Metal(II) Coordination Polymers Derived from Bis-pyridyl-bis-amide

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Metal(II) Coordination Polymers Derived from Bis-pyridyl-bis-amide Ligands and Carboxylates: Syntheses, Topological Structures, and Photoluminescence Properties Yun Gong,†,‡ Jian Li,‡ JianBo Qin,‡ Tao Wu,‡ Rong Cao,*,† and JingHua Li‡ †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China ‡ Department of Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, People's Republic of China

bS Supporting Information ABSTRACT: Using bis-pyridyl-bis-amide ligands N,N0 -bis(4-pyridyl)phthalamide (L1), N,N0 -bis-(4-pyridyl)iso -phthalamide (L2), hexanedioic acid bis-pyridin-4-ylamide (L3), and carboxylates, six metal(II) complexes formulated as Cd2(1, 4-chdc)(L1)2 3 4H2O (1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid) (1), Cd2(L1)2(in)4 3 3DMF (Hin = isonicotinic acid) (2), Zn(L1)(1,4-bdc) (1,4-H2bdc = 1,4-benzenedicarboxylic acid) (3), Cd(L2)(1,4-chdc) (4), Zn2(L2)2(tdc)2 3 DMF (H2tdc = thiophene-2,5-dicarboxylic acid) (5), and Zn(2,6-ndc)0.5(L3)0.5(SO4) 3 (CH3NHCH3) (2,6-H2ndc = 2,6-naphthalenedicarboxylic acid) (6) have been hydro(solvo)thermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a uninodal 6-connected noninterpenetrated three-dimensional (3D) network with {44.610.8}-mab topology, complex 2 exhibits a uninodal 6-connected 2-fold interpenetrated 3D framework with {412.63}-pcu topology, complex 3 shows a uninodal 8-fold interpenetrated 3D diamondoid framework, complexes 4 and 5 possess similar uninodal 2D layer with 44sql topology, and complex 6 shows a framework of 2D f 3D inclined polycatenation based on 44-sql layer. The six complexes show different thermal stability and photoluminescence properties. The emission band of complex 1 becomes strong after dehydration, and water can reduce the emission intensities of the six complexes to some extents.

’ INTRODUCTION The design and syntheses of metalorganic frameworks (MOFs) are of great current interest not only for their potential applications in sorption, electrical conductivity, smart optoelectronics, magnetism, and catalysis but also for their intriguing variety of architectures and fascinating new topologies.1,2 Although large numbers of coordination polymers with interesting structures and excellent properties have been widely reported in recent years, it is still a great challenge to exactly predict structures and compositions of MOFs built by coordination bonds and/or supramolecular contacts because very small tuning factors can dramatically change the framework structure.3,4 Of all of these factors, the organic ligand plays a crucial role. The structural change of the ligand such as the angle, distance, and relative orientation of the donor or functional groups can result in the variation of the coordination framework.5 Therefore, utilizing similar or isomeric ligands to construct MOFs is considered to be an effective way to investigate the influence of organic ligand on the structure. In recent years, the two-ligand assembly system has been widely adopted for the generation of new complexes.6,7 However, because of the complexity and difficult prediction of the resulting composition or structure, the influential principles in a twoligand system are less ascertained and not conclusive. r 2011 American Chemical Society

On the basis of the situation, in an attempt to investigate the influence of organic ligands on the structures of MOFs in twoligand systems, we synthesized three bidentate bis-pyridyl-bisamide ligands,810 N,N0 -bis-(4-pyridyl)phthalamide (L1), N,N0 bis-(4-pyridyl)iso-phthalamide (L2), and hexanedioic acid bispyridin-4-ylamide (L3) (Scheme 1). The three ligands are chosen in the present work based on the following considerations: (a) They possess similar composition, especially, and L1 and L2 are positional isomers. (b) Because of the rotation of the flexible CN single bonds in the structures, all of them possess cis- and trans-conformations (Scheme 1). (c) As N donor ligands, all of them can combine metal ions in the neutral form, and the secondary ligand, carboxylate anions can be incorporated into the metal complexes to get two-ligand system for the balance of charge. On the basis of the three ligands and five carboxylic ligands, 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc), isonicotinic acid (Hin), 1,4-benzenedicarboxylic acid (1,4-H2bdc), thiophene2,5-dicarboxylic acid (H2tdc), and 2,6-naphthalene-dicarboxylic acid (2,6-H2ndc), we got six metal(II) complexes: Cd2(1,4Received: December 1, 2010 Revised: March 6, 2011 Published: April 08, 2011 1662

