Construction of Ag(I)–Ln(III) Heterometallic Coordination Polymers

Article pubs.acs.org/crystal

Construction of Ag(I)−Ln(III) Heterometallic Coordination Polymers Based on Binuclear Ag2(DSPT)2 (H2DSPT = 4′-(2,4-Disulfophenyl)2,2′:6′2″-terpyridine) Rings and Ln(III) Dimeric Molecular Building Blocks Rui-Ling Chen, Xue-Yun Chen, Sheng-Run Zheng,* Jun Fan, and Wei-Guang Zhang* School of Chemistry and Environment, South China Normal University, Guangzhou, 510006, China S Supporting Information *

ABSTRACT: Four new 4d−4f heterometallic coordination polymers, namely, {[LnAg(DSPT)(mBDC)(H2O)2]·H2O}n [Ln = Sm, (1); Ln = Er, (2); H2DSPT = 4′-(2,4-disulfophenyl)-2,2′:6′2″-terpyridine); H2mBDC = 1,3benzenedicarboxylic acid], {[CeAg(DPST)(mBDC)(H2O)2]·H2O}n (3), and {[TbAg3(DPST)2(INC)2(H2O)]}n [HINC = isonicotinic acid, (4)], have been successfully synthesized under hydrothermal conditions and structurally characterized. The four components, including Ln(III) ions, Ag(I) ions, and the two organic ligands, are successfully incorporated into a single framework. They are all heterometallic complexes based on two kinds of molecular building blocks (MBBs), the Ag2(DSPT)2 ring (MBB I) and Ln2(COO)2 dimeric unit (MBB II). Complexes 1 and 2 are isostructural and exhibit a 2D network constructed by MBBs I and II, and further linked by Ag···π interactions to a 3D supramolecular framework. Complexes 3 and 4 are 3D frameworks with sqc-21 and sqc-495 topologies by considering MBB I and II as nodes and coordination bonds/Ag···O interactions as linkers. Complexes 1−4 represent rare examples of 4d−4f coordination polymers containing two kinds of organic ligands. Moreover, thermal gravimetric analysis and luminescence properties studies of selected complexes were also investigated.

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INTRODUCTION The functionality of coordination polymers (CPs) is mainly derived from metal ions and organic ligands; new properties may emerge from suitable interconnections between different components.1,2 Thus, the incorporation of an increasing number of components (more types of metal ions and organic ligands) into a single unique framework may result in new functions of such metal−organic materials.3 However, difficulties are also increased when more components are incorporated together into a single network. In this paper, multicomponent CPs (MCPs) are introduced to refer to CPs with multiple metal ion and organic ligand types, excluding other components, such as inorganic anions, coordinated solvent molecules, and guest molecules. The studies on CPs with more than two components are mainly based on CPs with two types of metal ions and one type of organic ligand (socalled heterometallic CPs),4 or one type of metal ion and two types of organic ligands (CPs with mixed organic ligands).5 Studies on MCPs with multiple types of ligands and metal ions, such as those that contain two types of metal ions plus two types of organic ligands, are still limited.3,6 From a structural standpoint, which may improve the ability to predesign desired frameworks, d−f heterometallic CPs can usually be constructed in four ways: (i) the framework can only be decomposed into single metal ions and ligands as nodes and rods, respectively (Scheme 1, Strategy I);7 (ii) the use of © 2013 American Chemical Society

Scheme 1. Schematic Representation of Five Strategies for Construction of Heterometallic Coordination Polymers

discrete heterometallic secondary building units (SBUs) and organic linkers (Scheme 1, Strategy II);8 (iii) the use of a homometallic two-dimensional (2D) layer (usually, Ln(III)− carboxylic layer) and metal-containing pillars (such as those containing Ag(I) ion), which results in a so-called pillar−layer structure (Scheme 1, Strategy III);9 and (iv) the use of a metalloligand as initial reactant (Scheme 1, Strategy IV).10 Received: June 20, 2013 Revised: August 11, 2013 Published: September 4, 2013 4428

