent
system generates compound 4 as orange crystals in 60%
yield. Crystallographic data for 4 are given in Table 1, and
selected interatomic distances and bond angles are given in
Table 4. Each Ag(I) atom is coordinated by one NS che-
lating moiety (Ag(1)-N(2) ) 2.477(4) and Ag(1)-S(1) )
-
2.8546(18) Å) from one L1, two O donors from two ClO4
Figure 11. Crystal packing of 4 (view down the chain direction).
anions (Ag(1)-O(4)#2 ) 2.463(4) Å), and one π donor
(Ag(1)-C(24)#1 ) 2.449(5) Å and Ag(1)-C(23)#1 ) 2.613-
(6) Å) to generate the five-coordinated sphere {AgNSO2π}
(Figure 8). Two trans-L1 ligands and two Ag(I) atoms again
constitute a boxlike moiety (Figure 9) which is the same as
that in 1 and 3. The difference is that the “glue” between these
moieties is a metal-heteroatom coordination bond instead of
the H-bonding interaction in 1 and 2 or metal-π interaction in
3. As shown in Figure 10, boxlike units are connected to each
uncoordinated benzene molecules are located between chains
and are vertical to the chain-extending direction (Figure 11).
Compound 5 was synthesized by the same method as for 4.
Single-crystal X-ray diffraction analysis revealed that 5 and 4
are isostructural. Crystallographic data for 5 are given in Table
2, and selected interatomic distances and bond angles are given
in Table 5. As indicated in Figure 12, the coordination environ-
ment of the Ag(I) atom in 5 is the same as that in 4. All the
bond lengths around Ag(I) centers are comparable with those
in 4.
-
other by coordinated ClO4 counterions into a linear chain
running along the crystallographic b axis.
It is worth pointing out that all these one-dimensional chains
are parallel (Figure 11), which is different from the case in
[Ag(C15H10N2O2)]ClO4, composed of a homologous furan-ful-
vene ligand and AgClO4 from the same solvent system, wherein
two sets of one-dimensional chains are perpendicular.7e In 4,
The common feature of compounds 1-5 lies in the fact that
they all possess a {Ag2(L1)2} molecular boxlike building block.
In compounds 1-5, L1 exhibits similar coordination behavior:
i.e., it uses both organometallic (cyclopentadienide) and inor-

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 453
Table 5. Interatomic Distances (Å) and Bond Angles (deg)
with Esds in Parentheses for 5-8
Compound 5
Ag(1)-O(4)
Ag(1)-O(4)#2
Ag(1)-C(8)#1
2.383(4)
2.465(4)
2.616(5)
Ag(1)-C(9)#1
Ag(1)-N(2)
Ag(1)-S(1)
2.451(5)
2.479(4)
2.8534(17)
O(4)-Ag(1)-C(9)#1
131.95(18) O(4)-Ag(1)-O(4)#2 75.87(16)
104.51(14)
103.56(13) O(4)#2-Ag(1)-N(2) 150.97(16)
102.26(18) C(9)#1-Ag(1)-C(8)#1 32.08(17)
C(9)#1-Ag(1)-O(4)#2 96.51(16) O(4)-Ag(1)-N(2)
C(9)#1-Ag(1)-N(2)
O(4)-Ag(1)-C(8)#1
O(4)#2-Ag(1)-C(8)#1 102.50(17) N(2)-Ag(1)-C(8)#1
O(4)-Ag(1)-S(1)
O(4)#2-Ag(1)-S(1)
C(8)#1-Ag(1)-S(1)
105.66(14)
115.24(13)
65.47(9)
111.70(14) C(9)#1-Ag(1)-S(1)
87.13(13) N(2)-Ag(1)-S(1)
146.02(12)
Compound 6
Ag(1)-N(1)#1
Ag(1)-S(1)
2.155(3)
3.0805(14)
Ag(1)-N(1)
2.155(3)
N(1)#1-Ag(1)-N(1) 174.51(16) N(1)#1-Ag(1)-S(1) 116.25(8)
N(1)-Ag(1)-S(1)
68.53(8)
C(11)-N(1)-O(1)
118.4(3)
Figure 13. Molecular structure of 6., with two L2 ligands binding
the Ag(I) ion in a face-to-face fashion to form a {S2O2} crown
ether like moiety.
Compound 7
Ag(1)-N(1)
Ag(1)-C(8)#1
2.253(5)
2.551(8)
Ag(1)-C(9)#1
Ag(1)-S(1)
2.335(7)
2.888(3)
N(1)-Ag(1)-C(9)#1
153.5(2) N(1)-Ag(1)-C(8)#1 144.2(2)
N(1)-Ag(1)-S(1) 73.10(15)
C(8)#1-Ag(1)-S(1) 128.98(19)
chelating metal rings formed by L1 are strained. Different metal-
to-ligand ratios (1:2, 1:3, and even 1:4) were tried, but
compounds 1-5 were always isolated as the only products. It
is interesting that the connectors between the {Ag2(L1)2} unit
change from an F‚‚‚H-C H-bond (1) to L1 (2) to a benzene
solvent molecule (3) and then to a counterion (4 and 5). The
only possible explanation for this change might be the different
coordinating strengths resulting from the different counterions,
due to all five reactions being carried out under exactly the same
conditions, including solvent system, metal-to-ligand ratio, and
temperature. The templating effect of the counterion in deter-
mining the type and topology of the product was well demon-
strated by many earlier studies.18 Compounds 1-5 reported
herein represent additional examples for this kind of phenom-
enon.
(d) Synthesis and Structural Analysis of 6. Compound 6
was obtained by combination of L2 with AgSbF6 in a benzene/
toluene mixed solvent system as yellow block crystals in 51%
yield. Crystallographic data for 6 are given in Table 2, and
selected interatomic distances and bond angles are given in Table
5. In 6, the Ag(I) center is linearly coordinated by two N donors
(N(1)#1-Ag(1)-N(1) ) 174.51(16)°) with a short Ag-N bond
distance of 2.155(3) Å. The two S donors from two NS chelating
sites are only weakly interacting with Ag(I) (Ag(1)-S(1) )
3.0805(14) Å). As shown in Figure 13, two cis-L2 ligands are
present, with two coordinating SN and two uncoordinating SO
chelating moieties being located on both sides of the N-Ag-N
axis. Two uncoordinated SO chelating sites form an {S2O2}
crown ether like cavity (S‚‚‚S and O‚‚‚O distances are ca. 5.6
and 5.2 Å, respectively) that provides a potential metal ion
recognition site. In the solid state, {Ag(L2)2} building blocks
are parallel and are driven by intermolecular π-π interactions
(the related aromatic ring centroid to ring centroid distance is
3.5 Å) into a one-dimensional chain along the crystallographic
C(9)#1-Ag(1)-C(8)#1 33.7(3)
C(9)#1-Ag(1)-S(1)
96.0(2)
Compound 8
Ag(1)-N(3)
Ag(1)-C(17)
Ag(2)-N(2)
Ag(2)-C(3)
2.283(7)
2.550(10)
2.273(7)
2.556(10)
Ag(1)-C(18)
Ag(1)-S(3)
Ag(2)-C(4)
Ag(2)-S(1)
2.349(9)
2.889(4)
2.340(9)
2.881(4)
N(3)-Ag(1)-C(18)
C(18)-Ag(1)-C(17)
C(18)-Ag(1)-S(3)
N(2)-Ag(2)-C(4)
C(4)-Ag(2)-C(3)
C(4)-Ag(2)-S(1)
154.9(3)
33.3(3)
97.7(3)
154.9(3)
34.3(3)
97.0(3)
N(3)-Ag(1)-C(17)
N(3)-Ag(1)-S(3)
C(17)-Ag(1)-S(3)
N(2)-Ag(2)-C(3)
N(2)-Ag(2)-S(1)
C(3)-Ag(2)-S(1)
144.0(3)
73.10(19)
130.3(3)
143.7(3)
73.05(19)
130.4(2)
ganic faces (SN chelating site) to bind the Ag(I) atom. It is
worth pointing out that, in 1-5, L1 always adopts a trans
conformation to form an {Ag2(L1)2} boxlike unit. The coor-
dination behavior of L1 herein is different from that of its
furan-fulvene analogue.7g As noted above, only one of two
NS chelating moieties in L1 involves the metal coordination
sphere and the other is free, which might indicate that two NS
(18) (a) Kuroda-Sowa, T.; Horrino, T.; Yamamoto, M.; Ohno, Y.;