dx.doi.org/10.1021/cg1016005 | Cryst. Growth Des. 2011, 11, 1662–1674

Crystal Growth & Design Scheme 1. trans- (Above) and cis- (Below) Conformations of L1 (a), L2 (b), and L3 (c)

chdc)(L1)2 3 4H2O (1), Cd2(L1)2(in)4 3 3DMF (2), Zn(L1)(1,4-bdc) (3), Cd(L2)(1,4-chdc) (4), Zn2(L2)2(tdc)2 3 DMF (5), and Zn(2,6-ndc)0.5(L3)0.5(SO4) 3 (CH3NHCH3) (6). As we know, the topological analyses of MOFs can simplify complicated frameworks of coordination polymers, and it plays an instructive role in the rational design of some predicted functional materials.11 In the present work, topological analyses reveal that the six complexes all display three-dimensional (3D) or two-dimensional (2D) frameworks with different topologies. The influence of organic ligands on the topologies of the metal(II) complexes has been discussed, and their thermal stability and photoluminescence properties have been investigated.

’ EXPERIMENTAL SECTION General Considerations. All chemicals purchased were reagent grade and used without further purification. C, H, and N elemental analyses were performed on an Elementar Vario Micro E III analyzer. IR

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spectra were recorded as KBr pellets on PerkinElmer spectrometer. Thermogravimetric analysis (TGA) was performed on a Netzsch STA 449C thermogravimetric analyzer in flowing N2 with a heating rate of 10 C min1. The powder X-ray diffraction (PXRD) data were collected on a Rigaku DMAX2500PC diffractometer using Cu KR radiation. The UVvis absorption spectra were recorded on a PE Lambda 900 UVvisible spectrophotometer in the region from 190 to 800 nm at room temperature. Solid-state photoluminescent spectra of all of the compounds were measured at room temperature with an Edinburgh FLS920 fluorescence spectrometer. The instrument is equipped with an Edinburgh Xe900 xenon arc lamp as the exciting light source. Synthesis of C18H14O2N4 (L1). The L1 ligand was prepared according to the literature method.8 Elemental anal. found: C, 67.83; H, 4.51; N, 17.53%. Calcd for C18H14O2N4: C, 67.92; H, 4.40; N, 17.61%. IR (cm1): 3049 (s), 1948 (m), 1696 (s), 1600 (s), 1509 (s), 1417 (s), 1205 (s), 1119 (s), 1060 (m), 1021 (s), 1001 (s), 891 (s), 825 (s), 725 (s), 606 (s), 544 (s). Synthesis of C18H14O2N4 (L2). Compound L2 was prepared according to the literature method.9 Elemental anal. found: C, 68.02; H, 4.50; N, 17.88%. Calcd for C18H14N4O2: C, 67.92; H, 4.40; N, 17.61%. IR (cm1): 3234 (s), 1950 (w), 1684 (s), 1600 (s), 1509 (s), 1415 (s), 1329 (s), 1290 (s), 1207 (s), 1073 (s), 995 (s), 828 (s), 715 (s), 580 (m), 539 (m). Synthesis of C16H18O2N4 (L3). Compound L3 was prepared according to the literature method.10 Elemental anal. found: C, 64.32; H, 6.01; N, 18.88%. Calcd for C16H18O2N4: C, 64.43; H, 6.04; N, 18.79%. IR (cm1): 3242 (s), 3159 (s), 2480 (m), 1954 (w), 1702 (s), 1600 (s), 1540 (s), 1418 (s), 1362 (s), 1298 (s), 1211 (s), 1171 (s), 1136 (s), 1101 (m), 1081 (m), 1055 (m), 1001 (s), 928 (m), 831 (s), 646 (m), 584 (m), 534 (s). Synthesis of