A Series of Coordination Polymers Constructed from a Multidentate N

Article pubs.acs.org/crystal

A Series of Coordination Polymers Constructed from a Multidentate N‑Donor Ligand and Varied Carboxylate Anions: Syntheses, Structures, and Luminescent Properties Zhe Zhang, Jian-Fang Ma,* Ying-Ying Liu, Wei-Qiu Kan, and Jin Yang* Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China S Supporting Information *

ABSTRACT: Ten new coordination polymers, [Zn2(Htrb)(L1)2]·8H2O (1), [Zn2(Htrb)(HL2)2(H2O)2]·4H2O (2), [Co2(Htrb)(HL2)2(H2O)2]·4H2O (3), [Cd2(Htrb)(HL2)2(H2O)2]·4H2O (4), [Cu3(Htrb)(L2)2(H2O)2]·8H2O (5), [Ag5(Htrb)(HL2)(L2)(H2O)2]·2H2O (6), [Ag6(Htrb)2(HL3)2(L4)]·2H3L3· 6H2O (7), [Ag4(Htrb)2(H2L5)2] (8), [Ag6(Htrb)2(HL6)2(H2O)3]·2H2O (9), and [Ag2(Htrb)]·2NO3 (10), based on a hexadentate N-donor ligand hexakis(1,2,4-triazol-ylmethy1)benzene (Htrb) and different carboxylates, have been synthesized (H2L1 = 5-OH-1,3-benzenedicarboxylic acid, H3L2 = 1,3,5benzenetricarboxylic acid, H3L3 = 1,2,4-benzenetricarboxylic acid, H2L4 = 2-CH2OH-1,4-benzenedicarboxylic acid, H4L5 = 3,3′,4,4′-benzophenone tetracarboxylate acid, and H4L6 = 4,4′-oxidiphthalic acid). Compounds 1−4 feature typical 2D binodal 4-connected networks with a (4·64·8)2(42·64) topology. Compound 5 exhibits a 3D (4,6)-connected (44·62)(44·610·8) framework. Compound 6 shows a 3D trinodal (6,8)-connected framework with a (34·44·52·65)2(34·412·54·68) topology. Compound 7 features an unusual 3D trinodal (4,6)-connected net with a (32·62·72)(3·4·5·62·8)2(32·42·52·64·72·83) topology. Compound 8 displays a 2D layer with a (3,4)-connected (4·62)2(42·62·82) topology. Compound 9 shows a uninodal 2D 4-connected network with a (44)(62) topology. Compound 10 reveals a 3D (4,8)-connected (46)2(412·612·84) net. The ligand effects on the complex structures were studied. Moreover, their luminescent emissions were studied at room temperature.

■

Scheme 1. Organic Ligands Examined in This Study

INTRODUCTION Coordination polymers (CPs) with intriguing architectures and diverse applications, such as magnetism, sorption, catalysis, electrical conductivity, and luminescent science, have received much attention from chemists.1−3 The CPs with flexible N-containing ligands have gained considerable interest of chemists.4 The flexible N-containing multidentate ligands with triazole nitrogen donors, such as tri(triazole) and tetra(triazole) ligands, have been widely studied in coordination chemistry. Through the use of these ligands, a number of aesthetic topological structures have been constructed.5−7 However, systematic investigation of the coordination chemistry of the poly(triazole) ligands, such as hexakis(triazole), still remains lacking. In this work, the hexakis(1,2,4-triazol-ylmethy1)benzene (Htrb) was chosen for the construction of CPs with unique architectures. First, the Htrb ligand with six triazole groups can afford multiple potential coordination sites to coordinate with metals in various modes. Second, the triazole groups of the Htrb can freely rotate and adjust bond angles with the coordination geometries of central metals.8 As we know, the carboxylates can influence the final structures of CPs during the assembly. For this purpose, varied organic polycarboxylates were elaborately selected in this system. In this work, 10 new CPs, [Zn2(Htrb)(L1)2]·8H2O (1), © XXXX American Chemical Society

Received: May 2, 2013 Revised: August 6, 2013

A

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Table 1. Crystal Data and Structure Refinements for Compounds 1−10 1

2

3

formula Mr space group a/Å b/Å c/Å α/deg ß/deg γ/deg V/Å3 Z Dc (g/cm3) GOF on F2 R1a [I > 2σ(I)] wR2b (all data) Rint

C40H48N18O18Zn2 1199.70 P1 10.0330(6) 10.9540(6) 12.8250(8) 68.518(6) 80.503(5) 84.620(5) 1292.74(13) 1 1.541 1.069 0.0525 0.1520 0.0400 4

C42H44N18O18Zn2 1219.69 P2/n 13.2860(9) 10.0240(5) 17.4370(10) 90 98.758(5) 90 2295.2(2) 2 1.765 1.021 0.0647 0.1274 0.0692 5

C42H44N18O18Co2 1206.81 P2/n 13.3020(4) 10.0260(3) 17.4500(5) 90 98.713(3) 90 2300.38(12) 2 1.742 1.035 0.0415 0.0940 0.0298 6

formula Mr space group a/Å b/Å c/Å α/deg ß/deg γ/deg V/Å3 Z Dc (g/cm3) GOF on F2 R1a [I > 2σ(I)] wR2b (all data) Rint

C42H44N18O18Cd2 1313.75 P2/n 13.3950(5) 10.1770(3) 17.6620(9) 90 96.925(3) 90 2390.14(17) 2 1.825 1.034 0.0345 0.0893 0.0280

C42H50N18O22Cu3 1349.62 P1 11.1920(6) 12.4010(8) 12.5660(7) 64.424(6) 75.586(5) 80.446(5) 1520.23(17) 1 1.474 1.103 0.0565 0.1754 0.0340

C42H39N18O16Ag5 1591.26 P1 9.3480(5) 12.3510(7) 12.4570(6) 100.015(5) 107.880(5) 111.846(5) 1200.99(11) 1 2.200 1.051 0.0310 0.0813 0.0177 10

formula Mr space group a/Å b/Å c/Å α/deg ß/deg γ/deg V/Å3 Z Dc (g/cm3) GOF on F2 R1a [I > 2σ(I)] wR2b (all data) Rint a

7

8

9

C93H83Ag6N36O35 2912.17 P1 9.7460(5) 15.2850(7) 18.6560(9) 107.339(4) 99.509(4) 92.536(4) 2603.5(2) 1 1.857 1.022 0.0590 0.1493 0.0392

