Rare Organosilver(I) Coordination Polymers Constructed from

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Rare Organosilver(I) Coordination Polymers Constructed from Hydroxyl-Substituted Benzenesulfonic Acids: Syntheses, Structures and Characterizations Zhao-Peng Deng, Ming-Shuai Li, Zhi-Biao Zhu, Li-Hua Huo,* Hui Zhao, and Shan Gao* Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China

bS Supporting Information ABSTRACT: Four rare organosilver(I) coordination polymers, namely [Ag2L1]n (1), [Ag2L1(H2O)]n (2), [Ag2L2(H2O)]n (3), and [Ag5(L3)(NH3)2(NO3)]n (4) (H2L1 = 2-hydroxy-5-chlorobenzenesulfonic acid, H2L2 = 2-hydroxy-5-bromobenzenesulfonic acid, H4L3 = 4,6-dihydroxy-1,3-benzenedisulfonic acid), have been successfully prepared and characterized by elemental analysis, IR, PL, TG, and single-crystal X-ray diffraction. Complex 1 possesses a two-dimensional (2-D) inorganic layer structure. The η1 silver(I)
benzene interactions brings the chlorophenyl moieties closer to the Ag
S
O layers and thus remarkably decreases the gallery height between the two adjacent layers. Complexes 2 and 3 contain pseudocubic tetranuclear units which are further bridged by the η2 silver(I)
benzene interactions to form a new type of 2-D hybrid layer structure which is completely different from that of 1. Complex 4 has a three-dimensional (3-D) organosilver(I) coordination framework, in which the fully deprotonated L34
tetraanion presents an unprecedented coordination mode and bridges 14 silver(I) ions; the unusual μ2-η3-benzene mode of the phenyl ring has not been reported to date.

’ INTRODUCTION Organosilver(I) complexes have attracted important attention due to their diverse, intriguing structures and potential applications in electrochemistry, luminescence, and organic catalysis.1
4 Of these, silver(I) complexes with silver(I)
arene interactions represent one of the main members and have been widely studied due to the overall planarity of the polycyclic aromatic hydrocarbons (PAHs) and the extended delocalized π-electron system.2 As research has expanded, π electron system substituted benzene or polycyclic aromatic ligands have also been employed.3,4 In contrast, organosilver(I) complexes bearing benzene or polycyclic aromatic ligands attached with coordination groups, such as sulfonic groups5 and carboxyl grousp6 have been rarely reported, as these groups easily coordinate to silver(I) ions and occupy the coordination sites around silver(I) ions, thus effectively decreasing the contact between silver(I) ion and the phenyl ring and making the synthesis of silver(I) complexes with silver(I)
benzene interactions difficult. Furthermore, in the present organosilver(I) complexes, a close inspection indicates that the detected coordination modes of the phenyl ring contain the usual η1, η2, η1:η1, η1:η2, and η2:η2 and the rare η3 and η6 (Scheme 1), and different coordination modes can highly influence the final structures and properties. Accordingly, further investigation of the coordination modes of the phenyl ring and the r 2011 American Chemical Society

design of organosilver(I) complexes bearing aromatic ligands attached with coordination groups remains a instructive challenge. Sulfonates are broadly classified as soft and weakly coordinating ligands.7 In this sense, silver(I) ion, with its soft Lewis acidic properties, is a particularly good match for the flexible coordinative tendencies of sulfonate anions. Consequently, arenesulfonates have been exhaustively used to fabricate silver(I) complexes, most of which have a 2-D layered “inorgano-organic” structure.7
9 However, only a few organosilver(I) complexes containing silver(I)
benzene interactions were reported in these series, in which the arenesulfonic acid includes 1,5-naphthalenedisulfonic acid,5a 1-naphthalenesulfonic acid, and 1-pyrenesulfonic acid.5b It should be noted that the existence of silver(I)
benzene interactions prevents the formation of a “common” layer structure by forming a new kind of layer, even 3-D networks.5a,b In comparison with the PAHs sulfonic acid, only one organosilver(I) complex constructed from p-toluenesulfonate has been detected to date.5c Hence, in order to further extend the coordination modes of the phenyl ring and synthesize organosilver(I) coordination polymers with substituted benzenesulfonic acid ligands, we present here the syntheses and Received: January 6, 2011 Published: March 17, 2011 1961