Maekawa, M.; Munakata, M. Inorg. Chem. 1997, 36, 6382. (b) Hennigar,
T. L.; MacQuarrie, D. C.; Losier, P.; Rogers, R. D.; Zaworotko. M. J. Angew.
Chem., Int. Ed. Engl. 1997, 36, 972. (c) Lu, J.; Paliwala, T.; Lim, S. C.;
Yu, C.; Niu, T.; Jacobson, A. J. Inorg. Chem. 1997, 36, 923. (d) Munakata,
M.; Ning, G. L.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Harino, T.
Inorg. Chem. 1998, 37, 5651. (e) Power, K. N.; Hennigar, T. L.; Zaworotko,
M. J. New J. Chem. 1998, 22, 177. (f) Jung, O. S.; Park, S. H.; Kim, K.
M.; Jang, H. G. Inorg. Chem. 1998, 37, 5781. (g) Withersby, M. A.; Blake,
A. J.; Champness, N. R.; Hubberstey, P.; Li, W.-S.; Schro¨der, M. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2327.
Figure 12. ORTEP drawing of 5.

454 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
Figure 14. One-dimensional chain in 6 driven by Ag‚‚‚S and π-π
interactions.
Figure 16. Coordination sphere around Ag(I) in 7.
Figure 15. Crystal packing of 6 (view down the chain direction).
c axis (Figure 14). The shortest intrachain Ag‚‚‚Ag distance is
3.70 Å, which is slightly longer than the sum of the van der
Waals radii of two silver atoms, 3.44 Å.19 At the same time,
additional weak Ag‚‚‚S interactions (3.355(4) Å) further strengthen
the one-dimensional chains. Thus, the S atom herein behaves
as a µ2-bridging atom. As shown in Figure 15, all of these one-
Figure 17. One-dimensional sinusoidal chain in 7.
-
dimensional chains align parallel; the uncoordinated SbF6
anions are located between chains. It is interesting that the
coordination behavior of L2 is different from that of L1 in this
specific reaction. As shown above, the cyclopentadienide moiety
in L2 was not involved in the Ag(I) coordination sphere, but it
was in L1. The coordination difference between L2 and L1
results in the different polymeric motifs of 6 and 1-5.
(e) Synthesis and Structural Analysis of 7 and 8. Com-
pound 7 was obtained as brown platelike crystals by combination
of L3 with AgPF6 in a benzene/toluene mixed solvent system
(yield 54%). Single-crystal analysis revealed that compound 7
crystallizes in the orthorhombic system with the space group
Pbca. Crystallographic data for 7 are given in Table 2, and
selected interatomic distances and bond angles are given in Table
5. As shown in Figure 16, the Ag(I) center lies in a five-
coordinated {AgSNπ2} coordination environment consisting of
one SN chelating site (dAg(1)-N(1) ) 2.253(5) Å and dAg(1)-S(1)
) 2.888(3) Å), two π-donors from a coordinated cyclopenta-
Figure 18. ORTEP drawing of 8.
dienide ring (dAg(1)-C(9)#1 ) 2.335(7) Å, and dAg(1)-C(8)#1
)
2.551(8) Å), and one coordinated toluene solvent molecule
(dAg(1)-C(23) ) 2.8507(5) Å). All other AgI-Ctoluene bond
distances are beyond the range of normal silver-carbon bond
lengths (2.47-2.80 Å).7 As shown above, the coordination
behavior of L3 is similar to that of L1. One of the two SN
chelating sites and cyclopentadienide ring on L3 are involved
in the Ag(I) coordination sphere.
In the solid state, Ag(I) centers are bound together through
SN chelating and cyclopentadienide π donors into a sinusoidal
chain running along the crystallographic b axis (Figure 17). The
coordinated toluene molecules are located on both sides of the
chain but apparently make no contribution to the topology of
the network. Uncoordinated PF6- counterions lie in the concave
part of the sinusoidal chain.
To explore the templating role of counterions in the self-
assembly process, AgSbF6 was used instead of AgPF6 to carry
out the reaction under the same reaction conditions. As shown
in Figure 18, there are two different crystallographic silver atoms
in 8; they are all trigonally coordinated by one SN chelating
donor (Ag-N bond lengths 2.273(7)-2.283(7) Å) and one
cyclopentadienide π donor (Ag(1)-C(18) ) 2.349(9) Å and
Ag(1)-C(17) ) 2.550(10) Å). No coordinated solvent molecules
were found in 8, which is different from the case in 7.
Crystallographic data for 8 are given in Table 2, and selected
interatomic distances and bond angles are given in Table 5. It
is noteworthy that two coordinated and uncoordinated thiophene
planes of L3 in 7 and 8 are perpendicular to each other, which
is a result of the steric influence of the phenyl ring adjacent to
the uncoordinated thiophene ring. As indicated in Figure 19,
the coordination pattern of 8 is the same as that of 7, which is
(19) Bertelli, M.; Carlucci, L.; Ciani, G.; Proserpio, D. M.; Sironi, A. J.
Mater. Chem. 1997, 7, 1271.

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 455
Table 6. Interatomic Distances (Å) and Bond Angles (deg)
with Esds in Parentheses for 9-13
Compound 9
Ag(1)-N(3)#1
Ag(1)-N(2)
2.219(8)
2.422(6)
Ag(1)-C(3)#2
Ag(1)-C(4)#2
2.402(8)
2.527(8)
N(3)#1-Ag(1)-C(3)#2 135.6(3) N(3)#1-Ag(1)-N(2)
C(3)#2-Ag(1)-N(2) 107.0(2) N(3)#1-Ag(1)-C(4)#2 130.6(3)
C(3)#2-Ag(1)-C(4)#2 33.2(3) N(2)-Ag(1)-C(4)#2 113.9(2)
113.2(2)
Figure 19. One-dimensional chain in 8.
Compound 10
Ag(1)-N(3)#1
Ag(1)-C(25)
2.196(7)
2.440(15)
Ag(1)-N(2)
Ag(1)-C(30)
2.305(5)
2.620(17)
N(3)#1-Ag(1)-N(2)
N(2)-Ag(1)-C(25)
N(2)-Ag(1)-C(30)
128.5(2)
122.5(3)
101.3(4)
N(3)#1-Ag(1)-C(25)
N(3)#1-Ag(1)-C(30)
C(25)-Ag(1)-C(30)
105.3(4)
130.3(4)
30.0(3)
Compound 11
Ag(1)-N(2)
Ag(1)-C(2)#1
2.262(5)
2.448(7)
Ag(1)-O(3)
Ag(1)-C(3)#1
2.333(5)
2.493(7)
N(2)-Ag(1)-O(3)
119.38(18) N(2)-Ag(1)-C(2)#1
134.20(19)
127.69(18)
O(3)-Ag(1)-C(2)#1 105.92(19) N(2)-Ag(1)-C(3)#1
O(3)-Ag(1)-C(3)#1 106.09(19) C(2)#1-Ag(1)-C(3)#1 32.5(2)
Compound 12
Ag(1)-N(4)#1
Ag(2)-N(3)#2
Ag(2)-C(28)
Ag(2)-C(3)
2.235(10)
2.350(11)
2.4698(13)
2.752(12)
Ag(1)-N(2)
Ag(2)-C(2)
Ag(2)-C(33)
2.274(8)
2.368(12)
2.7238(13)
N(4)#1-Ag(1)-N(2)
N(3)#2-Ag(2)-C(28)
N(3)#2-Ag(2)-C(33)
N(3)#2-Ag(2)-C(3)
C(28)-Ag(2)-C(3)
122.1(4)
95.7(3)
110.6(3)
129.9(4)
117.4(3)
N(3)#2-Ag(2)-C(2)
C(2)-Ag(2)-C(28)
C(2)-Ag(2)-C(33)
C(2)-Ag(2)-C(3)
C(33)-Ag(2)-C(3)
103.0(4)
143.7(3)
113.9(3)
30.0(3)
Figure 20. Molecular structure of 9.