C82H64Ag4N36O18 2273.17 P1 10.9860(7) 12.7110(7) 15.9970(9) 94.244(5) 109.288(5) 103.527(5) 1520.23(17) 1 1.867 1.024 0.0531 0.1276 0.0338

C80H72Ag6N36O23 2552.96 P1 12.9380(8) 14.0410(10) 15.3420(10) 106.161(6) 114.154(6) 99.768(6) 2311.2(3) 1 1.834 0.987 0.0646 0.1630 0.0413

C24H24Ag2N20O6 904.37 C2/c 24.9690(12) 8.3600(3) 17.3060(9) 90 120.024(7) 90 3127.7(2) 1 1.921 1.039 0.0373 0.1019 0.0255

R1 = ∑||Fo| − |Fc||/∑|Fo|. bwR2 = {∑[w(Fo2 − Fc2)2]/∑w(Fo2)2]}1/2.

H3L2 = 1,3,5-benzenetricarboxylic acid, H3L3 = 1,2,4-benzenetricarboxylic acid, H2L4 = 2-CH2OH-1,4-benzenedicarboxylic acid, H4L5 = 3,3′,4,4′-benzophenone tetracarboxylate acid, and H4L6 = 4,4′-oxidiphthalic acid) (Scheme 1). The Htrb coordination modes and the effects of carboxylates on the structures of CPs will be discussed in detail. In addition, their solid-state luminescent emissions were investigated at room temperature.

[Zn2(Htrb)(HL2)2(H2O)2]·4H2O (2), [Co2(Htrb)(HL2)2(H2O)2]·4H2O (3), [Cd2(Htrb)(HL2)2(H2O)2]·4H2O (4), [Cu3(Htrb)(L2)2(H2O)2]·8H2O (5), [Ag5(Htrb)(HL2)(L2)(H 2 O) 2 ]·2H 2 O (6), [Ag 6 (Htrb) 2 (HL3) 2 (L4)]·2H 3 L3· 6H2O (7), [Ag4(Htrb)2(H2L5)2] (8), [Ag6(Htrb)2(HL6)2(H2O)3]·2H2O (9), and [Ag2(Htrb)]·2NO3 (10), have been prepared (H 2 L1 = 5-OH-1,3-benzenedicarboxylic acid, B

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Figure 1. (a) Zn(II) coordination environment of 1. Symmetry codes: architecture in 1. (d) 2D binodal 4-connected network of 1.

■

Article

#1

x − 1, y, z;

#2

−x, −y, −z + 2. (b) 2D layer in 1. (c) 3D supramolecular

1273(s), 1209(m), 1132(s), 1001(m), 840(w), 806(m), 779(s), 738(m), 670(m), 639(m), 552(w), 445(w). Synthesis of [Zn2(Htrb)(HL2)2(H2O)2]·4H2O (2). 2 was isolated by using the similar method to that of 1, where H3L2 (21.0 mg, 0.1 mmol) was utilized in place of H2L1. Light yellow crystal products were isolated in a 62% yield. The pH value was about 6 for the final reaction system. Anal. Calcd for C42H44N18O18Zn2 (Mr = 1219.69): C, 41.36; H, 3.64; N, 20.67. Found: C, 41.17; H, 3.72; N, 20.49. IR data (KBr, cm−1): 3385(s), 3121(s), 1869(w), 1626(s), 1582(s), 1525(s), 1361(s), 1271(s), 1207(m), 1137(s), 1001(m), 931(w), 908(w), 837(w), 754(s), 670(m), 638(m), 515(w). Synthesis of [Co2(Htrb)(HL2)2(H2O)2]·4H2O (3). 3 was isolated by using the similar method to that of 2, where CoCl2·6H2O (23.8 mg, 0.1 mmol) was utilized in place of Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol). Pink crystal products were isolated in a 34% yield. The pH value was approximately 6 for the final reaction system. Anal. Calcd for C42H44N18O18Co2 (Mr = 1206.81): C, 41.80; H, 3.68; N, 20.89. Found: C, 41.59; H, 3.73; N, 20.77. IR data (KBr, cm−1): 3394(m), 3144(m), 1869(w), 1623(s), 1580(m), 1371(s), 1266(s), 1137(m), 983(w), 754(m), 732(s), 696(w), 671(m), 637(m), 515(w). Synthesis of [Cd2(Htrb)(HL2)2(H2O)2]·4H2O (4). 4 was isolated by the similar way to that of 3, where CdCl2·2.5H2O (22.8 mg, 0.1 mmol) was utilized in place of CoCl2·6H2O (23.8 mg, 0.1 mmol). Yellow crystal products were isolated in a 57% yield. The pH value was approximately 6 for the final reaction system. Anal. Calcd for C42H44N18O18Cd2 (Mr = 1313.75): C, 38.40; H, 3.38; N, 19.19. Found: C, 38.24; H, 3.43;

EXPERIMENTAL SECTION

Reagents and Instruments. The Htrb was obtained in accordance with the known method.9 The reagents and solvents were commercially obtained. Microanalytical data were carried out with a Perkin-Elmer 240 elemental analyzer. A Mattson Alpha Centauri spectrometer was used to conduct the FT-IR spectra on KBr pellets from 4000 to 400 cm−1. A Perkin-Elmer FLS-920 spectrometer was used to measure the solid-state emission/excitation spectra. A Rigaku Dmax 2000 X-ray diffractometer with graphite monochromatized Cu Kα radiation (λ = 0.154 nm) was used to carry out the PXRD patterns of the samples. For 1−10, the experimental PXRD peaks correspond well to the simulated ones (Figure S1, Supporting Information). Syntheses. During the syntheses of compounds 1−10, a series of parallel experiments were conducted in the pH values ranging from 3 to 9. However, for each compound, only one kind of product can be determined by single-crystal X-ray diffraction. The final pH values given below are the ones that can yield a quantity of the final crystal samples. Synthesis of [Zn2(Htrb)(L1)2]·8H2O (1). The Htrb (18.8 mg, 0.03 mmol), Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), distilled water (8 mL), and H2L1 (18.2 mg, 0.1 mmol) were sealed in a Teflon reactor and subjected to hydrothermal conditions at 130 °C for 3 days. Yellow crystal products were isolated in a 60% yield after cooling the mixture to room temperature at 10 °C·h−1. The pH value was about 6 for the final reaction system. Anal. Calcd for C40H48N18O18Zn2 (Mr = 1199.70): C, 40.04; H, 4.03; N, 21.01. Found: C, 39.92; H, 4.11; N, 21.12. IR data (KBr, cm−1): 3412(m), 3114(m), 1623(s), 1581(s), 1506(m), 1347(s), C