dx.doi.org/10.1021/om200009f | Organometallics 2011, 30, 1961–1967

Organometallics

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Scheme 1. Schematic Representation of Ag
Benzene Coordination Modes

structural characterizations of four rare organosilver(I) polymers, [Ag2L1]n (1), [Ag2L1(H2O)]n (2), [Ag2L2(H2O)]n (3), and [Ag5(L3)(NH3)2(NO3)]n (4) (H2L1 = 2-hydroxy-5-chlorobenzenesulfonic acid, H2L2 = 2-hydroxy-5-bromobenzenesulfonic acid, H4L3 = 4,6-dihydroxy-1,3-benzenedisulfonic acid). Complexes 1
3 exhibita 2-D layer structure containing common η1 and η2 silver(I)
benzene interactions, while the 3-D complex 4 involves unusual silver(I)
benzene interactions (μ2-η3-benzene).

’ EXPERIMENTAL SECTION General Procedures. All chemicals and solvents were of AR grade and were used without further purification in the syntheses. Elemental analyses were carried out with a Vario MICRO instrument from Elementar Analysensysteme GmbH, and the infrared spectra (IR) were recorded from KBr pellets in the range of 4000
400 cm
1 on a Bruker Equinox 55 FT-IR spectrometer. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer TG/DTA 6300 thermal analyzer under a flowing N2 atmosphere, with a heating rate of 10 °C/min. Luminescence spectra were measured on a Perkin-Elmer LS 55 luminance meter. Syntheses of Ligands. p-Chlorophenol, p-bromophenol, and resorcin were slowly added to 20% oleum with stirring, respectively. The mixture was left to react for 2 h at 80 °C and then cooled to room temperature. The white solids were separated and recrystallized from hot water. For H2L1: yield 81%; mp 60
63 °C. Anal. Calcd for C6H5O4SCl: C, 34.54; H, 2.42. Found: C, 34.51; H, 2.45. For H2L2: yield 79%; mp 71
74 °C. Anal. Calcd for C6H5O4SBr: C, 28.48; H, 1.99. Found: C, 28.45; H, 1.96. For H4L3: yield 72%; mp 168
170 °C. Anal. Calcd for C6H6O8S2: C, 26.67; H, 2.24. Found: C, 26.65; H, 2.26. Synthesis of [Ag2L1]n (1). Equal amounts of silver nitrate and H2L1 (5 mmol) were mixed in 12 mL of water, and then the pH value was adjusted to ca. 7 with the proper amount of ammonia. The mixture was stirred at room temperature for 10 min, followed by filtration. Colorless crystals of 1 were isolated from the filtrate after exclusion of light for several days. Yield: 61% (based on Ag). Anal. Calcd for C6H3O4SClAg2: C, 17.06; H, 0.72. Found: C, 17.08; H, 0.75. IR bands (cm
1): 3045 w, 1613 m, 1577 s, 1538 m, 1441 s, 1384 m, 1287 s, 1213 m, 1144 s, 1063 m, 1009 s, 813 s, 748 m, 676 m, 624 m. Synthesis of [Ag2L1(H2O)]n (2). Silver nitrate and H2L1 was mixed in 15 mL of water with a mole ratio of 2:1 (10:5 mmol), and then the pH value was adjusted to ca. 6 with the proper amount of ammonia. The mixture was stirred at room temperature for 10 min, followed by filtration. Colorless crystals of 2 were isolated from the filtrate after exclusion of light for several days. Yield: 58% (based on Ag). Anal. Calcd for C6H5O5SClAg2: C, 16.37; H, 1.14. Found: C, 16.34; H, 1.16.