Cd2(1,4-chdc)(L1)2 3 4H2O (1). A mixture of CdSO4 3 8/ 3H2O (0.05 mmol, 0.013 g), 1,4-H2chdc (0.05 mmol, 0.008 g), L1 (0.05 mmol, 0.016 g), and water (8 mL) was adjusted to pH 5.4 by NH3 3 H2O and then heated at 120 C in a Teflon-lined autoclave for 3 days, followed by slow cooling to room temperature. The resulting colorless prismatic crystals were collected (yield, ca. 40% based on Cd). Elemental anal. found: C, 49.15; H, 4.34; N, 8.85%. Calcd for C52H56Cd2N8O16: C, 49.02; H, 4.40; N, 8.80%. IR (cm1): 3429 (s), 1944 (w), 1687 (s), 1599 (s), 1512 (s), 1423 (s), 1333 (s), 1301 (s), 1263 (s), 1213 (s), 1115 (s), 1101 (m), 1018 (s), 891 (m), 833 (s), 777 (m), 715 (m), 603 (m), 535 (s). Synthesis of Cd2(L1)2(in)4 3 3DMF (2). A mixture of Cd(NO3)2 3 4H2O (0.05 mmol, 0.015 g), Hin (0.05 mmol, 0.006 g), L1 (0.05 mmol, 0.016 g), and DMF (8 mL) was heated at 120 C in a Teflon-lined autoclave for 2 days, followed by slow cooling to room temperature. The resulting colorless prismatic crystals were collected. The yield of the colorless prismatic crystals is ca. 30% based on Cd. Elemental anal. found: C, 52.89; H, 4.26; N, 13.73%. Calcd for Cd2C69H65O15N15: C, 52.84; H, 4.15; N, 13.40%. IR (cm1): 3416 (s), 1680 (s), 1593 (s), 1549 (s), 1520 (s), 1377 (s), 1334 (s), 1304 (m), 1262 (w), 1213 (m), 1119 (m), 1012 (m), 850 (m), 775 (m), 708 (m), 685 (m), 607 (w), 548 (w). Synthesis of Zn(L1)(1,4-bdc) (3). The synthesis of complex 3 was carried out as described above for complex 1 except that ZnSO4 3 7H2O and 1,4-H2bdc were used instead of CdSO4 3 8/3H2O and 1,4-H2chdc, respectively. The yield of the colorless prismatic crystals is ca. 50% based on Zn. Elemental anal. found: C, 57.13; H, 3.25; N, 10.33%. Calcd for ZnC26H18N4O6: C, 57.04; H, 3.29; N, 10.24%. IR (cm1): 3363 (s), 1934 (s), 1696 (s), 1674 (s), 1510 (s), 1429 (s), 1363 (s), 1331 (s), 1290 (s), 1209 (s), 1113 (s), 1026 (s), 887 (m), 827 (s), 744 (s), 711 (s), 669 (m), 613 (m), 521 (m). Synthesis of Cd(L2)(1,4-chdc) (4). The synthesis of complex 4 was carried out as described above for complex 1 except that Cd(NO3)2 3 4H2O and L2 were used instead of CdSO4 3 8/3H2O and L1, respectively. The yield of the colorless block crystals is ca. 30% based on Cd. Elemental anal. found: C, 52.13; H, 4.15; N, 9.38%. Calcd for CdC26H24N4O6: C, 52.00; H, 4.00; N, 9.33%. IR (cm1): 3456 (s), 1663

dx.doi.org/10.1021/cg1016005 |Cryst. Growth Des. 2011, 11, 1662–1674

Crystal Growth & Design

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Table 1. Crystal Data and Structure Refinements for Complexes 16a complex

2

3

4

5

6

empirical formula

Cd2C52H48 N8O19

Cd2C69H65O15N15

ZnC26H18 N4O6

CdC26H24 N4O6

Zn2C51H28N9O13S2

ZnC16H12 N3O7S

M

1313.80

1567.89

547.81

600.89

1169.74

455.75

crystal system

monoclinic

monoclinic

monoclinic

monoclinic

monoclinic

monoclinic

space group

P21/c

C2/c

P21/n

P21/n

C2/c

C2/c

a (Å)

12.294(1)

20.386(5)

9.589(3)

16.300(5)

29.482(1)

12.341(1)

b (Å)

16.220(2)

13.829(3)

18.861(4)

9.181(2)

9.779(3)

14.042(1)

c (Å)