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 2. (a) Zn(II) coordination environment of 2. Symmetry codes: #1 x + 1/2, −y + 2, z + 1/2; #2 x, y + 1, z. (b) 2D layer of 2. (c) 3D supramolecular motif formed through π−π stackings in 2. (d) 2D 4-connected network of 2. N, 19.35. IR data (KBr, cm−1): 3379(m), 3128(m), 1870(w), 1671(m), 1616(s), 1563(s), 1521(m), 1438(s), 1366(s), 1284(s), 1262(s), 1207(m), 1136(s), 1003(m), 901(w), 839(w), 733(s), 696(m), 670(s), 637(m), 524(w). Synthesis of [Cu3(Htrb)(L2)2(H2O)2]·8H2O (5). 5 was isolated by the similar method to that of compound 4, where CdCl2·2.5H2O (22.8 mg, 0.1 mmol) was replaced by CuCl2·2H2O (17 mg, 0.1 mmol). Blue crystal products were isolated in a 15% yield. The pH value was about 6.5 for the final reaction system. Anal. Calcd for C42H50N18O22Cu3 (Mr = 1349.62): C, 37.38; H, 3.73; N, 18.68. Found: C, 37.23; H, 3.66; N, 18.76. IR data (KBr, cm−1): 3433(s), 3126(m), 1616(s), 1563(s), 1435(m), 1359(s), 1291(m), 1209(w), 996(w), 933(w), 856(w), 762(m), 670(m), 598(w), 453(w). Synthesis of [Ag5(Htrb)(HL2)(L2)(H2O)2]·2H2O (6). 6 was isolated by the analogous method to that of 5, where AgNO3 (17.0 mg, 0.1 mmol) was utilized in place of CuCl2·2H2O (17 mg, 0.1 mmol). Colorless crystal products were isolated in a 32% yield. The pH value was about 6 for the final reaction system. Anal. Calcd for C42H39N18O16Ag5 (Mr = 1591.26): C, 31.70; H, 2.47; N, 15.84. Found: C, 31.49; H, 2.51; N, 15.95. IR data (KBr, cm−1): 3446(s), 3124(m), 3031(w), 1705(s), 1651(m), 1525(m), 1384(m), 1331(m), 1286(s), 1215(m), 1137(s), 1014(w), 890(w), 753(m), 671(m), 626(w). Synthesis of [Ag6(Htrb)2(HL3)2(L4)]·2H3L3·6H2O (7). 7 was isolated by the analogous method to that of 6, where H3L3 (21.0 mg, 0.1 mmol) was employed as the carboxylate. Colorless crystal products were isolated in a 12% yield. The pH value was about 5.5 for the final reaction system. Anal. Calcd for C93H83N36O35Ag6 (Mr = 2912.17): C, 38.36; H, 2.87; N, 17.32. Found: C, 38.54; H, 2.92; N, 17.24. IR data (KBr, cm−1): 3450(w), 3120(m), 3029(w), 1835(w), 1665(s), 1573(s), 1508(s), 1369(s), 1280(m), 1208(m), 1133(s), 1026(s), 986(m), 876(m), 770(w), 734(s), 667(s), 637(m), 544(m), 468(w), 407(w).

Figure 3. Co(II) coordination environment of 3. Symmetry codes: #1 x + 1/2, −y, z + 1/2; #2 x, y − 1, z.

Figure 4. Cd(II) coordination environment of 4. Symmetry codes: #1 x + 1/2, −y + 2, z + 1/2; #2 x, y − 1, z. Synthesis of [Ag4(Htrb)2(H2L5)2] (8). Compound 8 was prepared by the analogous method to that of 7, where H4L5 (32.0 mg, 0.1 mmol) was utilized to replace H3L3 (21.0 mg, 0.1 mmol). Colorless crystal products were acquired in a 54% yield. The pH value was about 5.5 for D

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 5. (a) Cu(II) coordination environments of 5. Symmetry codes: #1 x + 1, y, z − 1; #2 −x, −y, −z + 1; #3 −x + 1, −y, −z + 1; #4 −x + 2, −y + 1, −z + 1. (b) 1D chain constructed from the L2 anions and Cu(II) ions in 5. The digit “2” in the circle represents Cu1 and its symmetry-related species. (c) 3D framework of 5. (d) Schematic (4,6)-connected (44·62)(44·610·8) net in 5. the final reaction system. Anal. Calcd for C82H64N36O18Ag4 (Mr = 2273.17): C, 44.12; H, 2.84; N, 22.18. Found: C, 43.93; H, 2.81; N, 22.12. IR data (KBr, cm−1): 3648(s), 3597(s), 3131(w), 1556(w), 1204(w), 1159(m), 1125(w), 1078(m), 1021(m), 1002(w), 981(m), 930(s), 885(m), 866(s), 831(m), 807(s), 739(w), 670(w), 633(m), 460(s), 419(s). Synthesis of [Ag6(Htrb)2(HL6)2(H2O)3]·2H2O (9). Complex 9 was prepared by the similar way to that of 8, where H4L5 (32.0 mg, 0.1 mmol) was replaced by H4L6 (30.0 mg, 0.1 mmol). Colorless crystal products were isolated in a 62% yield. The pH value was about 6 for the final reaction system. Anal. Calcd for C80H72N36O23Ag6 (Mr = 2552.96): C, 37.64; H, 2.84; N, 19.75. Found: C, 37.81; H, 2.88; N, 19.63. IR data (KBr, cm−1): 3442(m), 3122(m), 1684(w), 1588(s), 1522(s), 1357(s), 1264(s), 1223(s), 1134(s), 1024(m), 984(m), 889(m), 862(m), 806(w), 774(m), 672(s), 636(m), 490(w). Synthesis of [Ag2(Htrb)]·2NO3 (10). Compound 10 was isolated by the similar way to that of 9, whereas organic acid was not present in the reaction system of 10. Yellow crystal products were acquired in a 53% yield. The pH value was about 7 for the final reaction system. Anal. Calcd for C24H24N20O6Ag2 (Mr = 904.37): C, 31.88; H, 2.68; N, 30.98. Found: C, 31.69; H, 2.57; N, 31.12. IR data (KBr, cm−1): 3394(w), 3109(m), 3012(w), 1741(w), 1518(s), 1360(s), 1283(m), 1135(s), 1013(m), 975(m), 866(w), 827(w), 734(w), 670(s), 636(m), 455(w). Crystallography. An Oxford Diffraction Gemini R Ultra diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) was used to collect single-crystal X-ray diffraction data of 1−10 at 293 K. A multiscan technique was used to perform absorption corrections. The structures were solved by the direct method.10a The full-matrix leastsquares techniques using the SHELXL-97 program within WINGX were

