DOI: 10.1021/cg1008472
Stepwise Synthesis of Charged and Neutral Two-Dimensional Networks via One-Dimensional Silver(I) Coordination Polymer Based on Bis(4-pyridylmethyl)sulfide
2010, Vol. 10 4148–4154
Ki-Min Park,*,† Joobeom Seo,† Suk-Hee Moon,‡ and Shim Sung Lee*,† † Department of Chemistry (WCU) and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, South Korea, and ‡Subdivision of Food Science, Kyungnam College of Information and Technology, Busan 616-701, South Korea
Received June 26, 2010; Revised Manuscript Received July 27, 2010
ABSTRACT: Stepwise synthesis and structural characterization of two-dimensional (2-D) coordination polymer frameworks with positive charged or neutral cavities are reported. First, reactions of bis(4-pyridylmethyl)sulfide (L) with silver salts (1: nitrate and 2: perchlorate) afforded the respective double-stranded one-dimensional (1-D) chains [Ag(L)NO3]n (1) and {[Ag2(L)2](ClO4)2}n (2), both of which are stabilized by face-to-face π-π interactions. In this case, the silver(I) center in the nitrato complex 1 shows four-coordinated distorted tetrahedral geometry, whereas that of the perchlorato complex 2 exhibits a distorted trigonal planar geometry. The difference of these structures indicates that the coordination ability of the anions has important effects on the silver(I) coordination environments. Interestingly, the perchlorato 1-D complex 2 allows further reactions with bridging ligands such as 4,40 -bipyridine (bpy) and terephthalate (tp2-) to give a 2-D positive-charged network {[Ag2(L)2(bpy)] 3 (ClO4)2 3 C6H6}n (3) and a 2-D neutral network {[Ag2(L)2(tp)] 3 2DMSO 3 6H2O}n (4), respectively. The nitrato 1-D complex 1, however, showed no reactivity with the bridging ligands in the same condition. The results show that the replacement of anion by the bridging ligand in the coordination sphere of the 1-D precursor plays crucial roles in determining the reactivity for the synthesis of higher dimensional open frameworks.
Introduction The fascination with self-assembled coordination polymer frameworks originates from the diverse network topologies as well as the scientific and technological applications.1-6 In particular, the open frameworks are more attractive than those of interpenetrating analogues because the former have much more available cavities and/or channels than latter.7,8 However, predictable construction of the open frameworks is difficult because of the high influences of various factors such as the coordination preference of metal ion, the functionality of ligand, and the coordinative ability of anion and solvent.9-12 For the advances of controlled engineering of solid-state structures with large and potentially useful cavities or channels, much effort has focused upon the use of a rationally designed ligand system and coordination characteristics of the metal ions. More subtle effects on the topological configuration such as anion control are also receiving renewed attention.11,12 Thus, it is desirable to be able to prevent interpenetration when needed and to be able to generate the structure with useful cavities or channels. The approach we have used to generate the anticipated open frameworks is a stepwise increment of the dimension via a two-step synthesis as depicted in Scheme 1. The proposed strategy to build a well-spanned framework to form a higher dimensional open framework is to utilize certain features of the potentially bridging ligands after obtaining the appropriate one-dimensional (1-D) framework based on the semirigid ligand. In this sense, the proposed bis(4-pyridylmethyl)sulfide (L) employs two pyridine nitrogen donors as a bridgehead for the required linear networking and possibly coordinates to a metal center in a T-shape via the *To whom correspondence should be addressed. E-mail: kmpark@gnu. ac.kr (K.-M.P);
[email protected] (S.S.L.). pubs.acs.org/crystal
Published on Web 08/09/2010
N2S donor set. In addition, 4,40 -bipyridine (bpy) has been shown to be a versatile neutral ligand as a bridge via two pyridine nitrogens. On the other hand, ligands of the dicarboxylate family such as terephthalate (tp2-) are the most widely used O-donor linker ligands with the negative charge. Taking into account the aforementioned points, we have investigated the effect of anion in the coordination environment of 1-D silver(I) coordination polymer precursors based on L, as well as the versatility of bridging ligands such as bpy and tp2- on the stepwise synthesis of the higher dimensional open frameworks with a neutral or positive charge.