88.9(3)
a result of the similar coordination preference of the Ag(I) ion
toward the ligand L3.
Compound 13
Ag(1)-N(7)#1
Ag(1)-N(3)#2
Ag(2)-N(4)#3
Ag(2)-O(3)
2.275(7)
2.370(7)
2.272(8)
2.374(9)
2.542(9)
Ag(1)-N(2)
Ag(1)-N(6)
Ag(2)-N(8)
Ag(2)-C(4)#4
2.350(6)
2.403(6)
2.279(8)
2.388(8)
3. Supramolecular Complexes Based on Unsymmetric
Ligands L4 and L5. The idea behind the use of ligands L4
and L5 is to explore the coordination chemistry and self-
assembly principles of this unsymmetric type of ligand. There
is no doubt that unsymmetrically bridging ligands with two or
more coordination sites with differing donor abilities are
expected to result in more unprecedented coordination polymers
or supramolecular complexes with novel topologies than can
be achieved with symmetric ligands.10
(a) Synthesis and Structural Analysis of 9. Compound 9
was obtained as yellow crystals by combination of L4 with
AgSbF6 in a benzene/toluene mixed solvent system at 57% yield.
As shown in Figure 20, compound 9 crystallizes in the
monoclinic system with the space group P21/c. Crystallographic
data for 9 are given in Table 3, and selected interatomic
distances and bond angles are given in Table 6. There is only
one type of crystallographic Ag(I) center in 9, and it lies in the
distorted inorganic tetrahedral coordination environment {AgN2π}
Ag(2)-C(3)#4
N(7)#1-Ag(1)-N(2)
N(2)-Ag(1)-N(3)#2
N(2)-Ag(1)-N(6)
N(4)#3-Ag(2)-N(8)
N(8)-Ag(2)-O(3)
N(8)-Ag(2)-C(4)#4
132.4(2) N(7)#1-Ag(1)-N(3)#2 97.9(2)
100.5(2) N(7)#1-Ag(1)-N(6)
109.4(2) N(3)#2-Ag(1)-N(6)
100.4(3) N(4)#3-Ag(2)-O(3)
103.2(2)
112.5(2)
109.3(3)
98.7(3)
N(4)#3-Ag(2)-C(4)#4 111.0(3)
130.8(3) O(3)-Ag(2)-C(4)#4
105.1(3)
99.9(3)
N(4)#3-Ag(2)-C(3)#4 138.0(3) N(8)-Ag(2)-C(3)#4
O(3)-Ag(2)-C(3)#4
103.5(3) C(4)#4-Ag(2)-C(3)#4 33.1(2)
-
toluene solvent molecules and SbF6 counterions are located
on both sides of the ring plane (Figure 22). In the solid state,
these two-dimensional nets stack parallel along the crystal-
lographic c axis. When the structure is viewed down the crystal-
lographic a axis, rectangular channels containing benzene and
-
toluene molecules and SbF6 anions have been found (Fig-
defined by two N donors from one -CN group (dAg(1)-N(3)#1
)
ure 23).
2.219(8) Å) and one pyridazine ring (dAg(1)-N(2) ) 2.422(6) Å)
on the other L4 ligand, respectively. The π donor comes from
cyclopentadienide with Ag(1)-C bond lengths of 2.402(8) and
2.527(8) Å, respectively. All of these bond distances are similar
to the corresponding bond lengths found in compounds 1-8
and previous polymeric Ag(I) complexes based on fulvene (II)
ligands.7
As shown in Figure 21, tridentate L4 ligands link silver atoms
through cyclopentadienide π-Ag and pyridazine N-Ag inter-
actions into zigzag chains running conversely. These two sets
of chains are further bound together alternately through the side
benzonitrile arm of L4 into a two-dimensional net extending in
the crystallographic ab plane (Figure 21). This net contains the
trinuclear squarelike ring {Ag3(L4)3}, in which the Ag‚‚‚Ag
distances are ca. 11, 9, and 8 Å. Uncoordinated benzene and
(b) Synthesis and Structural Analysis of 10. The idea
behind the use of ligand L5 is to control supramolecular motifs
through different donors’ orientations. It is well-known that the
relative different orientations of the terminal coordination donors
and also the different bridging spacing might result in unusual
building blocks, which can lead to the construction of supramo-
lecular motifs that have not been achieved using normal rigid
linear bidentate organic ligands.20 We earlier reported on a series
(20) (a) Barnett, S. A.; Champness, N. R. Coord. Chem. ReV. 2003, 246,
145. (b) Kaes, C.; Katz, A.; Hosseini, M. W. Chem. ReV. 2000, 100, 3553.
(c) Withersby, M. A.; Blake, A. J.; Champuess, N. R.; Cooke, P. A.;
Hubberstey, P.; Li, W.-S.; Schro¨der, M. Inorg. Chem. 1999, 38, 2259. (d)
Campos-Ferna´ndez, C. S.; Cle´rac, R.; Dunbar, K. R. Angew, Chem., Int.
Ed. 1999, 38, 3477. (e) Albrecht, M. Angew. Chem., Int. Ed. 1999, 38,
3463.

456 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
Figure 21. From one-dimensional zigzag chains to a two-dimensional net.
Figure 24. Ag(I) coordination environment and dinuclear metal-
lacycle in 10.
that compound 10 crystallizes in the triclinic system with the
space group P1h. Crystallographic data for 10 are given in Table
3, and selected interatomic distances and bond angles are given
in Table 6. As shown in Figure 24, the Ag(I) center lies in a
distorted triangular {AgN2π} coordination environment consist-
ing of one -CN donor (dAg(1)-N(3)#1 ) 2.196(7) Å), one
pyridazine (dAg(1)-N(2) ) 2.305(5) Å), and one π donor from a
coordinated benzene (dAg(1)-C(25) ) 2.440(15) Å and dAg(1)-C(30)
) 2.620(17) Å). The corresponding bond distances are very
close to those found in compounds 1-9. As indicated in Figure
24, two Ag(I) centers are connected to each other by two cis-
L5 ligands in a face-to-face fashion through -CN and Npyridazine
donors into a bimetallic 16-membered molecular {Ag2(L5)2}
Figure 22. Trinuclear squarelike ring {Ag3(L4)3} containing
benzene, toluene guest molecules, and SbF6 counterions.
-
-
ring. Two uncoordinated PF6 anions are situated on the both
sides of the ring plane. The intra-ring Ag‚‚‚Ag distance is 6.8
Å. Herein, L5 acts as an angular ligand (the bite angle between
one terminal -CN donor and its adjacent Npyridazine donor being
around 60°) which has a strong tendency to form a metallacyclic
moiety with inorganic metal ions. Such a type of geometric
configuration together with different electron donors would be
expected to form new metallacycle-containing coordination
polymers or supramolecular complexes. It is obvious that the
coordination motif of 10 is distinctly different from that of 9,
which does result from the different relative orientations of the
-CN donors on them. In addition, the cyclopentadienide moiety
remains uncoordinated, which is probably due to the solvent
benzene molecule taking its coordinating position.