used to refine all non-hydrogen atoms.10b In 6, the O5W atom is split over two sites (O5W, O5WA) with equal site occupation factors of 0.5. In 7, the atoms (Ag1 and Ag1A, Ag3 and Ag3A, O13 and O13A) were disordered and split over two sites (the total occupancy for each pair of disordered atoms is 1). The C47 atom is disordered by symmetry (site occupation factor is 0.5). O15 and O15A atoms of the half H2L4 ligand are disordered by symmetry (site occupation factors are 0.25 and 0.25, respectively). In 8, the Ag2 atom is split over two sites (Ag2, Ag2A) with equal site occupation factors of 0.5. In 9, the atoms (O1W, O1WA, and O1WB) were disordered and split over three sites (the total occupancy is 1). In 10, the Ag1 atom is split over two sites (Ag1, Ag1A) with equal site occupation factors of 0.5. Table 1 shows the detailed crystallographic parameters of 1−10. The OLEX program was used to analyze the networks of 1−10.11

■

RESULTS AND DISCUSSION Structure of [Zn2(Htrb)(L1)2]·8H2O (1). There exist one L1 anion, one Zn(II) ion, a half Htrb, and four free H2O molecules in the asymmetric unit of 1. The central Zn(II) ion is surrounded by two O atoms of distinct L1 anions, and two N atoms of Htrb ligands, displaying a tetrahedral geometry (Figure 1a). The Zn−O distances are 1.976(2) and 2.001(3) Å, respectively (Tables S1−S10, Supporting Information). The Zn−N bond distances are 2.019(3) and 2.020(3) Å, respectively. Each L1 anion exhibits a bidentate bridging mode and links adjacent Zn(II) ions into a chain. The Htrb ligand in a 1,3,5-up/ 2,4,6-down fashion bridges adjacent chains to yield a 2D sheet E

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 6. (a) Ag(I) coordination environments of 6. Symmetry codes: #1 −x, −y − 1, −z + 1; #2 −x − 1, −y − 1, −z + 1; #3 −x − 3, −y − 2, −z; #4 x − 1, y − 1, z; #5 −x, −y, −z; #9 x + 1, y, z. (b) 1D chain structure constructed from L2 anions and Ag(I) ions in 6. The digits “2” and “3” in the circles represent binuclear and trinuclear Ag(I) units, respectively. (c) 3D motif of 6. (d) 3D trinodal (6,8)-connected net of 6.

Figure 7. (a) Ag(I) coordination environments of 7. Symmetry code: #1 x + 1, y, z. (b) The Ag−organic fragment and the 3D structure of 7. (c) The 3D trinodal (4,6)-connected net of 7. F

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 8. (a) Ag(I) coordination environments of 8. Symmetry codes: #1 −x − 1, −y, −z; #2 x − 1, y − 1, z. (b) Ag−organic layer in 8. (c) View of the 3D supramolecular architecture in 8. (d) (3,4)-connected sheet in 8. The digit “2” in the circle represents the binuclear Ag(I) unit.

(Figure 1b). There exist the aromatic π−π stackings of L1 anions in the adjacent layers (centroid-to-centroid and plane-toplane distances are 3.70 and 3.56 Å, respectively) (Table S1, Supporting Information). These π−π stackings among 2D sheets led to a 3D supramolecular motif (Figure 1c). Topologically, if the central Zn(II) ions and the Htrb ligands are viewed as 4-connected nodes, respectively, the overall motif of 1 is a 2D binodal 4-connected (4·64·8)2(42·64) network (Figure 1d). Structure of [Zn2(Htrb)(HL2)2(H2O)2]·4H2O (2). Singlecrystal structure analysis reveals that compounds [Zn2(Htrb)(HL2)2(H2O)2]·4H2O (2), [Co2(Htrb)(HL2)2(H2O)2]·4H2O (3), and [Cd2(Htrb)(HL2)2(H2O)2]·4H2O (4) are isostructural (Figures 2−4). As a result, compound 2 is described in detail as a representative structure. 2 crystallizes with one Zn(II) ion, half a Htrb ligand, one HL2 anion, and three water molecules. The octahedral coordination geometry of the central Zn(II) ion is completed by four O atoms of two HL2 anions and one water molecule, and two N atoms of two distinct Htrb ligands. Each HL2 anion bridges two Zn(II) ions to yield infinite chains. The Htrb ligands in 1,2,4-up/3,5,6-down fashions link adjacent chains to yield a layer (Figure 2b). Further, the aromatic π−π interactions between HL2 anions link the adjacent layers, yielding a 3D supramolecular motif (centroid-to-centroid and

plane-to-plane distances are 3.45 and 3.33 Å, respectively) (Figure 2c). Topologically, both the Htrb ligands and the Zn(II) ions are viewed as 4-connected nodes, respectively. Thus, the 2D layer of 2 is a 4-connected network with a (4·64·8)2(42·64) topology. Structure of [Cu3(Htrb)(L2)2(H2O)2]·8H2O (5). The independent unit of 5 is composed of one L2 anion, one and a half Cu(II) ions, a half Htrb ligand, and five water molecules (Figure 5a). Cu1 shows a square-pyramidal coordination geometry, completed by two O atoms of two individual L2 anions, and three N atoms of three different Htrb ligands. The Cu1−N bond lengths are from 1.989(3) to 2.081(3) Å. The Cu1−O distances are 1.953(3) and 2.125(3) Å, respectively. Different from Cu1, Cu2 is bonded to four O atoms of two independent L2 anions, and the two terminal O atoms of two water molecules in an octahedral sphere. Each L2 anion, as a bridging ligand, links three Cu(II) ions to yield a chain. In this chain, two symmetry-related Cu1 atoms are linked together by the bridging carboxylate oxygen atoms, resulting in a binuclear Cu(II) unit (Figure 5b). Further, adjacent chains are bridged by Htrb ligands in hexadentate modes, yielding a complicated 3D framework (Figure 5c). Topologically, if the Htrb ligand and the binuclear Cu(II) unit (Cu1 and its symmetry-related species) are 6-connected and 4-connected nodes, respectively, the structure of 5 is a 3D binodal (4,6)-connected (44·62)(44·610·8) net (Figure 5d). G

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 9. (a) Ag(I) coordination environments of 9. Symmetry codes: #1 −x + 2, −y, −z; supramolecular architecture of 9. (d) 2D 4-connected sheet of 9 with (44)(62) topology.