Experimental Section General. All chemicals were of reagent grade and used without further purification. The IR spectrum was recorded on a VERTEX 80v FT-IR spectrometer with KBr pellet in the range 4000400 cm-1. The elemental analysis was carried out on a LECO CHNS-932 elemental analyzer. NMR spectrum was recorded on a Bruker 300 spectrometer (300 MHz), and mass spectra were obtained on a JEOL JMS-700 spectrometer. CAUTION: Although no problems were encountered in this work, transition metal perchlorates are potentially explosive. They should be prepared in small amounts and handled with care. r 2010 American Chemical Society
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cm-1): 3031 (w), 1603 (m), 1556 (w), 1498 (w), 1385 (s), 1223 (w), 1068 (w), 1003 (m), 822 (m), 571 (m), 486 (m). mp: 178.5-179.1 C (decomp.). Synthesis of {[Ag2(L)2](ClO4)2}n (2). The synthetic procedure was almost the same as for 1 except for the use of AgClO4 instead of AgNO3. Yield: 43%. Anal. Calc. for C24H24Ag2Cl2N4O8S2 (%): C, 34.02; H, 2.86; N, 6.61. Found: C, 34.45; H, 2.78; N, 6.74. ESI mass spectrum: m/z 323 [Ag(L)]þ, 539.02 [Ag(L)2]þ, 529 [Ag2(L)(ClO4)]þ, 745 [Ag2(L)2(ClO4)]þ. IR (KBr pellet, cm-1): 3076 (w), 3034 (w), 1603 (m), 1560 (w), 1495 (w), 1416 (m), 1215 (w), 1138 (s), 1088 (s), 841 (w), 814 (w), 750 (w), 710 (w), 627 (m), 577 (w), 490 (w). mp: 192.2-193.1 C (decomp.). Synthesis of {[Ag2(L)2(bpy)](ClO4)2 3 C6H6}n (3). A slightly excess amount of bpy (0.025 g, 0.157 mmol) was added to a solution of 2 (0.090 g, 0.106 mmol) in DMSO (10 mL). Colorless crystals of 3 were obtained by allowing benzene to slowly diffuse into a DMSO solution (5 mL) of 2 and bpy. Yield: 34%. Anal. Calc. for C40H38Ag2Cl2N6O8S2 (%): C, 44.42; H, 3.54; N, 7.77. Found: C, 44.17; H, 3.60; N, 7.70. ESI mass spectrum: m/z 262.92 [Ag(bpy)]þ, 323 [Ag(L)]þ, 479.04 [Ag(L)(bpy)]þ, 539.02 [Ag(L)2]þ, 744.77 [Ag2(L)2(ClO4)]þ. IR (KBr pellet, cm-1): 3029 (w), 1601 (s), 1558 (w), 1533 (w), 1495 (w), 1417 (m), 1221 (w), 1149 (m), 1090 (s), 1009 (w), 806 (m), 751 (w), 692 (w), 625 (m), 569 (w), 490 (w). Mp: 181.4-183.4 C (decomp.). Synthesis of {[Ag2(L)2(tp)] 3 2DMSO 3 6H2O}n (4). Colorless crystals of 4 were obtained by allowing an aqueous solution (5 mL) of Na2tp (0.053 g, 0.318 mmol) to slowly diffuse into a DMSO solution (5 mL) of 2 (0.090 g, 0.106 mmol) in a tube. Yield: 29%. Anal. Calc. for C36H52Ag2N4O12S4 (%): C, 40.15; H, 4.87; N, 5.20. Found: C, 40.47; H, 4.56; N, 4.89. ESI mass spectrum: m/z 539.02 [Ag(L)2]þ. Selected IR (KBr pellet, cm-1): 3433(br), 1564 (s), 1508 (m), 1390 (s), 1319 (m), 1097 (w), 1020 (m), 891 (m), 823 (s), 746 (s), 507 (s), 445 (m). Mp: 126.6-128.8 C (decomp.). X-ray Crystallography. All data were collected on a Bruker Smart diffractometer equipped with a graphite monochromated Mo KR (λ = 0.71073 A˚) radiation source and a CCD detector. The 45 frames of two-dimensional diffraction images were collected and processed to obtain