(c) Synthesis and Structural Analysis of 11. For exploring
the templating role of counterions in the self-assembly process,
AgSO3CF3 was used instead of AgPF6 to carry out the reaction
under the same reaction conditions. Combination of L5 with
AgSO3CF3 (1:2 ratio) in benzene/toluene at room temperature
afforded compound 11 as yellow crystals in 59% yield. Single-
crystal analysis revealed that compound 11 crystallizes in the
monoclinic system with the space group C/2c. Crystallographic
data for 11 are given in Table 3, and selected interatomic
Figure 23. Rectangular channels containing benzene, toluene
molecules, and SbF6 anions (view down the crystallographic a
axis).
-
of novel coordination polymers generated from rigid bidentate
4,4′-bipyridine- and 3,3′-bipyridine-type double Schiff-base
ligands. Indeed, our previous studies demonstrated that the
relative orientation of the coordinating sites is one of the most
important factors in controlling the polymeric motifs.7,21
Reaction of L5 with AgPF6 (1:2 ratio) in benzene/toluene at
room temperature afforded compound 10 as green-yellow
platelike crystals in 71% yield. Single-crystal analysis revealed
(21) (a) Dong, Y.-B.; Smith, M. D.; Layland, R. C.; zur Loye, H.-C.
Chem. Mater. 2000, 12, 1156. (b) Dong, Y.-B. Smith, M. D.; zur Loye,
H.-C. Inorg. Chem. 2000, 39, 4927. (c) Ciurtin, D. M.; Dong, Y.-B.; Smith,
M. D.; Barclay, T.; zur Loye, H.-C. Inorg. Chem. 2001, 40, 2825.

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 457
Figure 27. Two-dimensional H-bonded net in 11.
Figure 25. Coordination sphere of Ag(I) in 11.
Figure 26. One-dimensional zigzag chain in 11.
distances and bond angles are given in Table 6. The unsym-
metric unit contains only one type of Ag(I) ion, which lies in a
{AgNOπ} coordination sphere. One pyridazine N donor
(dAg(1)-N(2) ) 2.262(5) Å), one OOTf donor (dAg(1)-O(3) ) 2.333-
(5) Å), and the cyclopentadienide π donor (dAg(1)-C(2)#1 ) 2.448-
(7) Å and dAg(1)-C(3)#1 ) 2.493(7) Å) constitute the Ag(I)
coordination environment (Figure 25). It is noteworthy that the
-CN group was not involved in the silver coordination sphere.
We tried several times to change the metal-to-ligand ratios;
however, compound 11 was the only compound that could be
isolated from the reactions, probably due to the templating
Figure 28. ORTEP drawing of 12.
obtained from a benzene/toluene system. The yellow plate
crystals of 12 were obtained in 2 weeks in 63% yield when a
toluene solution of L6 was allowed to diffuse into a benzene
solution of AgSbF6. The single-crystal structure reveals that
compound 12 crystallizes in the triclinic system with the space
group P1h. Crystallographic data for 12 are given in Table 3,
and selected interatomic distances and bond angles are given
in Table 6. As indicated in Figure 28, the unsymmetric unit of
12 contains two different crystallographic Ag(I) centers. The
first Ag(I) atom is four-coordinated ({AgN2π2}) by one ben-
zonitrile N donor (dAg(1)-N(4)#1 ) 2.235(10) Å), one pyridazine
N donor (dAg(1)-N(2) ) 2.274(8) Å), and two π-donors from two
coordinated benzene molecules (dAg(1)-C(37) ) 2.879(8) Å,
dAg(1)-C(41) ) 2.777(8) Å, and dAg(1)-C(40) ) 2.878(8) Å). It is
worthwhile to point out that the two coordinated benzene
molecules behave as η2 and η1 spacers, respectively, which is
indicated by the Ag-C bond distances. The second Ag(I) ion
lies in a {AgNFπ2} coordination sphere which is composed of
-
effects of different counterions (from uncoordinated PF6 to
weakly coordinated SO3CF3-). As shown in Figure 26, L5 acts
as a bidentate linker to bunch silver atoms into zigzag chains
extended along the crystallographic b axis. In 11, weak
hydrogen-bonding interactions are present. As shown in Figure
27, the one-dimensional polymer chains of 11 have close
neighboring chains resulting from two sets of interpolymer
hydrogen-bonding interactions. The first set of hydrogen-
-
bonding system involves F(1) of the SO3CF3 group and
H(24) on the L5 ligand of the neighboring chain. The
F(1)‚‚‚H(24) contact is 2.7 Å, and the F(1)‚‚‚C(24) distance and
F(1)‚‚‚H(24)-C(24) angle are 3.3 Å and 123°, respectively. The
second hydrogen-bonding system consists of N(1) of the
uncoordinated -CN group and H(22) on the thiophene ring of
the neighboring chain. The N(1)‚‚‚H(22) contact is 2.7 Å, and
the N(1)‚‚‚C(22) distance and N(1)‚‚‚H(22)-C(22) angle are
3.3 Å and 119°, respectively. These interpolymer hydrogen-
bonding interactions give rise to a 2-D layered arrangement of
1-D polymers parallel to the crystallographic ab plane.
one NCN donor (dAg(2)-N(3)#2 ) 2.350(11) Å), one FSbF donor
6
(dAg(2)-F(1) ) 2.693(11) Å), and two π donors from one η2-
coordinated benzene molecule (Ag(2)-C(2) ) 2.368(12) Å and
Ag(2)-C(3) ) 2.752(12) Å) and one η2-cyclopentadienide
moiety (Ag(2)-C(28) ) 2.4698(13) Å and Ag(2)-C(33) )
2.7238(13) Å), respectively. It is worth pointing out that there
are four types of benzene molecules in 12. The first and second
types of benzene molecules act as the coligands attached to the
AgI-L6 chain, which contains a 19-membered metallacyclic
4. Supramolecular Complexes Based on Symmetric Ben-
zonitrile-Containing Ligands L6 and L7 and Ag(I) Ion. (a)
Synthesis and Structural Analysis of 12. Compound 12 was

458 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
rectangular channels (crystallographic dimensions ca. 18 × 9
Å) are evident in 13. The benzene guest molecules are located
in the center of the channels; when the structure is viewed down
the crystallographic b axis, distorted rectangular channels
(crystallographic dimensions ca. 15 × 5 Å) have been found,
and encapsulated benzene guest molecules are close to the wall
of the channels (Figure 34). When the structure is viewed down
the [-111] direction, distorted honeycomb-like channels could
be found. As indicated in Figure 35, the aromatic rings are
arrayed toward the channels, which potentially makes possible
the recognition of aromatic molecules.
5. Photoluminescence Properties. Inorganic-organic hybrid
coordination polymers have been investigated for fluorescence
properties and for potential applications as light-emitting diodes
(LEDs). Owing to the ability of inorganic-organic coordination
polymers to affect the emission wavelength of organic materials,
syntheses of these compounds by the judicious choice of organic
spacers and transition-metal centers can be an efficient method
for obtaining new types of luminescent materials,23 especially
for d10 or d10-d10 systems24 and conjugated ligand containing
complexes.25 We have been exploring the luminescent properties
of fulvene ligands and organic/inorganic coordination polymers
and supramolecular complexes based on them in the solid state.