Structure of [Ag5(Htrb)(HL2)(L2)(H2O)2]·2H2O (6). In the asymmetric unit of 6, there exist two and a half Ag(I) ions, one L2 anion, half a Htrb ligand, and two H2O molecules. As shown in Figure 6a, Ag1, Ag2, and Ag3 show five-, four-, and twocoordinated square-pyramidal (N3O2), tetrahedral (N2O2), and linear (O2) coordination environments, respectively. Each tetradentate L2 anion bridges four Ag(I) ions to yield a chain, where the carboxylate groups link Ag1 and its symmetry-related species to form a binuclear unit (Figure 6b). Ag3, Ag2, and their symmetry-related species are joined together by the carboxylates to result in a trinuclear cluster (Figure 6b). As illustrated in Figure 6c, neighboring chains are further extended by decadentate Htrb ligands in 1,2,3-up/4,5,6-down fashions into a 3D structure. Topologically, the overall structure of 6 is a 3D trinodal (6,8)connected net with a (34·44·52·65)2(34·412·54·68) topology, where the Htrb ligands and the multinuclear Ag(I) units are simplified as 8-connected and 6-connected nodes, respectively. Structure of [Ag6(Htrb)2(HL3)2(L4)]·2H3L3·6H2O (7). The asymmetric unit of 7 contains three Ag(I) ions, two halves of Htrb ligands, one partially deprotonated H3L3 anion, one H3L3 molecule, a half L4 anion (the 2-carboxyl group of L3 was reduced to hydroxymethyl group), and three lattice H2O molecules (Figure 7a). Both tetrahedral Ag1 and Ag2 are bonded to two O atoms of two individual HL3, and two N atoms of two different Htrb. Ag3 shows an approximately T-shaped

#2

−x + 1, −y + 1, −z + 1. (b) 2D sheet of 9. (c) 3D

coordination geometry, completed by one O atom of one L4 anion, and two N atoms of two Htrb ligands. In 7, there exist two types of different Htrb ligands, where the Htrb ligand with N1, N4, and N7 is assigned as Htrb-1 (the Ag−N bond lengths are 2.128(7), 2.136(9), and 2.124(5) Å, respectively), and the Htrb ligand with N10, N13, and N16 is assigned as Htrb-2 (the Ag−N bond lengths are 2.129(6), 2.126(5), and 2.195(8) Å, respectively). As shown in Figure 7b, each Htrb ligand in a 1,2,3-up/4,5,6-down fashion bridges six Ag(I) ions to furnish layers. The layers are further bridged by the bidentate L4 anions to gain a 3D structure. The partially deprotonated HL3 anion further coordinates to the Ag(I) ions of the 3D framework in a tridentate mode. In addition, the H3L3 molecule only acts as a free molecule. Topologically, if the Htrb-2, the Htrb-1, and the binuclear Ag(I) unit (Ag2 and Ag3) are defined as 6-connected, 4-connected, and 4-connected nodes, respectively, the 3D structure of 7 belongs to a trinodal (4,6)-connected (32·62·72)(3·4·5·62·8)2(32·42·52·64·72·83) topology (Figure 7c). Structure of [Ag4(Htrb)2(H2L5)2] (8). There exist two Ag(I) ions, one H2L5 anion, and two halves of Htrb ligands in the asymmetric unit of 8. Ag1 and Ag2 exhibit different T-shaped environments (Figure 8a). Ag1 coordinates to two N atoms of two Htrb ligands, and one O atom of one H2L5. However, Ag2 is coordinated by three nitrogen atoms of Htrb ligands. In 8, Htrb ligands show tetradentate and hexadentate fashions H

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

plane-to-plane distances are 3.88 and 3.29 Å, respectively), resulting in a 3D supramolecular architecture (Figure 8c). Topologically, if the Htrb ligands and the binuclear Ag(I) units (Ag1 and Ag2) are 4-connected and 3-connected nodes, respectively, the resulting structure of 8 will be a 2D (3,4)-connected (4·62)2(42·62·82) network (Figure 8d). Structure of [Ag6(Htrb)2(HL6)2(H2O)3]·2H2O (9). As shown in Figure 9a, there exist three Ag(I) ions, one HL6 anion, two halves of Htrb ligands, and two and a half coordinated H2O molecules in the asymmetric unit of 9. Each Ag(I) ion shows a T-shaped coordination geometry. Ag1 and Ag2 are bonded to two N atoms of two Htrb ligands and one water O atom. Differently, Ag3 is surrounded by one O atom of one HL6 and two N atoms of two Htrb. Each Htrb ligand links six Ag(I) ions in a 1,2,3-up/4,5,6-down fashion to produce layers. The HL6 anions are decorated to the layers in monodentate modes (Figure 9b). In addition, adjacent layers are joined together via the π−π stackings, yielding a 3D supramolecular motif (centroid-to-centroid and plane-to-plane distances are 3.73 and 3.45 Å between two phenyl rings of HL6 anions; centroid -to-centroid and plane-to-plane distances are 3.93 and 3.62 Å between triazole and phenyl rings of HL6 anions) (Figure 9c). Topologically, if Ag1 and Ag3 can be considered as linkers, and each Htrb is a 4-connected node, the resulting network of 9 will be a uninodal 4-connected (44)(62) sheet (Figure 9d). Structure of [Ag2(Htrb)]·2NO3 (10). The independent unit of 10 contains one Ag(I) ion, a half Htrb ligand, and one free nitrate anion. Ag1 is in a tetrahedral geometry, defined by four Htrb N atoms. The Htrb ligand as an octadentate ligand (1,2,3up/4,5,6-down) bridges eight Ag(I) ions to produce an intricate 3D framework. The nitrate anion is free as a counteranion (Figure 10b). Topologically, if the Ag(I) ions and the Hrtb ligands are 4-connected and 8-connected nodes, respectively, the structure of 10 will be a 3D CaF2 net with a (46)2(412·612·84) topology (Figure 10c). Coordination Modes of Htrb Ligand. The Htrb ligand can influence framework structures of the compounds. In 1−10, the Htrb ligand adopts six types of different coordination modes (Scheme 2). In compound 1, six identical triazole substituents of the Htrb ligand bridge four metals and dispose alternately above and below the benzene plane. This coordination mode can be described as a tetradentate 1,3,5-up/2,4,6-down fashion (mode I). In compounds 2−4, the Htrb ligands bridge four metals in tetradentate 1,2,4-up/3,5,6-down fashions (mode II). However, in compounds 5, 7, and 9, the Htrb ligands link six metals in hexadentate 1,2,3-up/4,5,6-down fashions (mode III). In compound 8, the Htrb ligands bridge four and six metals in tetradentate and hexadentate (1,2,3-up/4,5,6-down) modes (modes III and IV), respectively. In compound 6, the Htrb ligand links 10 metals and shows a decadentate 1,2,3-up/4,5,6down fashion (mode V). In compound 10, the Htrb ligand bridges eight metals in an octadentate 1,2,3-up/4,5,6-down