the cell parameters and orientation matrix. Decay was monitored by 50 standard data frames measured at the beginning and end of data collection. The crystal showed no significant decay. The frame data were processed to give structure factors using the SAINT-plus.13 The structure was solved by direct methods and refined by full matrix least-squares methods on F2 for all data using SHELXTL software.14 In the refined structure 3, all oxygen atom of perchlorate anion were disordered over two sites with occupancies of 0.5. All non-hydrogen atoms were refined with anisotropic displacement parameters. In 4, the positions of the hydrogen atoms for guest water molecules were located from the difference electron density maps and refined using a riding model. All others
Synthesis of Bis(4-pyridylmethyl)sulfide (L). Under the basic condition, a mixture of 4-pycoryl sulfide hydrochlorate (5.03 g, 0.031 mol), Na2S (2.61 g, 0.016 mol) in 100 mL of MeOH-water (7:3 v/v) was refluxed for 24 h with vigorous stirring. After cooling, the resultant solution was reduced in volume to give a red residue, which was dissolved in water (100 mL) and then extracted by CH2Cl2 (3 100 mL). Removing the CH2Cl2 under a vacuum gave rise to crude oil. Treatment of the crude product on a silica gel column eluted with MeOH-CH2Cl2 (5:95 v/v) gave pure product L as a pale yellow glassy solid (yield 2.65 g, 77%). Anal. calc. for C12H12N2S (%): C, 66.63; H, 5.59; N, 12.95; S, 14.82. Found: C, 66.43; H, 5.71; N, 12.61; S, 14.78. 1H NMR (300 MHz, CDCl3): 8.54 (4H, dd, J = 1.57 and 4.45 Hz), 7.18 (4H, dd, J = 1.46 and 4.51 Hz), 3.54 (4H, s). 13C NMR (125.7 MHz, CDCl3): 150.4, 146.9, 124.2, 34.9. Mp: 48.5-49.2 C. Synthesis of [Ag(L)NO3]n (1). A MeOH (5 mL) solution of AgNO3 (0.043 g, 0.254 mmol) was added dropwise to the MeOH solution (10 mL) of L (0.050 g, 0.231 mmol) at room temperature. The white precipitate in 92% yield formed immediately. The precipitate was filtered off, washed with methanol and diethyl ether, and dried in vacuo. Single crystals suitable for X-ray analysis were obtained by vapor diffusion of diethyl ether into DMSO solution. Yield: 52%. Anal. Calc. for C12H12AgN3O3S (%): C, 37.32; H, 3.13; N, 10.88. Found: C, 36.92; H, 2.99; N, 10.54. ESI mass spectrum: m/z 323 [Ag(L)]þ, 539 [Ag(L)2]þ, 708 [Ag2(L)2(NO3)]þ. IR (KBr pellet,
Scheme 1. Stepwise Assembly of 2-D Networks
Table 1. Crystallographic Data for Compounds 1-4 formula M T/C crystal system space group a/A˚ b/A˚ c/A˚ R/o β/o γ/o U/A˚3 Z Dc/g cm-3 μ/mm-1 reflections collected unique reflections (Rint) absorption correction GOF R1 indices [I > 2σ(I)] wR2 (all data)
1
2
3
4
C12H12AgN3O3S 386.18 298(2) triclinic P1 7.5728(10) 8.0887(10) 12.3471(15) 87.566(3) 78.346(2) 70.194(2) 696.63(15) 2 1.841 1.606 3991 2700 (0.0617) none 1.055 0.0386 0.1033
C24H24Ag2Cl2N4O8S2 847.23 173(2) triclinic P1 8.1239(5) 13.3351(8) 13.4270(8) 89.9040(10) 82.5010(10) 87.3820(10) 1440.63(15) 2 1.953 1.745 8275 5566 (0.0153) Multiscan (SADABS) 1.046 0.0232 0.0587