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Compared with Strategy I, the other strategies may have advantages in rational design because some molecular building blocks (MBBs) can be expected to be formed in special reaction systems. To enhance the possibility of obtaining MCPs, we followed and extended these strategies in the present work. Different homometallic MBBs were organized into a heterometallic framework (Scheme 1, Strategy V). By introducing a terpyridine-based ligand [4′-(2,4-disulfophenyl)2,2′:6′2″-terpyridine), H2DSPT], Ag(I) ion, Ln(III) ion, and aromatic acid [isonicotinic acid (HINC) or 1,3-benzenedicarboxylic acid (H2mBDC)] into the reaction system, we obtain four 4d−4f heterometallic coordination polymers, namely, {[LnAg(DSPT)(mBDC)(H2O)2]·H2O}n [Ln = Sm, (1); Ln = Er, (2)], {[CeAg(DSPT)(mBDC)(H2O)2]·H2O}n (3), and {[TbAg3(DSPT)2(INC)2(H2O)]}n (4). Interestingly, the four building units (Ln(III) ions, Ag(I) ions, and the two ligands) incorporated into a single framework. They are all heterometal−organic coordination polymers based on a well-defined Ag2(DPST)2 ring and Ln(III) dimeric MBBs (Scheme 2).

Article

EXPERIMENTAL SECTION

Materials and Measurements. The ligand H2DSPT was purchased at Jinan Henghua Sci. & Tec. Co., Ltd. Lanthanide chloride hydrates and lanthanide nitrate hydrates were prepared by dissolving the respective lanthanide oxides (99.5%) with concentrated HCl and concentrated HNO3, respectively, and then evaporating at 100 °C until the crystals were formed. Other materials were reagent grade obtained from commercial sources and used without further purification. Elemental analyses for C, H, and N were performed on a PerkinElmer 240C analytical instrument. IR spectra were recorded on a Nicolet FT-IR-170SX spectrophotometer in KBr pellets. X-ray powder diffraction measurements were measured by using a Bruker D8 Advance diffractometer at 40 kV, 40 mA with a Cu-target tube and a graphite monochromator. Thermogravimetric analyses were performed on a PerkinElmer TGA7 analyzer with a heating rate of 10 °C/min in a flowing N2 atmosphere. The luminescent spectra for the solid state were recorded at room temperature on a Hitachi F-2500 and Edinburgh-FLS-920 with a xenon arc lamp as the light source. In the measurements of emission and excitation spectra, the pass width is 5 nm. {[SmAg(DST)(mBDC)(H2O)2]·H2O}n (1). A mixture of SmCl2· 6H2O (0.075 mmol), AgNO3 (0.075 mmol), H2DSPT (0.075 mmol), H2mBDC (0.075 mmol), and H2O (3 mL) was sealed in a 10 mL Teflon-lined stainless steel reactor, heated at 170 °C for 70 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 2 °C/h. Pale yellow block crystals of 1 were collected by filtration and washed with distilled water and ethanol several times (48.9 mg; 0.052 mmol; 69% yield based on Sm). IR (KBr, ν/cm−1): 3413(m), 2999(m), 2666(m), 2552(m), 1693(s), 1611(s), 1544(w), 1479(w), 1458(w), 1412(s), 1281(s), 1241(m), 926 (w), 823(w), 729(m), 691(m), 610(w), 5464(w). {[ErAg(DSPT)(mBDC)(H2O)2]·H2O}n (2). An identical procedure as that for 1 was followed to prepare 2, except that SmCl2·6H2O was replaced by Er(NO3)3·6H2O. Pale yellow block crystals of 2 were collected by filtration and washed with distilled water and ethanol several times (27.4 mg; 0.029 mmol; 38% yield based on Er). Elemental analysis calcd (%) for C29H23N3O13S2AgEr: C, 36.25; H, 2.41; N, 4.37. Found: C, 36.22; H, 2.42; N, 4.39%. IR (KBr, ν/cm−1): 3444(s), 1693(s), 1611(s), 1474(w), 1418(m), 1280(s), 1197(s), 1037(s), 790(w), 691(w), 612(m), 546(w). {[CeAg(DSPT)(mBDC)(H2O)2]·H2O}n (3). An identical procedure as that for 1 was followed to prepare 3, except that SmCl2·6H2O was replaced by Ce(C2O4)3·6H2O. Pale yellow block crystals of 3 were collected by filtration and washed with distilled water and ethanol