Figure 10. (a) Ag(I) coordination environment in 10. Symmetry codes: #1 x + 1/2, y − 1/2, z; #2 x + 1/2, −y + 3/2, z + 1/2; #3 −x, −y + 1, −z + 1. (b) The 3D framework of 10. (c) The 3D CaF2 net with (46)2(412·612· 84) topology in 10.

(1,2,3-up/4,5,6-down). As shown in Figure 8b, the Htrb ligands bridge Ag(I) ions, yielding a layer. The H2L5 anion bridges Ag(I) ions of the layer, but it does not improve the dimension of 8. Moreover, the sheets are jointed together through the π−π stackings of triazole rings (the centroid-to-centroid and Scheme 2. Htrb Coordination Modes in 1−10

I

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 11. Emission spectra of the Htrb ligand and compounds 1, 2, 4, and 6−10 in the solid state at room temperature.

Luminescent Properties. Taking into account the excellent luminescent properties of coordination polymers with d10 metals,13 the luminescence properties of 1, 2, 4, 6−10 and the Htrb ligand were investigated. Their emission spectra at room temperature are depicted in Figure 11. The emission peaks of 1, 2, 4, and 6−10 are at 457 (λex = 300 nm), 488 (λex = 340 nm), 374 (λex = 340 nm), 471 (λex = 314 nm), 441 (λex = 240 nm), 474 (λex = 242 nm), 420 (λex = 253 nm), and 446 nm (λex = 260 nm), respectively. To know the emission nature, the luminescent property of the free Htrb ligand was studied. The free Htrb ligand exhibits a strong emission peak (λem = 501) upon excitation at 340 nm. In addition, the H2L1, H3L2, H4L5, and H4L6 show emission peaks at 346 (λex = 390 nm), 363 (λex = 300 nm), 557 (λex = 390 nm), and 415 nm (λex = 300 nm), respectively.14 These emissions can be originated from the π* → π or π*→ n transitions, as previously reported.15 Notably, the organic carboxylate anions almost do not contribute the emissions because of the effects of the electron-withdrawing substituents. However, the N-donor Htrb ligand has a significant contribution to the emissions of the compounds. Compared with the free Htrb ligand, the emission bands of these compounds exhibit blue shifts. This may come from the ligand-to-metal charge-transfer transition (LMCT) involving the Htrb ligand and the central metal ions.16

fashion (mode VI). It is noteworthy that the six identical triazole substituents are difficult to locate on the same side of the benzene plane. Thus, the steric hindrance of the giant hexakis(triazole) and the flexibility of the −CH2− groups between the benzene plane and six triazole substituents have synergic effects on the formation of the final coordination modes. The Htrb ligands used here are very easy to result in relatively high dimensional compound structures. For example, in compound 1, the Htrb ligand links four metal ions in mode I to furnish the 2D network. In compounds 2−4, the Htrb ligands, as tetradentate ligands in 1,2,4-up/3,5,6-down fashions (mode II), bridge four metals to yield a 2D layer. In compounds 5 and 7, the Htrb ligand bridges six metals in an 1,2,3-up/4,5,6-down fashion (mode III) to form the 3D framework. However, in compound 9, the Htrb ligand, as a hexadentate ligand in a 1,2,3-up/4,5,6-down mode (mode III), coordinates to six metals to produce a sheet. In compound 6, the Htrb ligand in a 1,2,3-up/4,5,6-down fashion (mode V) links 10 metals to produce a 3D net. In compound 8, the Htrb ligands, as tetradentate and hexadentate ligands (modes III and IV), join four and six metals to afford a 2D layer structure. In compound 10, the Htrb ligand, in an octadentate 1,2,3-up/4,5,6-down mode (mode VI), bridges eight metals to gain a 3D framework. Effect of Anions on the Framework. Organic anions have a crucial effect on the final motifs of compounds. Generally, the flexibilities, positions, and numbers of the carboxylate groups can influence the complex motifs.12 Compounds 6 and 7 indicate the effect of carboxylate positions on compound structures. For the dicarboxylates L2 in 6 and L4 in 7, the angles and positions of their carboxylates in benzene ring spacers are different. The angle of the two carboxylate groups in L2 is 60°, whereas the one in L4 is 180°. The different angles between the two carboxylate groups result in their coordination with Ag(I) ions in different directions. As a result, compound 6 displays a 3D trinodal (6,8)-connected net with the (34·44·52·65)2(34·412·54·68) topology. However, compound 7 shows a different 3D trinodal (4,6)-connected net with the (32·62·72)(3·4·5·62·8)2(32·42·52·64· 72·83) topology. Compounds 6 and 9 imply the carboxylate number effect on the compound structures. Compared with L6 (in 9), L2 (in 6) has an additional coordinated carboxylate group. Usually, the extra carboxylate group can increase the connection number of the ligand, which further results in different structure motifs. In compound 6, each L2, as a dicarboxylate anion, bridges Ag(I) ions to furnish a chain. However, in 9, each monocarboxylate L6 anion bridges one Ag(I) ion by the terminal oxygen atom (O1) to yield a discrete fragment. Clearly, the structural distinction of compounds 6 and 9 is primarily ascribed to the difference in the number of the carboxylate groups.