The results indicate that emission colors of organic spacers were
affected by their incorporation into metal-containing coordina-
tion compounds. The luminescence properties of L1, L3, L5,
and L7 and polymeric compounds 1-3 and 5 were investigated
in CH3OH and the solid state. In the solid-state case, single-
crystalline samples were used for the measurements. The ground
microcrystalline samples were housed in the solid sample quartz
carrier. The excitation and emission slit widths are 5 nm. The
fluorescence spectra of the ligands and their complexes are
summarized in Table 7. As indicated in Figure 36, in CH3OH,
L1 and L5 present two maxima at 400 and 387 nm for L1 and
349 and 367 nm for L5, respectively. L3 and L7 present one
maximum at 371 nm for L3 and 345 nm for L7. In the solid
state, L1, L3, L5, and L7 exhibit only one emission maximum
at 363, 390, 385, and 378 nm, respectively. As shown in Table
7, the emission colors of the Ag(I) complexes, in comparison
to those of their corresponding free ligands, for all the emission
bands in the solid state are red-shifted. Meanwhile, the emission
Figure 29. From a one-dimensional metallacyclic ring-containing
chain to a two-dimensional net.
Figure 30. Crystal packing of 12. Benzene guest molecules are
located between two-dimensional nets.
ring. Meanwhile, the third type of benzene molecule acts as a
bidentate spacer to bridge these one-dimensional chains into a
two-dimensional net which is composed of large (ca. 10 × 8
Å) and small (ca. 10 × 4 Å) rectangle-like cavities (Figure 29).
The fourth type of benzene molecule is located between these
layers as guest molecules (Figure 30).
(b) Synthesis and Structural Analysis of 13. The combina-
tion of L7 with AgSO3CF3 in a benzene/toluene mixed solvent
system generated compound 13 as yellow crystals in 68% yield.
Crystallographic data for 13 are given in Table 3, and selected
interatomic distances and bond angles are given in Table 6. As
in 12, the unsymmetric unit of 13 contains two crystallographi-
cally different Ag(I) atoms. The first Ag(I) center is defined by
four N donors (dAg(1)-N(7)#1 ) 2.275(7) Å, dAg(1)-N(2) ) 2.350-
(6) Å, dAg(1)-N(3)#2 ) 2.370(7) Å, and dAg(1)-N(6) ) 2.403(6) Å)
of two benzonitrile and two pyridazine moieties. The second
Ag(I) center lies in a {AgN2Oπ} coordination sphere which
consists of two benzonitrile N donors (dAg(2)-N(4)#3 ) 2.272(8)
(22) (a) Schmuck, C.; Angew. Chem., Int. Ed. 2003, 42, 2448. (b)
Ezuhara, T.; Endo, K.; Aoyama, Y. J. Am. Chem. Soc. 1999, 121, 3279.
(23) (a) Altmann, M.; Bunz, U. H. F. Angew. Chem. 1995, 34, 569. (b)
Bunz, U. H. F. Chem. ReV. 2000, 100, 1605. (c) Ciurtin, D. M.; Pschirer,
N. G.; Smith, M. D.; Bunz, U. H. F.; zur Loye, H.-C. Chem. Mater. 2001,
13, 2743. (d) Cariati, E.; Bu, X.; Ford, P. C. Chem. Mater. 2000, 12, 3385.
(e) Wu¨rthner, F.; Sautter, A. Chem. Commun. 2000, 445. (f) Burini, A.;
Bravi, R.; Fackler, J. P., Jr.; Galassi, R.; Grant, T. A.; Omary, M. A.;
Pietroni, B. R.; Staples, R. J. Inorg. Chem. 2000, 39, 3158. (g) Seward, C.;
Jia, W.-L.; Wang, H.-Y.; Enright, G. D.; Wang, S. Angew. Chem., Int. Ed.
2004, 43, 2933. (h) Wu, C.-D.; Ngo, H. L.; Lin, W. Chem. Commun. 2004,
1588. (i) Hu, N.-X.; Esteghamation, M.; Xie, S.; Popovic, Z.; Hor, A.-M.;
Ong, B.; Wang, S. AdV. Mater. 1999, 11, 1460. (j) Wang, J.; Wang, R.;
Yang, J.; Zheng, Z.; Carducci, M. D.; Cayou, T.; Peyghgambarian, N.;
Jabbour, G. E. J. Am. Chem. Soc. 2001, 123, 6179. (k) Catalano, V. J.;
Kar, H. M.; Bennett, B. L. Inorg. Chem. 2000, 39, 121.
(24) (a) Harvey, P. D.; Gray, H. B. J. Am. Chem. Soc. 1988, 110, 2145.
(b) Catalano, V. J.; Kar, H. M.; Bennett, B. L. Inorg. Chem. 2000, 39, 121.
(c) Tong, M.-L.; Chen, X.-M.; Ye, B.-H.; Ji, L.-N. Angew. Chem., Int. Ed.
1999, 38, 2237. (d) Burini, A.; Bravi, R.; Fackler, J. P., Jr.; Galassi, R.;
Grant, T. A.; Omary, M. A.; Pietroni, B. R.; Staples, R. J. Inorg. Chem.
2000, 39, 3158. (e) Seward, C.; Jia, W.-L.; Wang, R.-Y.; Enright, G. D.;
Wang, S.-N. Angew. Chem., Int. Ed. 2004, 43, 2933. (f) Yam, V. W.-W.;
Lo, K. K.-W. Chem. Soc. ReV. 1999, 28, 323.
-
Å and dAg(2)-N(8) ) 2.279(8) Å), one O donor from the SO3CF3
anion (dAg(2)-O(3) ) 2.374(9) Å), and a π donor from a
η2-cyclopentadienide group (Ag-C bond lengths from 2.388-
(8) to 2.542(9) Å) (Figure 31). In compound 13, cis- and trans-
L7 ligands are concomitant (Figure 32). As indicated in Fig-
ure 33, cis- and trans-L7 ligands arrange alternately and link
Ag(1) and Ag(2) atoms through the pyridazine group and one
of the two sets of benzonitrile groups into a novel double-helical
chain extending along the crystallographic [1-10] direction. The
intrachain Ag(1)‚‚‚Ag(1) and Ag(2)‚‚‚Ag(2) distances are ca.
10 Å. The other set of benzonitrile groups surrounds the column
and extends outward in four different directions. Each column
connects four other equivalent columns through Nbenzonitrile
-
(25) (a) Hu, N.-X.; Esteghamatian, M.; Xie, S.; Popovic, Z.; Hor, A.-
M.; Ong, B.; Wang, S.-N. AdV. Mater. 1999, 11, 1460. (b) de Silva, A. S.;
de Silva, M. A. A.; Carvalho, C. E. M.; Antunes, O. A. C.; Herrera, J. O.
M.; Brinn, I. M.; Mangrich, A. S. Inorg. Chim. Acta 1999, 292, 1. (c) Wang,
J.; Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Cayou, T.; Peygham-
barian, N.; Jabbour, G. E. J. Am. Chem. Soc. 2001, 123, 6179.
Ag interactions into a novel noninterpenetrating porous frame-
work. The network contains large channels with different shapes
extending in the different directions. When the structure is
viewed down the crystallographic [1-10] direction, large

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 459
Figure 31. Coordination environments of Ag(1) and Ag(2) in 13.
Figure 32. Cis and trans conformations of L7 in compound 13.
Figure 33. One-dimensional double-helical chain (left), three-dimensional framework (middle), and rectangular channel (right) in 13.
colors of these complexes in solution are blue-shifted, probably
due to the fact that the polymeric frameworks in polar solvent
break down and result in the formation of oligomers and even
discrete molecular complexes. As shown above, the middle
fulvene and two terminal thiophene or benzonitrile groups are
not coplanar but seriously twist, which is probably the reason
that the excitation wavelengths for the ligands and complexes
are relatively short.25 Overall, the emission colors of the free
ligands were significantly affected by their incorporation into
the Ag(I)-containing complexes, as evidenced by the large shift
in the emission.