13.808(2)

13.156(4)

13.288(4)

18.272(6)

18.036(7)

11.430(1)

R () β ()

90 95.703(1)

90 103.632(3)

90 106.102(3)

90 113.500(4)

90 101.689(6)

90 96.641(5) 90

γ ()

90

90

90

90

90

V (Å3)

2739.6(6)

3604.5(2)

2309.0(1)

2507.7(1)

5092(3)

1967.5(3)

Z

2

2

4

4

4

4

Dcalcd(g cm3)

1.593

1.295

1.576

1.592

1.526

1.539

μ (mm1)

0.859

0.654

1.116

0.920

1.099

1.397

no. of unique reflns

4825

3188

4067

4422

5792

3463

reflns used [I > 2σ(I)] F(000)

4055 1328

2277 1416

3081 1120

3078 1216

4706 2371

3167 924

goodness-of-fit on F2

1.039

1.315

1.000

1.042

1.099

1.116

final R indices

R1 = 0.0250,

R1 = 0.0423,

R1 = 0.0333,

R1 = 0.0332,

R1 = 0.0609,

R1 = 0.0309,

[I > 2σ(I)] a

1

wR2 = 0.0811

wR2 = 0.1808

wR2 = 0.0869

wR2 = 0.0911

wR2 = 0.1451

wR2 = 0.0836

R1 = Σ||F0| |Fc||/Σ|F0|; wR2 = Σ[w(F02 FC2)2]/Σ[w(F02)2]1/2.

1683 (s), 1604 (s), 1518 (s), 1419 (m), 1336 (m), 1296 (m), 1213 (m), 1097 (w), 1016 (m), 931 (w), 833 (m), 717 (m), 592 (w), 536 (w). Synthesis of Zn2(L2)2(tdc)2 3 DMF (5). The synthesis of complex 5 was carried out as described above for complex 2 but starting with the mixture of Zn(NO3)2 3 6H2O (0.1 mmol, 0.030 g), H2tdc (0.1 mmol, 0.017 g), L2 (0.1 mmol, 0.032 g), and DMF (8 mL). The yield of the colorless prismatic crystals is ca. 30% based on Zn. Elemental anal. found: C, 51.73; H, 3.25; N, 10.73%. Calcd for Zn2C51H39N9O13S2: C, 51.86; H, 3.31; N, 10.68%. IR (cm1): 3261 (s), 1678 (s), 1603 (s), 1513 (s), 1431 (s), 1333 (s), 1306 (s), 1209 (s), 1092 (m), 1028 (s), 933 (w), 837 (s), 773 (s), 717 (s), 660 (m), 594 (m), 536 (s). Synthesis of Zn(2,6-ndc)0.5(L3)0.5(SO4) 3 (CH3NHCH3) (6). The synthesis of complex 6 was carried out as described above for complex 2 but starting with the mixture of ZnSO4 3 7H2O (0.1 mmol, 0.029 g), 2,6H2ndc (0.1 mmol, 0.022 g), L3 (0.05 mmol, 0.015 g), and DMF (8 mL). The yield of the white prismatic crystals is ca. 30% based on Zn. Elemental anal. found: C, 41.55; H, 4.15; N, 9.13%. Calcd for ZnC16H19N3O7S: C, 41.56; H, 4.11; N, 9.09%. IR (cm1): 3516 (s), 1712 (s), 1603 (s), 1514 (s), 1396 (s), 1352 (s), 1215 (s), 1120 (s), 1028 (s), 841 (m), 789 (s), 619 (s), 555 (w). X-ray Crystallography. Single-crystal X-ray data for complexes 16 were collected on a Rigaku XCaliburE diffractometer using graphite monochromated Mo KR (λ = 0.71073 Å) radiation at room temperature. Empirical absorption correction was applied. The structures were solved by direct methods and refined by the full-matrix leastsquares methods on F2 using the SHELXTL-97 software.12 All nonhydrogen atoms were refined anisotropically. All of the hydrogen atoms were placed in the calculated positions. The solvent molecule in complex 2 was highly disordered and was impossible to refine using conventional discrete-atom models; thus, the contribution of partial solvent electron densities was removed by the SQUEEZE routine in PLATON.13 The final chemical formula was estimated from the SQUEEZE result combined with the TGA result. The crystal data and structure refinements for complexes 16 are summarized in Table 1. Selected bond lengths and angles for complexes 16 are listed in Table S1 in the Supporting Information. Further details are provided in the Supporting

Information. The CCDC reference numbers are as follows: 793329 for complex 1, 793332 for complex 2, 793330 for complex 3, 793331 for complex 4, 793333 for complex 5, and 793334 for complex 6.