IR bands (cm
1): 3335 m, 3069 w, 1617 s, 1565 m, 1537 m, 1449s, 1382 m, 1289 s, 1215 m, 1141 s, 1065 m, 1011 s, 817 s, 742 m, 656 m, 626 m. Synthesis of [Ag2L2(H2O)]n (3). The procedure was similar to that for 2 by replacing H2L1 with H2L2 and adjusting the pH value to ca. 6 with the proper amount of ammonia. Colorless crystals of 3 were obtained from the solution after exclusion of light for several days. Yield: 53% (based on Ag). Anal. Calcd for C6H5O5SBrAg2: C, 14.87; H, 1.04. Found: C, 14.89; H, 1.02. IR bands (cm
1): 3471 m, 1616 m, 1575 m, 1517 w, 1455 s, 1392 m, 1317 s, 1261 w, 1184 s, 1076 m, 1020 m, 829 m, 730 m, 636 m. Synthesis of [Ag5(L3)(NH3)2(NO3)]n (4). H4L3 (3 mmol) was dissolved in water, and the pH value was adjusted to ca. 8 with the proper amount of ammonia. Then, solid AgNO3 (12 mmol) was added to the above solution. After it was stirred for 10 min, the resulting mixture was filtered and allowed to evaporate slowly at room temperature with exclusion of light for 7 days. Yellowish crystals of 4 suitable for X-ray diffraction were isolated in 67% yield (based on Ag). Anal. Calcd for C6H8N3O11S2Ag5: C, 7.99; H, 0.89; N, 4.66. Found: C, 7.97; H, 0.85; N, 4.68. IR (v/cm
1): 3325 m, 3264 m, 1569s, 1542 m, 1481 m, 1459 m, 1359 s, 1299 m, 1176 s, 1108 m, 1056 m, 1025 s, 985 m, 808 m, 754 m, 653 m, 586 m. X-ray Crystallographic Measurements. All diffraction data were collected at 295 K on a Rigaku RAXIS-RAPID diffractometer with graphite-monochromated Mo KR (λ = 0.710 73 Å) radiation in ω-scan mode. All structures were solved by direct methods and difference Fourier syntheses. All non-hydrogen atoms were refined by full-matrix least-squares techniques on F2 with anisotropic thermal parameters. The hydrogen atoms attached to carbons were placed in calculated positions with C
H = 0.93 Å and U(H) = 1.2[Ueq(C)] in the riding model approximation. The hydrogen atoms of water molecules in complexes 2 and 3 and ammonia molecules in complex 4 were located in difference Fourier maps and were also refined in the riding model approximation, with O
H and N
H distance restraint (0.85(1) Å) and U(H) = 1.5[Ueq(O,N)]. All calculations were carried out with the SHELXL97 program.10 Selected bond distances for all complexes are presented in Table 1. Detailed crystallographic data and structure refinement parameters for complexes 1
4 are summarized in Table S1 (Supporting Information), and selected hydrogen bond distances and angles for complexes 2 and 3 are given in Table S2 (Supporting Information). CCDC reference numbers 806583
806585 and 801454.

’ RESULTS AND DISCUSSION Structure of [Ag2L1]n (1). In complex 1, there are two crystallographically independent silver(I) ions in the asymmetric 1962

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Table 1. Selected Bond Distances (Å) for Complexes 1
4a Complex 1 2.331(3)

Ag(2)
O(4)i

2.309(3)

i

2.353(4)

Ag(2)
O(3)iv

2.353(3)

Ag(1)
O(3)ii

2.463(3)

Ag(2)
O(2)

2.517(3)

Ag(1)
O(2)i

2.548(3)

Ag(2)
O(4)iv

2.534(3)

Ag(1)
O(2)iii

2.608(3)

Ag(2)
C(3)v

2.696(5)

Ag(1)
O(1) Ag(1)
O(4)

Complex 2 Ag(1)
O(4)i

2.458(2)

Ag(2)
O(1W)

2.135(4)

Ag(1)
O(1) Ag(1)
O(3)i

2.465(3) 2.487(3)

Ag(2)
O(4) Ag(2)
O(3)i

2.185(2) 2.937(3)

Ag(1)
O(4)

2.528(2)

Ag(2)
O(1)i

2.852(2)

ii

2.548(3)

S(1)
O(2)

1.444(2)

Ag(1)
C(3)ii

2.649(3)

S(1)
O(1)

1.460(3)

Ag(1)
Ag(1)i

3.3465(8)

S(1)
O(3)

1.467(3)

Ag(1)
C(4)

Complex 3 Ag(1)
O(4)

2.486(3)

Ag(2)
O(1W)

2.138(5)

Ag(1)
O(1) Ag(1)
O(4)i

2.492(4) 2.507(3)

Ag(2)
O(4) Ag(2)
O(1)i

2.197(3) 2.854(4)

Ag(1)
O(2)i

2.513(3)

Ag(2)
O(2)i

2.897(3)

Ag(1)
C(4)ii

2.580(4)

S(1)
O(3)

1.445(3)

Ag(1)
C(3)ii

2.684(4)

S(1)
O(2)

1.456(3)

Ag(1)
Br(1)iii

2.9324(9)