Conclusions
The seven new symmetric and unsymmetric ligands L1-L7
were synthesized. The results indicate that the coordination
chemistry of new fulvene ligands with the soft acid Ag(I) ion
is versatile. They can adopt either a cis or a trans conformation
to bind Ag(I) not only through the terminal N and central N
Figure 34. Three-dimensional framework in 13 (view down the
[1-10] direction).
donors but also through the cyclopentadienide group into
organometallic coordination polymers or discrete complexes.

460 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
δ relative to TMS. Element analyses were performed on a Perkin-
Elmer Model 240C analyzer. All fluorescence measurements were
carried out on a Cary Eclipse spectrofluorimeter (Varian, Australia)
equipped with a xenon lamp and quartz carrier at room temperature.
Safety note: Perchlorate salts of metal complexes with organic
ligands are potentially explosiVe and should be handled with care.
Preparation of Fulvene (II)-1, Fulvene (III)-1, and Fulvene
(IV)-1. A solution of 4-cyanobenzoyl chloride (1.76 g, 10.6 mmol)
and 2-thiophenecarbonyl (1.46 mL, 10.6 mmol) in anhydrous ether
(20 mL) was added dropwise to a solution of cyclopentadienyl
anions (31.8 mmol) in anhydrous ether at 0 °C, which was derived
from Cp (31.8 mmol) and PhLi (31.8 mmol) in anhydrous ether.
The mixture was stirred overnight at room temperature. The solvent
was then reduced to about 10 mL under vacuum. Hexane was added,
and an orange solid precipitated. The solid was washed with hex-
ane several times and stirred in HCl (5% in water) overnight. The
final product was purified by column chromatography on silica gel
(CH2Cl2/hexane, 2:1) to afford fulvene (II)-1, fulvene (III)-1, and
fulvene (IV)-1. Fulvene(II)-1: 0.63 g, yield 18.4%; corresponding
spectral data of fulvene(II)-1 are identical with those of reported
data.7d Fulvene (III)-1 (0.31 g, yield 10.2%): mp 106-108 °C; IR
(KBr pellet) ν (cm-1) 3480 (s), 3100 (s), 1615 (s), 1540 (s), 1510
(s), 1460 (s), 1400 (s), 1215 (vs), 1130 (vs), 1100 (vs), 1050 (vs),
830 (w), 710 (s); 1H NMR (300 MHz, CDCl3, 25 °C, TMS) δ 18.30
(s, 1H, -OH), 8.13 (d, 2H, -C4H3S), 8.02 (d, 2H, -C4H3S), 7.59
(d, 2H, -C4H3S), 7.33 (q, 2H, -C5H3), 6.64 (t, 1H, -C5H3). Anal.
Calcd for C15H10S2O2: C, 62.94; H, 3.50. Found: C, 62.77; H,
3.43. In addition, fulvene (III)-1 could be obtained by following
method as well: a solution of 2-thiophenecarbonyl (2.6 mL, 19
mmol) in anhydrous ether (20 mL) was added dropwise to a solution
of cyclopentadiene anion (2.4 mL, 28.5 mmol) in anhydrous ether
at 0 °C. The mixture was stirred overnight at room temperature.
The solvent was then reduced to about 10 mL under vacuum.
Hexane was added, and a yellow solid precipitated. The solid was
washed with hexane several times and stirred in HCl (5% in water)
overnight. The final product was purified by column chromatog-
raphy on silica gel (CH2Cl2/hexane, 1:1) to afford fulvene (III)-1
as a red-orange crystalline solid: yield 40.0%. Fulvene (IV)-1 (0.91
g, yield 28.1%): mp 114-117 °C; IR (KBr pellet) ν (cm-1) 3446
(s), 2229 (m), 1630 (s), 1539 (m), 1471 (s), 1420 (s), 1281 (vs),
Figure 35. Three-dimensional framework in 13 (view down the
[-111] direction).
Figure 36. Photoinduced emission spectra of L1-L3 and L7 in
EtOH at room temperature.
Table 7. Luminescence Properties of L1, L3, L5, L7, 1-3,
1
1229 (vs), 1129 (vs), 904 (vs), 849 (s), 707 (s); H NMR (300
and 5 in the Solid State and CH3OH
MHz, CDCl3, 25 °C, TMS) δ 18.33 (s, 1H, -OH), 8.26, 8.02, 7.93,
7.88 (m, 7H, -C4H3S, -C6H4), 7.34, 7.14, 6.63 (t, t, d, 3H, -C5H3).
Anal. Calcd for C18H11NO2S: C, 70.82; H, 3.61. Found: C, 70.73;
H, 3.52.
λex/λem (nm)
compd solid state CH3OH
λex/λem (nm)
compd
solid state
CH3OH
L1
L3
L5
L7
206/363
220/390
215/385
220/378
256/400, 387
247/371
242/349, 367
243/345
1
2
3
5
215/382
242/368
225/392, 404 241/348
214/394 222/384
235/405, 416 224/381
Preparation of Fulvene (II)-2, Fulvene (III)-1, and Fulvene
(IV)-4. Fulvene (II)-2, fulvene (III)-1, and fulvene (IV)-2 were
prepared by following the procedure descried for fulvene (II)-1,
fulvene (III)-1, and fulvene (IV)-1, except with 3-cyanobenzoyl
chloride (1.76 g, 10.6 mmol) instead of 4-cyanobenzoyl chloride
(1.76 g, 10.6 mmol), to afford fulvene (II)-2, fulvene (III)-1, and
fulvene (IV)-2 as orange crystalline solids. Fulvene(II)-2: 0.21 g,
yield 7.0%; corresponding spectral data of fulvene(II)-2 are identical
with those of reported data.7d Fulvene (III)-1: 0.73 g, yield 21.3%.
Fulvene (IV)-2: 1.21 g, yield 37.4%; mp 102-104 °C; IR (KBr
pellet) ν (cm-1) 3447 (s), 2231 (s), 1621 (s), 1545 (s), 1518 (s),
1478 (s), 1399 (s), 1131 (m), 1084 (m), 1052 (m), 803 (s), 759 (s),
716 (s); 1H NMR (300 MHz, CDCl3, 25 °C, TMS) δ 18.30 (s, 1H,
-OH), 8.18, 8.06, 7.77, 7.33 (m, 7H, -C4H6, -C4H3S), 7.15, 6.65
(m, 3H, -C5H3). Anal. Calcd for C18H11NO2S: C, 70.82; H, 3.61.
Found: C, 70.74; H, 3.51.
We are currently extending this result by preparing new fulvene
ligands of this type that have different substituted organic
functional groups. We anticipate this approach to be useful
for the construction of a variety of new transition-metal com-
plexes and luminescent coordination polymers with novel
structures that have the potential of leading to new fluorescent
materials.
Experimental Section
Materials and Methods. 4-Cyanobenzoyl chloride, 3-cyanoben-
zoyl chloride, and 2-thiophenecarbonyl were prepared according
to literature methods.7 Inorganic metal salts were purchased from
Acros and used without further purification. Infrared (IR) sam-
ples were prepared as KBr pellets, and spectra were obtained in
the 400-4000 cm-1 range using a Perkin-Elmer 1600 FTIR
spectrometer. 1H NMR data were collected using a JEOL FX 90Q
NMR or AM-300 spectrometer. Chemical shifts are reported in
Preparation of L1. A solution of fulvene (III)-1 (0.40 g) in
anhydrous EtOH (20 mL) and a large excess of N2H4‚H2O was
heated to reflux for about 7 h. After the mixture was cooled to
room temperature, the solvent was removed under reduced pressure
to give a red-orange solid. The product was recrystallized from
EtOH to give orange crystals of L1: yield 87.1%; mp 178-180

Ag(I) Polymers and Complexes with FulVene Ligands
Organometallics, Vol. 25, No. 2, 2006 461
°C; IR (KBr pellet) ν (cm-1) 3320 (s), 3150 (s), 1600 (s), 1540 (s),
Preparation of 1. Compound 1 was synthesized in 59% yield
by layering a benzene solution (10 mL) of AgSO3CF3 (14.4 mg,
0.06 mmol) over a CH2Cl2 solution (10 mL) of L1 (8.5 mg, 0.03
mmol). IR (KBr pellet): γ (cm-1) 3448 (s), 1643 (s), 1540 (s),
1399 (s), 1267 (vs), 1179 (s), 1034 (s), 847 (m), 704 (m), 646 (d).