’ RESULTS AND DISCUSSION Crystal Structure of Cd2(1,4-chdc)(L1)2 3 4H2O (1). Complex 1 crystallizes in the monoclinic space group P21/c, its asymmetric unit contains one Cd(II), one 1,4-chdc2, one L1, and 3.5 uncoordinated water molecules. Cd(1) is seven-coordinated by five O atoms of three carboxylate groups from three 1,4-chdc2 [CdO 2.290(2) 2.663(2) Å] and two N atoms from L1 in a pentagonal-bipyramidal coordination geometry [CdN 2.303(2) Å] with two N atoms located at the apical position (Figure 1a and Table S1 in the Supporting Information). The 1,4-chdc2 exhibits an e,a-cis-conformation (Figure 1b), and it adopts a penta-dentate coordination mode: One carboxylate group chelates one Cd(II) center, and another carboxylate group adopts a chelate/bridge tridentate coordination mode connecting two Cd(II) ions (Figure 1b). Two Cd(II) ions are linked by two chelate/bridge carboxylate groups from two 1,4chdc2 to form a Cd2 unit with a Cd 3 3 3 Cd separation of 3.808 Å. Different Cd2 units are connected by μ2-1,4-chdc2 resulting in a corrugated 2D layer (Figure 1b). In complex 1, the crystallographically independent L1 ligand exhibits a trans-conformation (Figure 1a and Scheme 1a). The dihedral angles between its phenyl ring and two pyridine rings are 136.5 and 129.7, respectively. Different 2D layers are linked by two strands of μ2-L1 ligands to form a 3D architecture. As shown in Figure 1a,b, each Cd2 unit is connected to six neighboring units through four chdc2 and two pairs of L1 ligands; thus, the Cd2 unit can be considered as a 6-connected node. Topological analysis14 reveals that it is a uninodal 6-connected noninterpenetrated network with {44.610.8}-mab topology (Figure 1c). The solvent-accessible volume of the unit cell of 1664



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Figure 1. ORTEP drawing of complex 1 with thermal ellipsoids at 30% probability (H atoms omitted for clarity), in which the 6-connected Cd2 unit is constructed by four carboxylate groups and two pairs of L1 ligands (a). Cd2 units linked by μ2-1,4-chdc2 to form 2D layer in complex 1 (H atoms and C, O atoms of L1 omitted for clarity) (b). Schematic illustrating the {44.610.8}-mab topology of the uninodal 6-connected 3D architecture in complex 1 (c). 1665



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Figure 2. 2D layer consisting of Cd(II) and in ions in complex 2 (H atoms and C, O atoms of L1 omitted for clarity) (a). 3D architecture constructed by 2D layers and L1 pillars (H atoms omitted for clarity) (b). Schematic illustrating the 2-fold interpenetrated 3D framework with {412.63}-pcu topology in complex 2 (c). 1666



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Figure 3. ORTEP drawing of complex 3 with thermal ellipsoids at 50% probability (above); the representative circuit in complex 3 constructed by six Zn(II) nodes, two (or four) L1, and four (or two) 1,4-bdc2- (H atoms omitted for clarity) (below) (a). Schematic illustrating the diamondoid topology of complex 3 (b). Schematic view of the 8-fold interpenetrated framework of complex 3 (c).