■

CONCLUSIONS Ten novel CPs based on the hexakis(triazole) ligand and varied organic polycarboxylates have been reasonably designed and hydrothermally synthesized. These compounds exhibit intriguing and fascinating 2D and 3D structural motifs. The systematic investigations of their structural diversities demonstrate that the Htrb ligand can act as a versatile building block with diverse coordination modes. Additionally, the numbers and positions of the carboxylate groups play critical roles in inducing the final structures. The results may portray a guideline for the rational synthesis and construction of targeted CPs with promising properties and potential applications. The solid-state fluorescence spectra show that compounds 1, 2, 4, and 6−10 have strong emissions at room temperature. Further studies on the coordination polymers based on related multidentate ligands are underway.

■

ASSOCIATED CONTENT

* Supporting Information S

X-ray crystallographic data in CIF format, selected bond lengths and angles, and PXRD patterns of compounds 1−10. This material is available free of charge via the Internet at http://pubs. acs.org. J

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

■

Article

3161. (d) Yang, J.; Ma, J.-F.; Liu, Y.-Y.; Ma, J.-C.; Jia, H.-Q.; Hu, N.-H. Eur. J. Inorg. Chem. 2006, 6, 1208. (6) (a) Dong, B.-X.; Xu, Q. Inorg. Chem. 2009, 48, 5861. (b) Su, Z.; Chen, M.; Okamura, T.-a.; Chen, M.-S.; Chen, S.-S.; Sun, W.-Y. Inorg. Chem. 2011, 50, 985. (c) Kan, W.-Q.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Dalton Trans. 2012, 41, 11062. (7) (a) Ohtsu, H.; Shimazaki, Y.; Odani, A.; Yamauchi, O.; Mori, W.; Itoh, S.; Fukuzumi, S. J. Am. Chem. Soc. 2000, 122, 5733. (b) Mukherjee, S.; Lan, Y.-H.; Kostakis, G. E.; Clérac, C. E. A.; Powell, A. K. Cryst. Growth Des. 2009, 9, 1577. (c) Liu, H.-Y.; Wu, H.; Ma, J.-F.; Liu, Y.-Y.; Liu, B.; Yang, J. Dalton Trans. 2011, 40, 602. (8) (a) Yang, J.; Ma, J.-F.; Liu, Y.-Y.; Ma, J.-C.; Batten, S. R. Inorg. Chem. 2007, 46, 6542. (b) He, Y.-C.; Yang, J.; Yang, G.-C.; Kan, W.-Q.; Ma, J.-F. Chem. Commun. 2012, 48, 7859. (c) Song, S.-Y.; Song, X.-Z.; Zhao, S.-N.; Qin, C.; Su, S.-Q.; Zhu, M.; Hao, Z.-M.; Zhang, H.-J. Dalton Trans. 2012, 41, 10412. (d) Kan, W.-Q.; Ma, J.-F.; Liu, Y.-Y.; Yang, J.; Liu, B. CrystEngComm 2012, 14, 2268. (9) (a) Zhang, Z.; Ma, J.-F.; Liu, Y.-Y.; Kan, W.-Q.; Yang, J. CrystEngComm 2013, 15, 2009. (b) Zhang, Z.; Yang, J.; Liu, Y.-Y.; Ma, J.F. CrystEngComm 2013, 15, 3843. (10) (a) Sheldrick, G. M. SHELXS-97: Programs for X-ray Crystal Structure Solution; University of Göttingen: Göttingen, Germany, 1997. (b) Farrugia, L. J. WINGX: A Windows Program for Crystal Structure Analysis; University of Glasgow: Glasgow, UK, 1988. (11) (a) Dolomanov, O. V. OLEX; http://www.ccp14.ac.uk/ccp/webmirrors/lcells/index.htm. (b) Dolomanov, O. V.; Blake, A. J.; Champness, N. R.; Schröder, M. J. Appl. Crystallogr. 2003, 36, 1283. (12) (a) Bai, H.-Y.; Ma, J.-F.; Yang, J.; Liu, Y.-Y.; Wu, H.; Ma, J.-C. Cryst. Growth Des. 2010, 10, 995. (b) Du, M.; Li, C.-P.; Liu, C.-S.; Fang, S.-M. Coord. Chem. Rev. 2013, 257, 1282. (13) (a) Cui, Y.-J.; Yue, Y.-F.; Qian, G.-D.; Chen, B.-L. Chem. Rev. 2012, 112, 1126. (b) Niu, D.; Yang, J.; Guo, J.; Kan, W.-Q.; Song, S.-Y.; Du, P.; Ma, J.-F. Cryst. Growth Des. 2012, 12, 2397. (c) Xie, Z.-G.; Ma, L.Q.; deKrafft, K. E.; Jin, A.; Lin, W.-B. J. Am. Chem. Soc. 2010, 132, 922. (d) Rocha, J.; Carlos, L. D.; Paz, F. A. A.; Ananias, D. Chem. Soc. Rev. 2011, 40, 926. (e) Eliseeva, S. V.; Bunzli, J. C. G. Chem. Soc. Rev. 2010, 39, 189. (f) Binnemans, K. Chem. Rev. 2009, 109, 4283. (g) Carlos, L. D.; Ferreira, R. A. S.; de Zea Bermudez, V.; Escribano, P. Chem. Soc. Rev. 2011, 40, 536. (h) Hwang, S. H.; Moorefield, C. N.; Newkome, G. R. Chem. Soc. Rev. 2008, 37, 2543. (14) (a) Li, S.-L.; Lan, Y.-Q.; Ma, J.-C.; Ma, J.-F.; Su, Z.-M. Cryst. Growth Des. 2010, 10, 1161. (b) Bai, H.-Y.; Ma, J.-F.; Yang, J.; Liu, Y.-Y.; Ma, J.-C. Cryst. Growth Des. 2010, 10, 995. (15) (a) Yang, J.; Li, B.; Ma, J.-F.; Liu, Y.-Y.; Zhang, J.-P. Chem. Commun. 2010, 46, 8383. (b) Chu, Q.; Liu, G.-X.; Huang, Y.-Q.; Wang, X.-F.; Sun, W.-Y. Dalton Trans. 2007, 4302. (c) Yang, J.; Yue, Q.; Li, G.D.; Cao, J.-J.; Li, G.-H.; Chen, J.-S. Inorg. Chem. 2006, 45, 2857. (16) (a) Zhang, L.-P.; Ma, J.-F.; Yang, J.; Liu, Y.-Y.; Wei, G.-H. Cryst. Growth Des. 2009, 9, 4660. (b) Kan, W.-Q.; Yang, J.; Liu, Y.-Y.; Ma, J. F. Inorg. Chem. 2012, 51, 11266.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (J.-F.M.), yangjinnenu@yahoo. com.cn (J.Y.). Fax: +86-431-85098620 (J.-F.M.). Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (Grant Nos. 21071028, 21001023, 21277022), the Science Foundation of Jilin Province (201215005, 20100109), and the Fundamental Research Funds for the Central Universities for support.