C40H38Ag2Cl2N6O8S2 1081.52 298(2) triclinic P1 10.2624(11) 10.3350(11) 10.9124(12) 77.773(2) 75.062(2) 81.616(2) 1087.8(2) 1 1.651 1.177 6247 4231 (0.0523) Multiscan (SADABS) 1.050 0.0516 0.1708
C36H52Ag2N4O12S4 1076.80 298(2) triclinic P1 7.6202(14) 12.079(2) 13.207(2) 73.250(3) 85.746(4) 74.538(4) 1121.9(3) 1 1.594 1.120 6460 4365 (0.0546) none 1.011 0.0506 0.1327
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Park et al. were placed in calculated positions and refined with a riding model. The crystallographic data for metallopolymers 1-4 are summarized in Table 1.
Results and Discussion
Figure 1. Double-stranded 1-D chain structure of 1, [Ag(L)NO3]n: (a) coordination environment and (b) perspective view of the unit cell along the a-axis [symmetry codes: (i) -x þ 1, -y, -z; (ii) -x þ 1, -y, -z þ 1].
We present the synthesis and structural characterization of four supramolecular complexes (1-4) for L that involve the stepwise networking of L by means of anion substitution and bridging of ligands. The synthetic procedures were carried out in the darkness to avoid photodecomposition. In the first step, an investigation of the anion effect on the 1-D products obtained with silver salts was carried out. Through successive reactions of the 1-D silver complex with the bridging ligands, 2-D coordination polymers with charged or uncharged cavity were isolated (Scheme 1); all structures were characterized by X-ray analysis (Figures 1-4). Anion Effect on the Formation of Infinite 1-D Silver(I) Complexes (1 and 2). Self-assembly reactions of L with silver salts (1: NO3- and 2: ClO4-) were attempted (Scheme 1). First, the reaction of silver nitrate with L in methanol yielded a colorless precipitate. Vapor diffusion of diethyl ether into the DMSO solution of the complex gave crystalline 1. The X-ray analysis revealed that 1 is a twisted-ribbon type doublestranded 1-D chain of formula [Ag(L)(NO3)]n (Figure 1). Selected geometric parameters are presented in Table 2. The asymmetric unit of 1 contains one L, one Ag atom, and one NO3-.
Figure 2. Double-stranded 1-D chain structure of 2, {[Ag2(L)2](ClO4)2}n: (a) coordination environment, (b) perspective view of the unit cell, and (c) space-filling representation two chains cross-linked by perchlorate ions showing a ladder-type structure [symmetry codes: (i) x, y - 1, z; (ii) x, y þ 1, z; (iii) -x þ 1, -y þ 1, -z].
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Figure 3. Brick-wall type 2-D network structure of 3, {[Ag2(L)2(bpy)](ClO4)2 3 C6H6}n: (a) coordination environment, (b) 2-D positive framework filled with anions and solvent molecules, (c) space-filling structure of the 2-D positive framework (anions and solvent molecules are omitted), and (d) side view of packing arrangement of 2-D layers (ABC-type) [symmetry codes: (i) x, y - 1, z þ 1; (ii) -x, -y þ 1, -z þ 1; (iii) -x þ 1, -y þ 1, -z þ 2].