complex 1 is 381.3 Å3, which is approximately 13.9% of the unit cell volume (2739.6 Å3).15 Crystal Structure of Cd2(L1)2(Hin)4 3 3DMF (2). When Hin was introduced in place of 1,4-H2chdc, complex 2 was obtained. Complex 2 crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half independent Cd(II) atom, half L1, one in, and 1.5 uncoordinated solvent molecules. Cd(1) exhibits a slightly distorted octahedral coordination geometry, defined by two oxygen atoms from two monodentate carboxylate groups of two in [CdO 2.304(4) Å] and two N atoms from another two in in the equatorial positions and two N atoms from two L1 [CdN 2.359(5)2.390(5) Å] in the apical positions (Figure 2a and Table S1 in the Supporting Information). In complex 2, the crystallographically independent L1 ligand also shows a trans-conformation (Scheme 1a and Figure 2b), and the dihedral angles between its phenyl ring and two pyridine rings are 41.0. Cd(II) ions are linked by in to give a 2D square grid network (Figure 2a). The 2D layers are further connected by L1 ligands to form a 3D architecture (Figure 2b). If Cd(II) is defined as a 6-connected node, complex 2 exhibits a uninodal 6-connected 2-fold interpenetrated 3D

framework with {412.63}-pcu topology14 (Figure 2c). The solvent-accessible volume of the unit cell of complex 2 is 1157.3 Å3, which is approximately 32.1% of the unit cell volume (3604.5 Å3).15 As described above, L1 ligands in complexes 1 and 2 exhibit similar trans-conformation, and the two complexes are uninodal 6-connected 3D frameworks. However, complex 1 displays a noninterpenetrated mab topology, whereas complex 2 possesses a 2-fold interpenetrated pcu-network, which is a result of the different linking modes of the L1 pillars between the layers in the two complexes. In complex 1, two sets of L1 ligands along the aand b-axis cross-link the 2D layers (Figure 1c), whereas in complex 2, all of the L1 ligands are along the a-axis (Figure 2b), and the parallel connection leads to large void within the interlayer, so interpenetration is observed in complex 2. Crystal Structure of Zn(L1)(1,4-bdc) (3). When 1,4-H2bdc was used instead of Hin, we got complex 3. Complex 3 crystallizes in the monoclinic space group P21/n, and its asymmetric unit contains one Zn(II), one 1,4-bdc2, and one L1. Zn(1) exhibits a distorted tetrtahedral coordination geometry, being coordinated by two O atoms from two monodentate carboxylate 1667



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Figure 4. ORTEP drawing of Cd(L2)(1,4-chdc) (4) with thermal ellipsoids at 50% probability (H atoms omitted for clarity) (a). Corrugated 2D layer in complex 4 (H atoms omitted for clarity) (b). Schematic illustrating the 44-sql topology of complex 4 (c). 1668