S(1)
O(1)

1.464(3)

Ag(1)
Ag(1)i

3.3919(8)

Ag(1)
O(4)i Ag(1)
O(4)

2.377(5) 2.497(5)

Complex 4 Ag(2)
O(1)ii Ag(2)
O(3)i

2.341(5) 2.389(4)

Ag(1)
C(1)ii

2.5022(9)

Ag(2)
O(4)

2.398(4)

Ag(1)
O(1)

2.528(5)

Ag(3)
N(2)

2.051(16)

Ag(1)
Ag(1)i

3.2304(14)

Ag(3)
N(3)

2.107(10)

Ag(2)
O(5)

2.334(8)

Symmetry codes are as follows. For 1: (i)
x þ 1, y þ 1/2,
z þ 3/2; (ii) x,
y þ 3/2, z
1/2; (iii) x,
y þ 3/2, z þ 1/2; (iv)
x þ 1,
y þ 1,
z þ 2; (v)
x þ 1,
y þ 1,
z þ 1. For 2: (i)
x þ 1,
y þ 1,
z þ 1; (ii) x,
y þ 3/2, z þ 1/2. For 3: (i)
x þ 1,
y þ 1,
z; (ii)
x þ 1, y
1 /2,
z þ 1/2; (iii)
x þ 1,
y þ 1,
z þ 1. For 4: (i)
x þ 1/2,
y þ 1 /2,
z þ 1; (ii)
x þ 1/2,
y þ 1/2,
z. a

unit, and both of them are five-coordinate with distorted-squarepyramidal geometry (Figure 1A). The Ag1 ion is coordinated by five O atoms from four distinct L12
groups, while the Ag2 ion is bound by four O atoms from three distinct L12
groups and one C atom from another L12
group. The Ag
C distance of 2.696(5) Å implies the existence of silver(I)-benzene interaction in a commom η1 mode. In turn, each L12
group coordinates to seven silver(I) ions, with the sulfonate group and deprotonated hydroxyl group adopting μ6-η3:η2:η1- and μ3-η3-bridging coordination modes (Scheme 2). Subsequently, adjacent silver(I) ions are connected into an inorganic network substructure which consists of 1-D chains of Ag2 linked through dimers of Ag1 by sharing atoms O2, O3, and O4, as illustrated in Figure 1B. The chlorophenyl moieties protrude into the interlayer region in the direction of the a axis (Figure 1C). The interlayer distance, defined as the perpendicular distance between planes of Ag(I) ions, is 11.682(2) Å, and the thickness of a single lamella, defined as the Ag
S
O layers, is 3.592(2) Å. Thus, the gallery height present in complex 1 is 8.09(2) Å, which is obviously shorter than that of silver p-toluenesulfonate (11.41 Å).11 The remarkable decrease of gallery

Figure 1. (A) Molecular structure of complex 1 showing the coordination environments around silver centers and the bridging mode of the L12
group, with ellipsoids at the 50% probability level. H atoms are omitted for clarity. (B) The inorganic layer formed by Ag2 chains and Ag1 dimers (green circles). (C) Perspective view of 1, showing the overall lamellar network with chlorophenyl moieties protruding into the interlayer region.

height can be attributed to the formation of Ag
C interactions, which place the chlorophenyl moieties closer to the Ag
S
O layers. Structures of [Ag2L1(H2O)]n (2) and [Ag2L2(H2O)]n (3). Single-crystal X-ray diffraction analysis indicates that complexes 2 and 3 possess the same P21/c space group and similar chemical formulas. However, there still exist some differences between the two structures. For complex 2, as illustrated in Figure 2A, the asymmetric unit contains two Ag(I) ions, one L12
group and 1963

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Scheme 2. Coordination Modes of Ligands in the Four Organosilver(I) Polymers