Anal. Calcd for C19H13N2AgF3O3S3: C, 39.45; H, 2.25; N, 4.84.
Found: C, 39.28; H, 2.21; N, 4.67.
1510 (s), 1450 (s), 1405 (m), 1385 (s), 1300 (vs), 1245 (vs), 1200
1
(vs), 1100 (vs), 910 (vs), 850 (s), 700 (s); H NMR (300 MHz,
DMSO, 25 °C, TMS) δ 14.09 (s, 1H, -NH), 8.03, 7.75, 7.38 (s, s,
m, 6H, -C4H3S), 7.28, 7.17 (s, d, 3H, -C5H3). Anal. Calcd for
C15H10N2S2: C, 63.83; H, 3.55; N, 9.93. Found: C, 63.95; H, 3.67;
N, 9.81.
Preparation of 2. Compound 2 was synthesized in 64% yield
by layering a toluene solution (10 mL) of AgSO3CF3 (14.4 mg,
0.06 mmol) over a benzene solution (10 mL) of L1 (8.5 mg, 0.03
mmol). IR (KBr pellet): γ (cm-1) 3448 (s), 1643 (s), 1540 (s),
1399 (s), 1267 (vs), 1179 (s), 1034 (s), 847 (m), 704 (m), 646 (d).
Anal. Calcd for C44H30Ag2F6N4O6S6: C, 42.83; H, 2.43; N, 4.54.
Found: C, 42.68; H, 2.31; N, 4.29.
Preparation of 3. Compound 3 was synthesized in 41% yield
by layering a toluene solution (7 mL) of L1 (8.5 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (20.6 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 3450 (s), 1616 (s), 1361 (s), 1021 (s),
890 (s), 752 (s), 661 (s). Anal. Calcd for C18H15AgF6N2OS2Sb: C,
31.63; H, 2.20; N, 4.10. Found: C, 31.41; H, 2.13; N, 4.05.
Preparation of 4. Compound 4 was synthesized in 60% yield
by layering a toluene solution (7 mL) of L1 (8.5 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgClO4 (12.75 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 3449 (s), 1625 s), 1520 (m), 1388 (s),
1358 (s), 1144 (s), 1117 (s), 1083 (s), 891 (s), 747 (s), 630 (s).
Anal. Calcd for C18H13AgClN2O4S2: C, 40.85; H, 2.46; N, 5.30.
Found: C, 40.97; H, 2.31; N, 5.19.
Preparation of L2. L2 was prepared by following the procedure
described for L1, except with NH2OH instead of N2H4‚H2O, to
afford L2 as an orange crystalline solid: 0.28 g, yield 70.3%; mp
84-86 °C; IR (KBr pellet) ν (cm-1) 1613 (s), 1540 (s), 1510 (s),
1450 (s), 1398 (m), 1385 (s), 1300 (vs), 1245 (vs), 1200 (vs), 1100
1
(vs), 905 (vs), 846 (s), 708 (s); H NMR (300 MHz, DMSO, 25
°C, TMS) δ 14.09 (s, 1H, -NH), 8.03, 7.75, 7.38 (s, s, m, 6H,
-C4H3S), 7.28, 7.17 (s, d, 3H, -C5H3). Anal. Calcd for
C15H9NOS2: C, 63.60; H, 3.18; N, 4.95. Found: C, 63.54; H, 3.12;
N, 4.90.
Preparation of L3. L3 was prepared by following the procedure
described for L1, except with PhNHNH2 instead of N2H4‚H2O, to
afford L3 as a yellow-orange crystalline solid: 0.42 g, yield 82.7%;
mp 212-216 °C; IR (KBr pellet) ν (cm-1) 3200 (vs), 1595 (s),
1560 (s), 1540 (s), 1500 (s), 1410 (s), 1320 (s), 1310 (s), 1230 (s),
1
1170 (s), 1090 (s), 850 (s), 700 (s); H NMR (300 MHz, DMSO,
25 °C, TMS) δ 8.02, 7.54, 7.47, 7.38, 7.24 (m, t, m, s, m, 11H,
-C6H5, -C4H3S), 7.18, 7,03 (m, t, 3H, -C5H3). Anal. Calcd for
C21H14N2S2: C, 70.39; H, 3.91; N, 7.82. Found: C, 70.23; H, 3.67;
N, 7.74.
Preparation of 5. Compound 5 was synthesized in 64% yield
by layering a toluene solution (7 mL) of L1 (8.5 mg, 0.03
mmol) over a benzene solution (10 mL) of AgPF6 (14.4 mg, 0.06
mmol). IR (KBr pellet): γ (cm-1) 3421 (s), 3120 (w), 1600 (s),
1538 (m), 1510 (m), 1438 (s), 1398 (vs), 1278 (s), 1234 (vs), 1170
(s), 918 (m), 850 (m), 759 (m), 706 (s), 630 (s). Anal. Calcd for
C44H32N4Ag2F6O6S6: C, 42.79; H, 2.59; N, 4.54. Found: C, 42.15;
H, 2.41; N, 4.61.
Preparation of 6. Compound 6 was synthesized in 51% yield
by layering a toluene solution (7 mL) of L2 (8.4 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (20.6 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 3420 (s), 3122 (w), 1603 (s), 1536 (m),
1616 (s), 1361 (s), 1024 (s), 891 (s), 752 (s), 662 (s). Anal. Calcd
for C30H18AgF6N2O2S4Sb: C, 39.55; H, 1.98; N, 3.08; Found: C,
39.25; H, 1.77; N, 2.99.
Preparation of 7. Compound 7 was synthesized in 54% yield
by laying a toluene solution (7 mL) of L3 (11.4 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgPF6 (14.4 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 1637 (s), 1618 (s), 1453 (s), 1400 (s),
1306 (s), 1398 (s), 1158 (s), 849 (s), 778 (m), 750 (m), 701 (m),
620 (s). Anal. Calcd for C28H22AgF6N2PS2: C, 47.80; H, 3.13; N,
3.98. Found: C, 47.71; H, 3.10; N, 3.91.
Preparation of 8. Compound 8 was synthesized in 57% yield
by layering a toluene solution (7 mL) of L3 (11.4 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (20.6 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1): 1632 (s), 1557 (s), 1536 (s), 1492 (s),
1445 (s), 1398 (s), 1346 (s), 1321 (s), 1222 (s), 1171 (s), 1031 (s),
931 (m), 878 (s), 776 (m), 749 (m), 700 (s), 670 (vs). Anal. Calcd
for C56H44Ag2F12N4S4Sb2: C, 42.31; H, 2.77; N, 3.53. Found: C,
42.22; H, 2.71; N, 3.47.
Preparation of L4. L4 was prepared by following the procedure
described for L3, except with fulvene (IV)-1 instead of fulvene
(III)-1, to afford L4 as a yellow-orange crystalline solid: 0.31 g,
yield 78.0%; mp 113-116 °C; IR (KBr pellet) ν (cm-1) 3446 (s),
3316 (s), 2221 (s), 1610 (vs), 1591 (s), 1395 (s), 1365 (s), 1240
1
(vs), 1095 (vs), 1061 (vs), 894 (vs), 853 (s), 755 (s), 717 (s); H
NMR (300 MHz, DMSO, 25 °C, TMS) δ 14.20 (s, 1H, -NH),
8.05-8.28 (q, 4H, -C6H4), 7.88-7.43 (m, 3H, -C4H3S), 7.12-
6.94 (m, 3H, -C5H3). Anal. Calcd for C18H11N3S: C, 71.76; H,
3.65; N, 13.95. Found: C, 71.47; H, 3.48; N, 13.67.