Crystal Growth & Design groups of two 1,4-bdc2 [ZnO 1.935(2)1.967(2) Å] and two N atoms from L1 [ZnN 2.051(2)2.084(2) Å] (Figure 3a and Table S1 in the Supporting Information). In complex 3, the 1,4bdc2 adopts a bis-monodentate bridging coordination mode, and the L1 ligand shows a cis-conformation (Scheme 1b and Figure 3a). The dihedral angles between the phenyl ring and the two pyridine rings of L1 are 12.7 and 5.5, respectively. If Zn(II) is considered a 4-connected node, complex 3 can be regarded as a uninodal 3D diamondoid framework (Figure 3b). Eight-fold interpenetrating nets are observed in complex 3, which can be best described as two sets of a normal 4-fold net. The two sets are related to a symmetry center (i). The interpenetration vector in each set is along the a-axis. Therefore, compound 3 is regarded as a [4 þ 4] interpenetrating diamondoid system.16 A high degree of interpenetration is observed in complex 3, which is related to the coordination geometry of Zn(II) and the length of L1 ligand. Because of the entanglement, no solvent-accessible volume is found in the structure, and complex 3 is nonporous.15 Crystal Structure of Cd(L2)(1,4-chdc) (4). Compound L2 is the isomer of L1. If L1 is considered as a linear molecule, L2 can be regarded as an angular one (Scheme 1a,b). When L2 was utilized instead of L1 in the synthesis of complex 1, complex 4 was obtained. Complex 4 crystallizes in the monoclinic space group P21/n, it contains one Cd(II), one 1,4-chdc2, and one L2 in the asymmetric unit. Cd(1) exhibits a distorted octahedral coordination geometry supplied by four O atoms from two chelating carboxylate groups of two 1,4-chdc2 [CdO 2.268(3)2.443(3) Å] and two N atoms from two L2 ligands [CdN 1.94(3)2.39(2) Å] (Figure 4a and Table S1 in the Supporting Information). In complex 4, 1,4-chdc2 shows a similar e,a-cisconformation (Figure 4a) and its two carboxyate groups all chelate with Cd(II) centers. The crystallographically independent L2 ligand exhibits a cis-conformation (Figure 4a,b and Scheme 1b), and the dihedral angles between its phenyl ring and two pyridine rings are 145.2 and 31.8, respectively. As shown in Figure 4b, each Cd(II) is connected to four neighboring Cd(II) centers through two chelating 1,4-chdc2 and two μ2-L2 ligands; thus, Cd(II) can be considered as a 4-connnected node and complex 4 exhibits a uninodal corrugated 2D layer with 44-sql topology14 (Figure 4b,c). Different layers are linked by strong interlayer H bonds. For example: H1N1, 0.86 Å; H1 3 3 3 O4A, 2.139 Å; N1 3 3 3 O4A, 2.982 Å; — N1H1 3 3 3 O4A, 166.49; H2N2, 0.86 Å; H2 3 3 3 O5A, 2.094 Å; N2 3 3 3 O5A, 2.898 Å; — N2H2 3 3 3 O5A, 155.28 (atom with additional label A refers to the symmetry operations: x þ 3/2, y þ 1/2, z þ 1/2). No solvent-accessible volume is found in the structure of complex 4.15 As described above, complexes 1 and 4 are constructed by the same metal ion and carboxylate ligand except different N donor coligands. Different geometrical shapes of L1 and L2 lead to the completely different coordination modes of 1,4-chdc2 and different frameworks of the two complexes. Crystal Structure of Synthesis of Zn2(L2)2(tdc)2 3 DMF (5). In the presence of L2, if 1,4-chdc was replaced by H2tdc, we got complex 5. Complex 5 crystallizes in the monoclinic space group C2/c, and it contains one Zn(II), one tdc2, one L2, and one disordered uncoordinated DMF molecules in the asymmetric unit. Two C atoms from one pyridine ring of L2 are disordered over two locations (C17 and C170 and C18 and C180 ), and their occupancy factors are 0.8 and 0.2, respectively. Two O atoms from one carboxylate group of tdc2 are disordered over two

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Figure 5. 2D square grid framework of complex 5 (H atoms omitted for clarity).

locations (O5 and O50 and O6 and O60 ) with occupancy factors of 0.6 and 0.4. Zn(1) is disordered over three locations, and each site is 1/3 occupied. Zn(II) exhibits a distorted tetragonal pyramidal geometry supplied by two N atoms from two L2 [ZnN 1.94(3)2.208(2) Å] and three O atoms from one bridging monodentate and one chelating carboxylate groups of two tdc2 [ZnO 1.95(3)2.554(2) Å] (Figure 5 and Table S1 in the Supporting Information). The tdc2 ligand shows a tridentate coordination mode with one chelating and one bridging monodentate carboxylate groups (Figure 5). In complex 5, the crystallographically independent L2 ligand shows a transconformation (Figure 5), and the dihedral angles between its phenyl ring and two pyridine rings are 112.9 and 35.4, respectively. As shown in Figure 5, Zn(II) ions are linked by μ2-tdc2 and μ2-L2 ligands to form a 2D square grid network (Figure 5). Similar to the Cd(II) in complex 4, the Zn(II) in complex 5 can also be defined as a 4-connected node, and complex 5 displays a similar uninodal 2D layer with 44-sql topology.14 Strong interlayer H bonds are also observed. For example: H1N1, 0.86 Å; H1 3 3 3 O2A, 2.129 Å; N1 3 3 3 O2A, 2.984 Å; — N1H1 3 3 3 O2A, 172.53; H2N2, 0.86 Å; H2 3 3 3 O4A, 2.060 Å; N2 3 3 3 O4A, 2.891 Å; — N2H2 3 3 3 O4A, 162.31. The solvent-accessible volume of the unit cell of complex 5 is 678.5 Å3, which is approximately 13.3% of the unit cell volume (5092.0 Å3)15 and occupied by the disordered DMF solvent molecules. Complexes 4 and 5 show similar 2D frameworks with 44-sql topology based on different carboxylate ligands, 1,4-H2chdc and H2tdc, which is due to the similar geometrical sizes of the two carboxylate ligands and the flexibility of L2. Flexible L2 can be rotated to suitable position and angle to fit the distance between two metal(II) centers to construct gridlike layer. Compound L2 ligands exhibit cis- and trans-conformations in complexes 4 and 5, respectively. Crystal Structure of Zn(2,6-ndc)0.5(L3)0.5(SO4) 3 (CH3NHCH3) (6). Complex 6 was obtained by utilizing a more flexible ligand, L3. Complex 6 crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains two half Zn(II), one SO42, half L3, half 2,6-ndc2, and one disordered uncoordinated dimethyl amine. SO42 is disordered over two locations, and each site is half-occupied. The N atom from dimethyl amine is disordered over two locations, and each site of them has 50% occupancy. The dimethyl amine molecule comes from the decomposition of 1669