In 1, as might be expected, two pyridine N atoms from two different ligands in one strand appear to bind strongly to the silver center [Ag1-N1i 2.351(3) A˚, Ag1-N2ii 2.309(3) A˚]. And one S donor from the other ligand in the adjacent parallel strand binds to the silver center [Ag-S 2.5176(11) A˚] with a typical bond distance, resulting in the cross-linked doublestranded chain. The coordination sphere in 1 is completed by an O atom from NO3- bound in a monodentate manner with a bond length (Ag-O 2.492(4) A˚) that falls within the range observed for other monodentate nitrate complexes of silver.15
Thus, the Ag atom is effectively four-coordinate, with the “tetrahedral” angles falling in the range 90.84(14)120.56(9). In addition, the pyridine rings in each strand form the face-to-face π-π stacking interactions (dihedral angle: 0 and centroid-to-centroid distance: 4.06 A˚) to stabilize the double-stranded chains. To examine the influence of counteranions in the formation of silver complexes of L, the reaction was repeated with AgClO4. Again, the reaction of silver perchlorate with L in methanol yielded a colorless precipitate. Vapor diffusion of
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Figure 4. Brick-wall type 2-D network structure of 4, {[Ag2(L)2(tp)] 3 2DMSO 3 6H2O}n: (a) coordination environment, (b) 2-D neutral framework filled with solvent molecules, (c) space-filling structure of the 2-D neutral framework (solvent molecules are omitted), (d) side view of packing arrangement of 2-D layers (ABCD-type), and (e) top view and (f) side view of the unit cavity showing H-bonds (dotted lines) [symmetry codes: (i) x, y - 1, z; (ii) -x þ 1, -y þ 1, -z; (iii) x, y þ 1, z; (iv) -x þ 1, -y, -z; (v) -x, -y, -z þ 1; (vi) -x, -y þ 1, -z þ 1].
diethyl ether into the DMSO solution of the complex gave crystalline 2. The X-ray analysis revealed that 2 is also a double-stranded 1-D chain of formula {[Ag2(L)2](ClO4)2}n
exhibiting a similar connectivity pattern of 1 (Figure 2). Selected geometric parameters are presented in Table 2. The asymmetric unit of 2 consists of two crystallographically
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Crystal Growth & Design, Vol. 10, No. 9, 2010 Table 3. Hydrogen Bonds (A˚ and deg) for Compound 4a
Table 2. Selected Bond Lengths (A˚) and Angles (deg) for Compounds 1-4 Compound 1a Ag1-S1 Ag1-N2ii S1-Ag1-N1i S1-Ag1-O1 N1i-Ag1-O1
2.5176(11) 2.309(3) 120.56(9) 118.59(9) 90.84(14)
Ag1-N1i Ag1-O1 S1-Ag1-N2ii N1i-Ag1-N2ii N2ii-Ag1-O1
2.351(3) 2.492(4) 115.68(10) 103.37(12) 103.91(15)
Compound 2b Ag1-S2 Ag1-N2i Ag2-N3 S2-Ag1-N1 N1-Ag1-N2i S1-Ag2-N4ii
2.4575(6) 2.301(2) 2.256(2) 125.69(5) 99.12(7) 108.59(5)
Ag1-N1 Ag2-S1 Ag2-N4ii S2-Ag1-N2i S1-Ag2-N3 N3-Ag2-N4ii
Compound 3c ii
Ag1-S1 Ag1-N2i S1ii-Ag1-N1 S1ii-Ag1-N3 N1-Ag1-N3
2.5233(19) 2.290(5) 101.00(14) 115.61(15) 96.35(19)