Scheme 2. Schematic Representation of MCP Formation Based on Ag2(DPST)2 Ring and Ln(III) Dimeric MBBs

Table 1. Crystallographic Data and Structure Refinement Summary for Complexes 1−4

a

complex

1

2

3

4

empirical formula formula weight crystal system space group a/Å b/Å c/Å α/deg β/deg γ/deg V/Å3 Z D/g cm−3 μ/mm−1 T/K Ra/wRb total/unique/Rint

C29H23N3O13S2AgSm 943.84 monoclinic P2(1)/c 8.948(4) 10.202(4) 18.399(8) 92.234(5) 99.486(5) 105.651(5) 1589.0(12) 2 1.973 2.650 298(2) 0.0634/0.1736 9131/6630/0.0418

C29H23N3O13S2AgEr 960.75 monoclinic P2(1)/c 8.8190(9) 10.1316(10) 18.4266(18) 92.3950(10) 99.6150(10) 105.2440(10) 1559.8(3) 2 2.046 3.507 298(2) 0.0576/0.1498 9237/6575/0.1549

C29H23N3O13S2AgCe 933.61 monoclinic P2(1)/c 9.1855(13) 9.8587(14) 18.413(3) 96.172(2) 99.566(2) 108.848(2) 1532.7(4) 2 2.023 2.317 298(2) 0.0435/0.1185 8992/6426/0.0242

C54H36N8O17S4Ag3Tb 1679.68 monoclinic P2(1)/c 11.1247(18) 14.592(2) 16.648(3) 97.718(2) 92.917(2) 91.768(2) 2672.6(7) 2 2.087 2.631 298(2) 0.0659/0.2484 15 718/11 233/0.0432

R1 = ∑||Fo| − |Fc||/|Fo|. bwR2 = [∑w(Fo2 − Fc2)2/∑w(Fo2)2]1/2, where w = 1/[σ2(Fo2) + (aP)2 + bP]. P = (Fo2 + 2Fc2)/3. 4429

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Figure 1. (a) The coordination environment of Ag(I) and the Ag2(DPST)2 ring in 1. (b) The coordination environment of Sm(III) and the Sm(III) dimeric MBBs in 1. (c) The Sm(III) dimeric MBBs in 1. (d) The 2D network in 1. (e) The 3D framework in 1. The Ag···π interactions are shown in green dashed lines. (f) The Ag···π interactions in 1. All H atoms and noncoordinated water molecules are omitted for clarity. several times (49.0 mg; 0.053 mmol; 70% yield based on Ce). Elemental analysis calcd (%) for C29H23N3O13S2AgCe: C, 37.31; H, 2.48; N, 4.50. Found: C, 37.22; H, 2.51; N, 4.52%. IR (KBr, ν/cm−1): 3445(m), 1690(s), 1609(s), 1542(s), 1481(w), 1384(s), 1267(m), 1035(m), 923(w), 792(w), 733(s), 682(w), 608(w). {[TbAg3(DSPT)2(INC)2(H2O)]}n (4). A mixture of TbCl3·6H2O (0.05 mmol), AgNO3 (0.05 mmol), H2DSPT (0.05 mmol), HINC (0.05 mmol), and H2O (2 mL) was sealed in a 10 mL Teflon-lined stainless steel reactor, heated at 170 °C for 60 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 3 °C/h. Pale yellow block crystals of 4 were collected by filtration and washed with distilled water and ethanol several times (9.8 mg; 0.006 mmol; 35% yield based on Ag). IR (KBr, ν/cm−1): 3460(s), 1600(m), 1544(w), 1473(w), 1412(m), 1199(s), 1037(s), 775 (w), 682 (m), 613(m), 548(w). X-ray Data Collection and Structure Refinement. The intensity data were measured on a Bruker Smart Apex II diffractometer with graphite monochromated Mo K radiation (λ = 0.71073 Å) at room temperature for all complexes. Multiscan absorption corrections were applied by using SADABS.11 The four structures were solved by direct methods and refined with full-matrix least-squares refinements based on F2 by using SHELXS-9712 and SHELXL-9712 program packages, respectively. All non-H atoms were refined with anisotropic thermal parameters. All the hydrogen atoms on organic ligands were placed in idealized positions. The hydrogen atoms on water molecules were located in different density maps and were also refined using a riding model via the instruction AFIX 3. Crystal parameters and details of data collections and refinements for complexes 1−4 are summarized in Table 1. The selected bond lengths and angles are listed in Table S1 (Supporting Information). The CCDC reference numbers 942133−