Preparation of L5. L5 was prepared by following the procedure
described for L4, except with PhNHNH2 and fulvene (IV)-2 instead
of N2H4‚H2O and fulvene (IV)-1, to afford L5 as a yellow-orange
crystalline solid: 0.40 g, yield 80.0%; mp 186-189 °C; IR (KBr
pellet) ν (cm-1) 3223 (s), 2226 (s), 1650 (s), 1576 (s), 1520 (s),
1488 (s), 1434 (s), 1309 (s), 1182 (s), 1093 (vs), 900 (vs), 849 (s),
806 (s), 754 (s), 699 (s); 1H NMR (300 MHz, DMSO, 25 °C, TMS)
δ 7.79-8.38 (m, 4H, -C6H4), 7.47-7.31 (m, 8H, -C4H3S, -C6H5),
7.10-6.90 (m, 3H, -C5H3). Anal. Calcd for C24H15N3S: C, 76.39;
H, 3.98; N, 11.14. Found: C, 76.26; H, 3.89; N, 11.22.
Preparation of L6. L6 was prepared by following the procedure
described for L5, except with fulvene (II)-1 instead of fulvene (IV)-
2, to afford L6 as a yellow-orange crystalline solid: 0.30 g, yield
75.4%; mp 194-197 °C; IR (KBr pellet) ν (cm-1) 3433 (s), 2233
(s), 1681 (s), 1620 (m), 1546 (s), 1450 (s), 1400 (s), 1112 (vs),
951 (vs), 902 (vs), 835 (vs), 800 (vs), 691 (s); 1H NMR (300 MHz,
DMSO, 25 °C, TMS) δ 14.12 (s, 1H, -NH), 8.38-7.40 (m, 8H,
-C6H4), 7.29, 7.20, 6.89 (s, s, s, 3H, -C5H3). Anal. Calcd for
C21H12N4: C, 78.75; H, 3.75; N, 17.50. Found: C, 78.64; H, 3.63;
N, 17.14.
Preparation of 9. Compound 9 was synthesized in 57% yield
by layering a toluene solution (7 mL) of L4 (11.3 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (20.6 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 3442 (s), 2248 (s), 1634 (s), 1400 (s),
1021 (s), 848 (s), 779 (s), 657 (vs). Anal. Calcd for C34H26N3AgF6
SSb: C, 47.89; H, 3.05; N, 4.93. Found: C, 47.76; H, 3.00; N,
4.87.
Preparation of L7. L7 was prepared by following the procedure
described for L6, except with fulvene (II)-2 and N2H4‚H2O instead
of fulvene (II)-1 and PhNHNH2, to afford L7 as a yellow-orange
crystalline solid: 0.60 g, yield 77.8%; mp 175-177 °C; IR (KBr
pellet) ν (cm-1) 2229 (m), 1610 (m), 1580 (s), 1490 (m), 1410
(vs), 1326 (s), 1185 (m), 1120 (m), 850 (s), 760 (s), 730 (m), 633
1
(m); H NMR (300 MHz, DMSO, 25 °C, TMS) δ 8.38-7.37 (m,
13H, -C6H4, -C6H5), 7.05, 6.63 (d, p, 3H, -C5H3). Anal. Calcd
for C27H16N4: C, 81.80; H, 4.07; N, 14.13. Found: C, 81.91; H,
4.31; N, 14.03.
Preparation of 10. Compound 10 was synthesized in 71% yield
by layering a toluene solution (7 mL) of L5 (11.3 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgPF6 (14.5 mg, 0.06 mmol).

462 Organometallics, Vol. 25, No. 2, 2006
Dong et al.
IR (KBr pellet): γ (cm-1) 3419 (s), 3128 (s), 2264 (s), 1631 (s),
1400 (s), 1337 (m), 1127 (s), 924 (s), 839 (s), 750 (s), 637 (s), 557
(s). Anal. Calcd for C30H21AgF6N3PS: C, 51.82; H, 2.96; N, 5.93.
Found: C, 51.71; H, 3.10; N, 5.76.
Preparation of 11. Compound 11 was synthesized in 59% yield
by layering a toluene solution (7 mL) of L5 (11.3 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgOTf (14.4 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 3226 (s), 2231 (s), 1621 (s), 1580 (s),
1510 (s), 1488 (s), 1434 (s), 1263 (vs), 1100 (s), 911 (s), 846 (s),
806 (s). Anal. Calcd for C25H15AgF3N3O3S2: C, 47.29; H, 2.36;
N, 6.62. Found: C, 47.16; H, 2.31; N, 6.54.
Preparation of 12. Compound 12 was synthesized in 63% yield
by layering a toluene solution (7 mL) of L6 (11.9 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (20.6 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 2230 (s), 1612 (s), 1580 (s), 1504 (s),
1402 (s), 1325 (s), 1124 (s), 842 (s), 776 (m), 700 (s), 670 (vs).
Anal. Calcd for C48H37Ag2F12N4Sb2: C, 42.45; H, 2.73; N, 4.13.
Found: C, 45.33; H, 2.65; N, 4.02.
(Mo KR radiation, λ ) 0.710 73 Å). The raw frame data for 1-13
were integrated into SHELX-format reflection files and corrected
for Lorentz and polarization effects using SAINT.27 Corrections
for incident and diffracted beam absorption effects were applied
using SADABS.27 There was no evidence of crystal decay during
data collection for any compound. Space groups were determined
by a combination of systematic absences in the intensity data,
intensity statistics, and the successful solution and refinement of
the structures. All structures were solved by direct methods followed
by difference Fourier synthesis and refined against F2 by the full-
matrix least-squares technique, using SHELX.26 Crystal data, data
collection parameters, and refinement statistics for 1-13 are listed
in Tables 1-3. Relevant interatomic bond distances and bond angles
for them are given in Tables 4-6.
Acknowledgment. We are grateful for financial support from
the National Natural Science Foundation of China (No. 20371030)
and Shangdong Natural Science Foundation (No. Z2004B01).
Preparation of 13. Compound 13 was synthesized in 68% yield
by layering a toluene solution (7 mL) of L7 (9.6 mg, 0.03 mmol)
over a benzene solution (10 mL) of AgSbF6 (14.4 mg, 0.06 mmol).
IR (KBr pellet): γ (cm-1) 2233 (s), 1605 (s), 1501 (s), 1398 (s),
1136 (s), 878 (s), 776 (m), 749 (m), 674 (vs). Anal. Calcd for
C50H30Ag2F6N8O6S2: C, 48.66; H, 2.43; N, 9.08; Found: C, 48.53;
H, 2.36; N, 9.01.
Crystallography. Suitable single crystals of 1-13 were selected
and mounted onto thin glass fibers. X-ray intensity data were
measured on a Bruker SMART APEX CCD-based diffractometer
Supporting Information Available: CIF files giving crystal-
lographic data for 1-13. This material is available free of charge
via the Internet at http://pubs.acs.org.
OM0507169
(26) Hay, C.; Hissler, M.; Fischmeister, C.; Rault-Berthelot, J.; Toupet,
L.; Nyula´szi, L.; Re´au, R. Chem. Eur. J. 2001, 7, 4222.
(27) SMART Version 5.624, SAINT Version 6.02, SADABS and
SHELXTL Version 5.1; Bruker Analytical X-ray Systems, Inc., Madison,
WI, 1998.