Ag1-N1 Ag1-N3 S1ii-Ag1-N2i N1-Ag1-N2i N2i-Ag1-N3
2.381(5) 2.367(6) 125.97(14) 114.8(2) 99.7(2)
Compound 4d ii
Ag1-S1 Ag1-N2i S1ii-Ag1-N1 S1ii-Ag1-O1 N1-Ag1-O1
2.5253(17) 2.367(5) 110.25(14) 118.38(13) 90.16(18)
Ag1-N1 Ag1-O1 S1ii-Ag1-N2i N1-Ag1-N2i N2i-Ag1-O1
D-H 3 3 3 A O1W-H1WA 3 3 3 O1 O1W-H1WB 3 3 3 O3i O2W-H2WA 3 3 3 O1W O2W-H2WB 3 3 3 O3 O3W-H3WA 3 3 3 O2W O3W-H3WB 3 3 3 O2ii a
2.273(2) 2.5227(7) 2.309(2) 128.42(5) 129.94(5) 117.07(7)
2.363(5) 2.513(4) 121.77(14) 94.60(18) 113.05(19)
a Symmetry codes: (i) -x þ 1, -y, -z; (ii) -x þ 1, -y, -z þ 1. Symmetry codes: (i) x, y - 1, z; (ii) x, y þ 1, z. c Symmetry codes: (i) x, y - 1, z þ 1; (ii) -x, -y þ 1, -z þ 1. d Symmetry codes: (i) x, y - 1, z; (ii) -x þ 1, -y þ 1, -z. b
different Ag ions, two L, and two perchlorate ions. Notably, the change of the anion from nitrate (1) to perchlorate (2), however, has led not only the change of coordination geometry around the Ag atom but also the symmetry of the chain structure. For example, the geometry of two independent Ag atoms in 2 is a trigonal plane: each silver atom links two pyridine units [Ag-N 2.256(2)-2.309(2) A˚] and also is coordinated to one S atom [Ag-S 2.5227(7) and 2.4575(6) A˚] from an adjacent L. It is of importance to note that perchlorate anions interact with the Ag centers in bi- and tridentate manners (Figure 2b). For example, one μ2-ClO4- ion links two adjacent parallel double-stranded chains in a tridentate manner [Ag 3 3 3 O 2.658(2)-3.164(2) A˚], generating a ladder-type array in which the anions act as rungs (Figure 2c). Another terminal ClO4- ion interacts to the Ag center from the outside of the ladder in a bidentate manner [Ag 3 3 3 O 2.833(2) and 3.178(2) A˚]. The Ag atoms are displaced out of the trigonal N2S coordination plane by 0.348(1) A˚ for Ag1 and 0.284(1) A˚ for Ag2 due to the Ag 3 3 3 ClO4- interaction. The interligand face-toface π-π stacking interactions [dihedral angles: 19.57(8) and 1.9(1)o and centroid-to-centroid distances: 4.06 and 4.05 A˚] between pyridine rings along the chain also stabilize the double-stranded chain structure. From 1-D to 2-D Frameworks. Having obtained two anion-independent 1-D silver(I) coordination polymers 1 and 2, we proceeded to the preparation of the coordination polymers with higher dimension by employing the organic bridging ligands (bpy and tp2-). As shown in the reaction pathways (Scheme 1), the nitrato-type complex 1 shows no further reactivity with the bridging ligands, whereas the perchlorato-type complex 2 reacts with the bridging ligands to give the 2-D frameworks 3 and 4.
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d(D-H) 0.85 0.86 0.84 0.85 0.82 0.84
d(H 3 3 3 A) 1.91 2.10 2.06 1.90 2.44 2.04
d(D 3 3 3 A) 2.761(8) 2.940(11) 2.880(10) 2.747(10) 3.076(10) 2.878(8)
— (DHA) 175.5 164.6 164.0 176.0 134.9 173.7
Symmetry codes: (i) -x, -y þ 1, -z þ 1; (ii) x, y þ 1, z.