942136 contain the supplementary crystallographic data for complexes 1−4.

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RESULTS AND DISCUSSION

Crystal Structures of 1 and 2. Single-crystal X-ray diffraction analyses reveal that complexes 1 and 2 are all crystallized in the monoclinic system with P1̅ space group and possess 2D coordination frameworks consisting of [Ag2(DSPT)2] and [Ln2(mBDC)2(DSPT)2] MBBs. Because they are isostructural, only the structure of 1 is described in detail. In complex 1, there are one Sm(III) ion, one Ag(I) ion, one DSPT2− anion, one INC− anion, two coordinated water molecules, and one uncoordinated water molecule in the asymmetric unit. The Ag(I) ion is four-coordinated with three nitrogen atoms and one oxygen atom from two individual DSPT3− ligands, forming a distorted quadrilateral geometry (Figure 1a). The Ag−N bond lengths are in the range of 2.350(8)−2.460(9) Å, while the Ag−O bond is 2.276(7) Å; all of them are comparable to those reported for other related Ag(I) complexes.13 The coordination polyhedron around the central Sm(III) ion can be visualized as a distorted bicapped trigonal prism geometry with a [SmO8] coordination mode: four carboxyl oxygen atoms from three different INC− anions, two oxygen atoms from two different DSPT2− anions, and two oxygen atoms from two water molecules (Figure 1b). The Sm− O distances range from 2.319(5) to 2.481(5) Å. The bond angles around the central Sm(III) atom vary from 52.81(18)° 4430

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C−C bond between the terpyridine and benzene group can rotate and the angle between these two planes is about 50.09(23)°, which makes the 2-SO3− group suitable to coordinate to the Ag(I) ion but does not have influence on the 4-SO3− group. Such a binuclear ring can be seen as an MBB (MBB I) that can further connect to other ions via the 4-SO3− groups. The two Sm(III) ions are connected by two carboxyl groups and two 4-SO3− groups to form a dimeric Sm(III) MBB (MBB II), in which the Sm···Sm distance is 4.4496(15) Å, as shown in Figure 1b,c. The MBBs II are linked by mBDC2− to form a 1D chain (along the b axis). The chains are connected along the c axis by MBB I, generating a 2D heterometallic layer extending along the bc plane (Figure 1d). If we consider each MBB as a node, the 2D network can simply be as a (4,4) net on topological view. The 2D networks are packing along the a direction by Ag···π interactions15 involving a pyridyl ring of DSPT. The distance between Ag(I) and the centroid is 3.3993(15) Å. Such Ag···π interactions and OH···O hydrogen bonds between coordinated water O and carboxyl O atoms on mBDC2− (with O···O distance range from 2.718 to 2.722 Å) contribute to the stabilization of the 3D supramolecular framework (Figure 1e). Although the topology of the 2D layer is simple, it contains two types of metal ions and two types of organic ligands, which is indeed still rarely reported.