one coordinated water molecule. Ag1 ion is five-coordinated by four O atoms from two different L12
groups and an η2 interaction with two phenyl atoms of the L12
group to complete a distortedsquare-pyramidal geometry, while the Ag2 ion exists in a tetrahedron defined by three O atoms from two different L12
groups and a water molecule. In contrast, the asymmetric unit of complex 3 is similar to that of complex 2 by replacing the L12
group with the L22
group, and the Ag2 ion has the same coordination environment and geometry as in complex 2. However, Ag1 ion is sixcoordinated by an additional Br atom from the L22
group to complete a slightly distorted octahedron (Figure 2B). Both the L12
and L22
groups in complexes 2 and 3 adopt the same coordination modes but different from those of complex 1, with the sulfonate group and deprotonated hydroxyl group adopting μ3-η2:η2- and μ3-η3-bridging coordination modes (Scheme 2), and link two pairs of silver(I) ions to generate two pseudocubes sharing a Ag2O2 base plane (Figure 2C). The noncoordinating oxygen atom has a slightly shorter S
O bond length (1.444(2) Å in 2 and 1.445(3) Å in 3) relative to the two coordinating O atoms (1.460
1.467(2) Å in 2 and 1.456
1.464(3) Å in 3), indicative of more double-bond character. The Ag 3 3 3 Ag distances of 3.347 and 3.392 Å (Ag1 3 3 3 Ag1i) in the two complexes are nearly identical and are slightly shorter than the sum of the van der Waals radii of two silver atoms (3.44 Å),12 indicating the existence of a weak Ag 3 3 3 Ag interaction. In complex 3, there is a significant Ag
Br bond (2.9324(9) Å), which falls in the reported range of 2.7
3.0 Å.13 With such an Ag
Br bond, adjacent tetranuclear units are linked into a 1-D double chain with 14-membered rings. Then, both the chains in complex 3 and the tetranuclear units in complex 2 are further extended by the silver(I)
benzene interactions at both the b and c axes, thus giving rise to a 2-D (4,4) hybrid layer structure which is different from the common layered “inorgano-organic” structure, where the inorganic component is composed of sulfonatebridged silver(I) centers and the organic moiety is substituted phenyl groups (Figure 3). The Ag
C distances of 2.548(3) and 2.649(3) Å in 2 and 2.580(4) and 2.684(4) Å in 3 are well located

Figure 2. (A) Molecular structure of complex 2 showing the coordination environments around silver centers and the bridging mode of the L12
group, with ellipsoids at the 50% probability level. (B) Molecular structure of complex 3 showing the coordination environments around silver centers and the bridging mode of the L22
group, with ellipsoids at the 50% probability level. (C) View of the two pseudocubes by sharing a Ag2O2 base plane.

in other compounds with similar η2 Ag
C interactions.14 Offset face-to-face π
π stacking interactions between adjacent phenyl rings further stabilize the layer structure, with the centroid to centroid and perpendicular distances being 3.534 and 3.225 Å for 2 and 3.575 and 3.283 Å for 3. Moreover, the layer structures are further connected into 3-D networks through the hydrogen 1964

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Figure 3. (A) Layer structure of 2 extended by the silver(I)
benzene interactions. The aromatic π
π interactions between phenyl rings are shown as dashed lines. (B) Layer structure of 3 extended by the Ag
Br and silver(I)
benzene interactions. The aromatic π
π interactions between phenyl rings are shown as dashed lines.

bonds between coordinated water molecules and sulfonate groups (Figures S1 and S2 and Table S2 in the Supporting Information). Structure of [Ag5(L3)(NH3)2(NO3)]n (4). Single-crystal X-ray diffraction analysis indicates a 3-D organosilver(I) coordination polymer of 4 containing three different silver(I) ions. The Ag1 ion is six-coordinated by five O atoms from two different L34
groups and a η3 interaction with three phenyl C atoms of L34
group to complete a distorted-trigonal-prismatic geometry. The Ag2 ion has a trigonal-bipyramidal geometry defined by five O atoms from three different L34
groups and two O atoms from a nitrate ion. Ag3 exhibits a tetrahedral geometry with two O atoms from two different L34
groups and two ammonia molecules (Figure 4A). The distances from Ag(I) ions to oxygen atoms of L34
groups and nitrate anions range from 2.334(8) to 2.850(5) Å (Table 1). Interestingly, the fully deprotonated L34
tetraanion, as a small organic molecule, shows an intriguing and unprecedented coordination mode of μ14-2η5(
SO3):2η3(
O):2η3(C
. C
. C), as depicted in Scheme 2. To the best of our knowledge, this is the first example of a small anion bridging 14 metal ions. Moreover, the nitrate ion acts in an unusual μ4-η6 fashion with the impressive κ4 oxygen atom O6, which is also reported for the first time to date (Figure S3 in the Supporting Information). Another alluring feature of 4 is the μ2-η3-benzene mode, which has not been reported so far despite the fact that Ag
benzene interactions have been extensively investigated in many ways (Scheme 1). As shown in Figure 4B, two Ag1 ions interconnect with each other by sharing two O4 atoms and generate an Ag2O2 unit with an Ag 3 3 3 Ag distance of 3.230 Å, which are further linked to