Preparation and Structure of a 2-D Network with Positive Charge (3). As mentioned above, through the successive reaction of the 1-D perchlorato complex 2 with bpy as a neutral bridging ligand in DMSO/benzene, the 2-D framework species 3 of formula {[Ag2(L)2(bpy)](ClO4)2 3 C6H6}n was isolated (Figure 3). The selected geometric parameters for 3 are listed in Table 2. The X-ray analysis revealed that 3 is made up of a brick-wall type 2-D network with the positive charge by linking of the 1-D chain with bpy in a bidentate manner. Each Ag atom in 3 is four-coordinate being bound to two nitrogen atoms from two different L, one nitrogen atom from one bpy, and one S atom from different L. Thus, the coordination sphere of the Ag center is distorted tetrahedral, with the “tetrahedral” angles falling in the range 96.35(19)-125.97(14) A˚. In the resulting 2-D brick-wall structure, the unit rectangular cavity with the positive charge consists of four Ag(I) ions, two L and two bpy. The size of each cavity is ca. 11.8 13.3 A˚. Each cavity is filled with two perchlorate ions and two benzene molecules. No significant interactions between the cavity frameworks and the guest species are observed (Figure 3b). As depicted in Figure 3d, the 2-D sheets are extended along the (111) plane and interlayer separation is ca. 5.4 A˚. Because of the ABCABC stacking pattern arrangement of the 2-D sheets, the porous channels formed are tilted. Preparation and Structure of a 2-D Network with Neutral Charge (4). In contrast to 3, synthesis of the 2-D network species with neutral charge was also accomplished. In this case, we used tp2- instead of bpy. Our strategy is realized by isolating 4 of formula {[Ag2(L)2(tp)] 3 2DMSO 3 6H2O}n from layering an aqueous solution of Na2tp on a DMSO solution of 2 (Figure 4). The selected geometric parameters for 4 are listed in Table 2. X-ray analysis shows that 4 is also a brickwall type 2-D open framework whose structure is similar to that of 3 except substituting tp2- for bpy. Notably, introduction of the anionic bridging ligand leads to neutralizing the charge of the cavity for the 2-D framework. Therefore, each neutral cavity in 4 is filled with the solvent molecules used in the synthesis procedure. The Ag(I) atom is in a distorted tetrahedral geometry coordinated by two nitrogen atoms and one sulfur atoms from three different L ligands, and one carboxylate oxygen atom of tp2-. Each tp2- binds two Ag(I) ions of the neighboring double-stranded 1-D metallopolymers {[Ag2(L)2]2þ}n to form the slightly tilted brick-wall type 2-D sheet (Figure 4b,c). As depicted in Figure 4d, the 2-D sheets are propagated along the (202) plane and stacked parallel to one another with an interlayer separation of ca. 6.64 A˚. Accordingly, the porous channels generated by the stacking of 2-D sheets are running along the a-axis. The size of the neutral rectangular cavity in 4 (ca. 11.6 12.1 A˚) is about 10% smaller than that of 3 due to the shorter length of tp2- than that of bpy. As mentioned, each cavity in 4 is occupied by six H2O and two DMSO molecules which
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interact by hydrogen bonds (Figure 4d,e). The range of the hydrogen bond distances are from 2.75(1) to 3.08(1) A˚ (Table 3). Conclusion We have described an approach adopted for the stepwise synthesis of 2-D open frameworks through the bridging of 1-D chain assembled by bis(4-pyridylmethyl)sulfide and silver(I) salts (NO3- and ClO4-). The perchlorato-type 1-D chain complex leads the formation of 2-D open frameworks with neutral or positive charge by the reactions of the corresponding bridging ligands. However, the nitrato-type 1-D chain complex showed no reactivity in same condition. The observed anion influence might be explained by its coordination ability toward the metal center because the NO3- ion having a larger affinity for silver center than that of ClO4- ion interferes significantly in further product formation. Instead, the perchlorato-complex acts as a precursor in the reactions of the bridging bidentate ligands to give 2-D networks because the weaker-bound perchlorate ions can be replaced by bridging ligands easily. This approach has the potential to prepare other 2-D open frameworks with charged and uncharged cavities. Further investigation using the 1-D chain precursor, aimed at the production of higher dimension structures with the different cavities or channels, is in progress. Acknowledgment. This research was supported by Grant No. R32-2008-000-20003-0 from the WCU project of MEST and NRF through Gyeongsang National University. Supporting Information Available: Crystallographic information file is available free of charge via the Internet at http://pubs.acs.org.
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