to 147.2(2)°, all of which are within the range of those observed for other nine-coordinate Sm(III) complexes.14 The coordination modes of DSPT2− and mBDC2− are shown in Scheme 3 (modes I and IV, respectively). For DSPT2−, the Scheme 3. Coordination Modes of the H2BSPT, H2mBDC, and HINC Ligands in Complexes 1−4

terpyridine unit binds to a Ag(I) ion, the sulfo group on the 4position (4-SO3−) binds to two Sm(III) ions in a cis conformation, and that on the 2-position (2-SO3−) binds to one Ag(I) ion. The mBDC2− adopts a usual coordination mode named μ3-kO,O′:kO″,O‴ to simultaneously bridge one Sm(II) ion in bis-O,O′-chelating and two Sm(III) ions in monodentate fashion (Scheme 3, mode IV). Two DSPT2− and two Ag(I) ions are joined together to form a binuclear ring with a Ag···Ag distance of 4.8399(21) Å (Figure 1a). The formation of such a binuclear ring is due to the coordination geometry demand of the Ag(I) ion and the conformation of DSPT2− anions. The

Figure 2. (a) The coordination environment of Ce(III) and the Ce(III) dimeric MBBs in 3. (b) The coordination environment of Ag(I) and the Ag2(DPST)2 ring in 3. (c) The 2D layer in 3. (d) The 3D framework in 3. (e) The six-connected and four-connected nodes in 3. (f) The (4,6)connected topology in 3. All H atoms and noncoordinated water molecules are omitted for clarity. 4431

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Figure 3. (a) The coordination environment of Tb(III) and the Tb(III) dimeric MBBs in 4. (b) The coordination environment of Ag2 and the Ag2(DPST)2 ring in 4. (c) The coordination environment of Ag4 in 4. (d) The 2D layer in 4. (e) The 3D framework in 4. (f) The eight-connected and two types of three-connected nodes in 4. (g) The (3,8)-connected topology in 4. All H atoms and noncoordinated water molecules are omitted for clarity.

complexes 1−3. The carboxylate group of mBDC2− anions takes on the μ3-kO,O′:kO″,O‴kO‴ coordination mode (Scheme 3, mode V), which bridges two Ce(III) ions into a dimeric Ce(III) MBB with a Ce···Ce distance of 4.4407(7) Å. The coordination behavior of the 4-SO3− group is significantly different from that in complex 1. It connects to two different MBBs II in complex 3, while it just helps to bind two Ln(III) ions in the same MBB I in complex 1. Such a difference makes the combination of Ce(III), mBDC2− anions, and 4-SO3− groups into a 2D layer extending along the ab plane (Figure 2c). The 2D layer is also a (4,4) net on topological view, with MBB II as nodes and mBDC2− anions and 4-SO3− groups as linkers. The adjacent Ce···Ce distance in different MBBs II is 4.9264(7) and 9.8578(14) Å. Furthermore, such 2D layers are pillared by MBBs I via Ce−O bonds between Ce(III) and 4SO3− into a 3D framework (Figure 2d). To better understand the whole structure of 3, the topological analysis approach was employed. As similar to that in complex 1, we also consider each MBB as a topological point. Therefore, every MBB II links to four other adjacent MBBs II and four MBBs I and can be seen as an eight-connected node, whereas every MBB I connects to four MBBs II and can be seen as a four-connected node. On the basis of the simplified, complex 3 can be described as a bimodal (4,8)-connected sqc-21 type 3D framework with the Schläfli symbol {32·42·52}{34·48·512·64} (long vertex symbol [3·3·3·3·4·4·4·4·4·4·6(3)·6(3)·6(3)·6(3)· 6(3)·6(3)·6(3)·6(3)·*·*·*·*·*·*·*·*·*·*][3·3·4·4·6(2)·6(2)]) as analyzed by TOPOS.17 Crystal Structure of 4. By replacing H2mBDC with HINC, we obtained complex 4. Single-crystal X-ray diffraction study unambiguously revealed that complex 4 crystallizes in the monoclinic system with P1̅ space group. The asymmetric unit of 4 contains one Tb(III) ion, three Ag(I) ions, two BSPT2− anions, two INC− anions, and one coordinated water molecule.