Figure 4. (A) Molecular structure of complex 4 showing the coordination environments around silver centers and the bridging mode of the L34- group, with ellipsoids at the 50% probability level. (B) Layer structure of 4 (Ag1, green balls; Ag2, sky blue balls). The yellow ring represents the 12-membered ring of Ag 6O4C2. (C) View of the 3-D framework in 4 (Ag1, green balls; Ag2, sky blue balls; Ag3, light green balls). 1965

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Organometallics Scheme 3. Schematic Representation of the Geometrical Parameters of Ag
Benzene Interaction

ARTICLE

Table 2. Comparison of the Geometrical Parameters of the Four Silver(I) Complexes complex

Ag 3 3 3 C/Å

mode

d/Å

β/deg

Δ/Å

coordination

1

1

2.696(5)

η

2.65

35.04

1.86

square pyramid

2

2.548(3) 2.649(3)

η2

2.44

32.23

1.60

tetrahedron square pyramid

3

2.580(4)

η2

2.47

31.18

1.57

2.684(4) 4

adjacent four Ag2O2 units through Ag
C interactions and Ag1
O6 bonds to generate a 2-D lamellar network consisting of 12-membered rings of Ag6O4C2. Each pair of Ag2 ions caps the two sides of the 12-membered ring (Figure S4 in the Supporting Information). Subsequently, the Ag3 tetrahedra bridge adjacent layers through the O2 atoms to afford the 3-D framework (Figure 4C). The difference of 3.47 Å between the interlayer distance (11.78 Å) and the thickness of a single lamella (8.31 Å) constitutes the gallery height, which is obviously shorter than that in 1. Silver(I)
Benzene Interactions. Kochi15 defined a series of parameters (d, β, and Δ; see Scheme 3) which describe the relative positioning of the Ag center and the arene ring in a series of structures. As given in Table 2, the values of d, β, and Δ in the four complexes are all within the limits of those in other compounds discussed by Kochi, with the exception of the d value in 1, which falls slightly beyond the longer limit of 2.58 Å. In essence, the silver ion is situated less above the arene ring than in other complexes, most likely due to the other intermolecular stacking and silver(I) sulfonate bonding effects present, while it maintains comparable Ag
C bond distances. The Ag
C distances in the four complexes are lie well within the limits from 2.337 to 3.069 Å observed in the reported silver(I)
aromatic complexes2a,3g,14,16 and below the upper limit of 2.92 Å for an effective π interaction between silver(I) and an aryl carbon atom,17 indicating the existence of the Ag
benzene interactions. Thus, the coordination modes can be regarded as η1, η2, and μ2-η3 and the benzene moieties are subsequently best considered as being involved in the coordination spheres of the silver(I) ions. A Cambridge Structural Database CSD (version 5.27 with 14 updates) search18 yielded 224 crystal structures containing silver(I)
benzene π interactions. Of these, the most common modes for the phenyl ring are η1 and η2, which accounted for 93.3% of the crystallographically characterized organosilver(I) complexes. In contrast, only around 15 of the 224 reported crystal structures possess the η3 (8) and η6 (7) modes. Scheme 1 presents the basic modes of the silver(I)
benzene interactions. Surprisingly, no identical two or more carbon atoms acted as the bridge to link the silver(I) ions was detected. Thus, the current μ2-η3-benzene mode is a brand-new coordination mode in reported organosilver(I) complexes so far (mode j in Scheme 1). TG Analysis. To examine the thermal stability of complexes 1
4, thermogravimetric (TG) analyses were carried out from room temperature to 900 °C at a rate of 10 °C min
1 under a nitrogen atmosphere. Complex 1 loses the organic moieties in the temperature range 295
850 °C in nearly one step (Figure S5 in the Supporting Information). The observed weight loss of 49.27% is close to the calculated value (48.92%). Complexes 2 and 3 show similar thermal behaviors with two main steps of