■

REFERENCES

(1) (a) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B. Chem. Rev. 2012, 112, 1001. (b) Yang, J.; Ma, J.-F.; Batten, S. R. Chem. Commun. 2012, 48, 7899. (c) Jiang, H.-L.; Tatsu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010, 132, 5586. (d) Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F. Acc. Chem. Res. 2005, 38, 217. (e) Wu, H.; Yang, J.; Su, Z.-M.; Batten, S. R.; Ma, J. F. J. Am. Chem. Soc. 2011, 133, 11406. (f) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460. (g) Batten, S. R.; Neville, S. M.; Turner, D. R. Coordination Polymers: Design, Analysis and Application; RSC Publishing: Cambridge, U.K., 2009. (h) Corma, A.; García, H.; Llabresi Xamena, F. X. Chem. Rev. 2010, 110, 4606. (i) Eliseeva, S. V.; Bunzli, J. C. G. Chem. Soc. Rev. 2010, 39, 189. (2) (a) Li, J.-R.; Sculley, J. L.; Zhou, H.-C. Chem. Rev. 2012, 112, 869. (b) Jiang, H.-L.; Tatsu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010, 132, 5586. (c) Inokuma, Y.; Kawano, M.; Fujita, M. Nat. Chem. 2011, 3, 349. (d) Wei, L. L.; Jagadese, J. V. Chem. Rev. 2011, 111, 688. (e) Cook, T. R.; Zheng, Y.-R.; Stang, P.-J. Chem. Rev. 2013, 113, 734. (f) Barry, N. P. E.; Abd Karim, N. H.; Vilar, R.; Therrien, B. Dalton Trans. 2009, 10717. (g) Demessence, A.; Horcajada, P.; Serre, C.; Boissiere, C.; Grosso, D.; Sanchez, C.; Ferey, G. Chem. Commun. 2009, 7149. (h) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D. W. Chem. Rev. 2012, 112, 782. (i) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Ferey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232. (3) (a) Ling, Y.; Deng, M.-L.; Chen, Z.-X.; Xia, B.; Liu, X.-F.; Yang, Y.T.; Zhou, Y.-M.; Weng, L.-H. Chem. Commun. 2013, 49, 78. (b) Minyoung, Y.; Renganathan, S.; Kimoon, K. Chem. Rev. 2012, 112, 1196. (c) O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem. Res. 2008, 41, 1782. (d) Grünker, R.; Bon, V.; Heerwig, A.; Klein, N.; Stoeck, U.; Baburin, I. A.; Mueller, U.; Senkovska, I.; Kaskel, S. Chem.Eur. J. 2012, 18, 13299. (e) Farha, O. K.; Eryazici, I.; Jeong, N. C.; Hauser, B. G.; Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. Q.; Nguyen, S. T.; Yazaydin, A. Ö .; Hupp, J. T. J. Am. Chem. Soc. 2012, 134, 15016. (f) Hannon, M. J. Chem. Soc. Rev. 2007, 36, 280. (g) Vajpayee, V.; Song, Y.-H.; Jung, Y.-J.; Kang, S.-C.; Kim, H.; Kim, I. S.; Wang, M.; Cook, T. R.; Stang, P. J.; Chi, K.-W. Dalton Trans. 2012, 41, 3046. (h) Jayaramulu, K.; Narayanan, R. P.; George, S. J.; Maji, T. K. Inorg. Chem. 2012, 51, 10089. (i) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105. (4) (a) Kitagawa, S.; Kitaura, R.; Noro, S. I. Angew. Chem., Int. Ed. 2004, 43, 2334. (b) Wu, H.; Liu, H.-Y.; Liu, Y.-Y.; Yang, J.; Liu, B.; Ma, J.-F. Chem. Commun. 2011, 47, 1818. (c) Zheng, S.-T.; Zhang, J.; Li, X.-X.; Fang, W.-H.; Yang, G.-Y. J. Am. Chem. Soc. 2010, 132, 15102. (d) Guo, J.; Ma, J.-F.; Li, J.-J.; Yang, J.; Xing, S.-X. Cryst. Growth Des. 2012, 12, 6074. (e) Sudik, A. C.; Côté, A. P.; Wong-Foy, A. G.; O’Keeffe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. 2006, 45, 2528. (f) Dinca, M.; Long, J. R. J. Am. Chem. Soc. 2007, 129, 11172. (g) Bain, R. L.; Shriver, D. F.; Ellis, D. E. Inorg. Chim. Acta 2001, 325, 171. (h) Lee, S. J.; Hupp, J. T. Coord. Chem. Rev. 2006, 250, 1710. (i) Chand, D. K.; Biradha, K.; Fujita, M.; Sakamoto, S.; Yamaguchi, K. Chem. Commun. 2002, 2486. (5) (a) Xie, Y.-P.; Ma, J.-F.; Yang, J.; Su, Z.-M. Dalton Trans. 2010, 39, 1568. (b) Tranchemontagne, D. J.; Mendoza Cortes, J. L.; O’Keeffe, M.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1257. (c) Zhang, J.; Chen, Y.-B.; Chen, S.-M.; Li, Z.-J.; Cheng, J.-K.; Yao, Y.-G. Inorg. Chem. 2006, 45, K

dx.doi.org/10.1021/cg400680r | Cryst. Growth Des. XXXX, XXX, XXX−XXX