Crystal Structure of 3. Structure determination shows that complex 3 crystallizes in the monoclinic form with space group P1̅ and features a 3D Ce(III)−Ag(I) heterometallic−organic framework. The asymmetric unit of 3 contains one Ce(III) ion, one Ag(I) ion, one DSPT2− anion, one mBDC2− anion, two coordinated water molecules, and one uncoordinated water molecule. Because the Ce(III) ion is larger than the Sm(III) and Er(III) ions, the coordination number of Ln(III) is larger than that in complexes 1 and 2. The Ce(III) ions adopt a distorted tricapped trigonal prism geometry, which is coordinated by five oxygen atoms from three mBDC2− ligands, two oxygen atoms from two DSPT2− anions, and two water oxygen atoms (Figure 2a). The Ce−O bond lengths range from 2.472(3) to 2.785(3) Å, and the O−Ce−O bond angles vary from 48.01(10)° to 147.26(10)°, all of which are within the normal range.16 The coordination environment of Ag(I) is the same as that in complex 1, which is surrounded by the terpyridine unit and 2-SO3− groups (Figure 2b). The Ag−N bonds lengths are in the range of 2.377(4)−2.422(4) Å, while the Ag−O bond is 2.402(5) Å; the Ag−N bonds lengths are comparable to those in complex 1, while the Ag−O is slight longer. The coordination modes of BSPT2− and mBDC2− anions are similar to that in complex 1, except that the 4-SO3− group binds to two Ce(III) ions and takes on a trans conformation. Hence, similar MBBs I are found in complex 3. Two BSPT2− anions and two Ag(I) ions are joined together to form a binuclear MBB. The skeleton of such MBB I is the same as that in complex 1, but they have differences in their conformations, which may be seen from the twist angle between the terpyridine and benzene groups. Such an angle in 3 is 63.89(10)°, which is larger than that in complex 1. The Ag··· Ag distance [4.3421(8) Å] is smaller than that in complex 1. All the data imply the slightly different conformation of MBB I in 4432

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The Tb(III) ion is seven-coordinated by seven oxygen atoms from three INC− anions, three different BSPT2− anions, and one coordinated water molecule (Figure 3a). The Ag1 and Ag2 have a similar coordination environment to that in complexes 1−3, with Ag−N bonds ranging from 2.343(13) to 2.427(13) Å and the Ag−O distance of 2.326(10) and 2.356(8) Å (Figure 3b). The Ag3 ion is coordinated by two pyridyl groups displaying a linear geometry (Figure 3c). The Ag−N bonds are 2.130(11) and 2.145(11) Å. One O atom on the 4-SO3− group approaches to the Ag3 ion with a Ag···O distance of 2.845(15) Å, which can be seen as a Ag···O weak interaction.18 The coordination mode of DSPT2− in complex 4 (Scheme 3, mode III) is similar to those in complexes 1 and 2, except for the 2-SO3− group in complex 3 not only binds to a Ag(I) ion but also binds to another Ln(III) ion. The INC− anion adopts a usual coordination mode observed in many heterometallic CPs, that is, use the carboxyl group binds Ln(III) ions and the N atom binds Ag(I) ion (Scheme 3, mode VI). MBB I and MBB II are also formed in the structure of complex 4 (Figure 3a,b). The MBB I displays the same skeleton to that in complexes 1− 3, and the corresponding angles between terpyridine and benzene groups are 55.53(33)° and 66.50(31)°, which means the conformation is changeable and makes the MBB I flexible to some extent. The MBB II is formed by two Tb(III) bridged by two carboxyl and two 4-SO3− groups as similar to that in 1. The MBBs I, MBBs II, and Ag3 ions are connected together into a 2D layer extend into the ab plane (Figure 3d). Such a 2D layer is packing along the xxx direction in abab fashion, resulting in a complicated 3D supramolecular framework. We found that the Ag···O weak interactions are important for the fomation of the 3D supramolecular framework, so we try to analysis the framework by considering both the coordination bonds and the Ag···O weak interactions, in order to clarify the organization of different MBBs into a unique framework. In the whole framework, we can see that every MBB II linking to four MBBs I and four Ag3 ions can be seen as a eight-connected node, the MBB I connecting to two MBBs II and one Ag3 ion can be seen as a three-connected node, and the Ag3 ions that connect to two MBBs II and one Ag(I) MBB is also a threeconnected node. Therefore, the resulting framework is a 3D (3,8)-connected bimodal framework with the point symbol is {32·42·52}{34·48·512·64} (long vertex symbol [3·3·3·3·4·4·4·4·4· 4·6(3)·6(3)·6(3)·6(3)·6(3)·6(3)·6(3)· 6(3)·*·*·*·*·*·*·*·*·*·*][3·3·4·4·6(2)·6(2)]) as analyzed by TOPOS.17 XRPD and TGA. X-ray powder diffraction (XRPD) experiments were performed for complexes 1−4 in order to check the purity of the bulk materials. The results are shown in Figures S1−S4 (Supporting Information). As seen from Figures S2 and S3 (Supporting Information), the peak positions displayed in simulated and experimental patterns for complexes 2 and 3 are in good agreement with each other, thus confirming the phase purity of the synthesized samples. However, for complexes 1 and 4, most experimental peak positions in low angles are in good agreement with the simulated one, but some abnormal peaks are observed in higher angles, which may due to the photolysis of complexes containing Ag(I) ions (the products may be Ag2O, Ag, and so on). Thermogravimetric analysis (TGA) of complex 2 shows weight losses in the temperature range of 25−120 °C, as seen from Figure 4, corresponding to release of coordinated and uncoordinated water molecules (found 5.5%, calculated 5.6%). The second weight loss from 240 to 280 °C may due to the