2.5022(9)

tetrahedron octahedron

μ2-η3

2.50

28.95

1.39

trigonal prism

2.863(6)

trigonal bipyramid

2.915(6)

tetrahedron

weight losses (Figures S6 and S7 in the Supporting Information). The first step occurs from 140 to 225 °C for 2 and from 135 to 230 °C for 3, corresponding to the release of coordinated water molecules with weight losses of 3.58% (calcd 3.87%, 2) and 3.45% (calcd 3.72%, 3). The following weight loss ended at 655 and 775 °C for 2 and 3, due to the decomposition of the organic ligands (for 2, obsd 47.15%, calcd 46.92%; for 3, obsd 51.53%, calcd 51.78%). The TGA curve of 4 is shown in Figure S8 in the Supporting Information. The first weight loss occurring between 170 and 303 °C corresponds to the release of two ammonia molecules and one nitrate ion. The observed weight loss of 10.81% is close to the calculated value (10.66%). Further decomposition occurred at 303
546 °C with a weight loss of 29.38%, attributed to the loss of the tetraanion (calcd 29.52%). Luminescent Properties. The luminescent behaviors of the free ligands H2L1, H2L2, and H4L3 and complexes 1
4 were investigated at room temperature in the solid state. As depicted in Figures S9 and S10 in the Supporting Information, excitation at 260 nm leads to strong purple fluorescent emission bands at 335 and 313 nm for free H2L1 and H4L3. Unfortunately, almost complete quenching of the fluorescence down to the baseline was observed for complexes 1
4, which has also been detected in other organosilver(I) complexes.12b Moreover, owing to the existence of a bromine atom in the ligand H2L2, no clear luminescence was detected.

’ CONCLUSIONS In summary, four novel organosilver(I) coordination polymers have been successfully constructed from the reaction of silver nitrate and three hydroxyl-substituted benzenesulfonic acids. Complexes 1
3 possess 2-D layer structures with the usual η1- and η2-benzene modes, while complex 4 exhibits a 3-D framework with the novel μ2-η3-benzene mode. This study clearly demonstrates that the introduction of the hydroxyl group can not only enrich the coordination modes of the sulfonate groups but also activate the neighboring carbon atoms to form silver(I)
benzene interactions. Subsequently, new topological structures in 2 and 3 and an unusual μ2-η3-benzene mode in 4 can be discovered. Further investigations on syntheses, structures, and properties of organosilver(I) coordination polymers with well-designed ligands will be undertaken in our laboratory. ’ ASSOCIATED CONTENT

bS

Supporting Information. Figures giving additional structures, TGA curves, and photoluminescence spectra and CIF files

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Organometallics giving X-ray crystallographic data. This material is available free of charge via the Internet at http://pubs.acs.org.

’ ACKNOWLEDGMENT This work was financially supported by the Key Project of Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation team of Education bureau of Heilongjiang Province (No. 2010td03), and Program for New Century Excellent Talents in University (NCET-06-0349). We thank the University of Heilongjiang (Hdtd2010-04) for supporting this study. ’ REFERENCES (1) (a) Ogawa, K.; Kitagawa, T.; Ishida, S.; Komatsu, K. Organometallics 2005, 24, 4842–4844. (b) Fernandez, E. J.; Laguna, A.; Lopezde-Luzuriaga, J. M.; Monge, M.; Montiel, M.; Olmos, M. E.; RodriguezCastillo, M. Organometallics 2006, 25, 3639–3646. (2) (a) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Ning, G. L.; Kojima, T. J. Am. Chem. Soc. 1998, 120, 8610–8618. (b) Olmstead, M. M.; Maitra, K.; Balch, A. L. Angew. Chem., Int. Ed. 1999, 38, 231–233. (c) Munakata, M.; Ning, G. L.; Suenaga, Y.; Kuroda-Sowa, T.; Maekawa, M.; Ohta, T. Angew. Chem., Int. Ed. 2000, 39, 4555–4557. (d) Munakata, M.; Wu, L.-P.; Ning, G.-L. Coord. Chem. Rev. 2000, 198, 171–203. (e) Zhong, J. C.; Munakata, M.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Konaka, H. Inorg. Chem. 2001, 40, 3191–3199. (f) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Ohta, T.; Konaka, H. Inorg. Chem. 2003, 42, 2553–2558. and references therein.(g) Xu, Z. Coord. Chem. Rev. 2006, 250, 2745–2757. (h) Petrukhina, M. A. Coord. Chem. Rev. 2007, 251, 1690–1698. (i) Fern
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