Figure 4. TG curves for complexes 2 and 3.

decarboxylation of the H2mBDC (found 88.3%, calculated 85.3%). Then, a major weight loss occurs in the range of 460− 620 °C, suggesting decomposition of the coordination framework. For complex 3, the weight loss found of 4.8% (calculated 5.8%) below 180 °C was due to the loss of coordinated water molecules. After the loss of coordinated water molecules, the framework was stable to about 520 °C and then it began to decompose. The relative higher stability of 3 may be due to its higher dimension framework compared to 2. Photoluminescent Properties. Besides complex 4, all the other complexes have not shown significant fluorescent emission from 200 to 750 nm. Complex 4 only exhibits very weak fluorescent emission under our experimental conditions (Figure 5). When excited at 328 nm, the complex 4 displays the

Figure 5. Solid-state emission spectrum for 4 in the solid state at room temperature (excited at 396 nm).

characteristic transition of 5D4 → 7FJ (J = 3−6) of the Tb(III) ion. Two intense sharp line emission bands at 489 and 546 nm are ascribed to 5D4 → 7F6 and 5D4 → 7F5 transitions, whereas the weaker emission bands at 586 and 622 nm originate from the 5D4 → 7F4 and 5D4 → 7F3 transitions, respectively. Additionally, complex 4 also displays weak broad bands around 400 nm, which may be due to ligand−metal charge transfer (LMCT) from the conjugated systems on the H2DSPT ligands to Ag(I). Compared with the strong emission of the H2DSPT ligand, the intensities of complex 4 are much weaker, suggesting that it is indicative of a heavy-atom quenching effect and the energy transitions from the organic ligands to the Tb(III) centers are very ineffective. In conclusion, we have successfully synthesized four new d−f coordination frameworks based on H2DSPT and HINC/ 4433

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Crystal Growth & Design

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H2mBDC ligands. Those complexes are the rare examples of 3D 4d−4f heterometal−organic coordination polymers containing two kinds of organic ligands based on well-defined Ag(I) and Ln(III) MBBs. Our results provide an intriguing example of preparing coordination polymers with multitype metal ions and ligands. Further systematic studies for the design and synthesis of such crystalline materials with desirable properties based on the H2DSPT ligand with other auxiliary ligands are currently under way.

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ASSOCIATED CONTENT

S Supporting Information *

Additional structural figures for the related complexes, tables of selected bond lengths and angles, PXRD, and X-ray crystallographic files in CIF format for complexes 1−4 are available in the Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*Phone: +86-20-39310383. Fax: +86-20-39310187. E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of P. R. China (grant no. 21003053 and 21171059), and the Natural Science Foundation of Guangdong Province (grant no. 10451063101004667).

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REFERENCES

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dx.doi.org/10.1021/cg400926q | Cryst. Growth Des. 2013, 13, 4428−4434