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Figure 6. 2D sql-layer in complex 6 constructed by Zn2 unit and μ2-2,6-ndc2- and μ2-L3 (a). Schematic illustration of the polycatenation in complex 6 (b). Inset: the topological links of the four-membered windows.

DMF under the solvothermal condition.17 The two half crystallographically independent Zn(II) exhibit a distorted tetrahedral coordination geometry completed by one N atom from L3 [ZnN 2.027(3)2.035(4) Å], one O from one bridging monodentate carboxylate group of 2,6-ndc2 and two O atoms from one SO42 [ZnO 1.843(13)2.129(12) Å] (Figure 6a and Table S1 in the Supporting Information). The 2,6-ndc2 links two Zn(II) centers in a bis-monodentate fashion (Figure 6a). The crystallographically independent L3 ligand shows a trans-conformation, and the dihedral angle between the two pyridine rings is 0, indicating that they are parallel (Figure 6a). Two Zn(II) ions are linked by two strands of SO42 bridges to form a Zn2 unit with a Zn 3 3 3 Zn separation of 4.538 Å. As shown in Figure 6a, each Zn2 unit is connected to four neighboring units through two 2,6-ndc2 and two L3 ligands resulting in a 2D layer. If the Zn2 unit is considered as a 4-connnected node, the 2D layer possesses a 44-sql topology,14 and the rectangular window

of the 2D motif has a dimension of ca. 13.17 19.91 Å2. Packing of the layers generates two sets of layers oriented toward the [1, 2, 1] and [1, 2, 1] direction, respectively, which is different from the parallel layers in complexes 4 and 5. In complex 6, each sheet passes through an inclined one, as shown in Figure 6b, and finally gives a 2D f 3D inclined polycatenation structure. The angle between the two sets of layers is 76.8, and the polycatenation is of the type p-p (parallelparallel).18 Further insight into one window of a sheet shows that each window is catenated with other eight windows from four different layers in the other set via Hopf links (Figure 6b).19,20 Alternatively, it can be described that each window encircles four rods passing through it (Figure 6b, inset). The p-p inclined polycatenation of sql-net was ever reported in our previous work.20a Differently, in complex 6, each window is catenated with more windows from different layers as a result of the large size of the window, which is related to the long length of L3 ligand. 1670


Crystal Growth & Design Because of the polycatenation, the solvent-accessible volume of the unit cell of complex 6 is reduced to be 398.6 Å3, which is approximately 20.3% of the unit cell volume (1967.5 Å3) and occupied by disordered solvent molecules.15 Complexes 4 and 5 possess similar 2D layer with 44-sql topology; however, complex 6 shows a 2D f 3D polycatenated architecture based on 44-sql layer. That is due to the structural differences of L2 and L3 in the three complexes. Compound L3 in complex 6 is more flexible than L2 in complexes 4 and 5, making the polycatenation possible in complex 6. Thermal Stability of the Complexes. The PXRD patterns of complexes 16 are shown in Figure S1 in the Supporting Information. All of the peaks of the six compounds can be indexed to their respective simulated PXRD patterns, which indicate that each of the six compounds is pure phase. To examine the thermal stability of the six complexes, TGAs were carried out. The samples were heated up to 900 C in N2. The TGA curve of complex 1 shows a one step weight loss of 6.3% between 30 and 130 C corresponding to the loss of the lattice water molecules (calcd 6.5 wt %). The anhydrous sample remained stable up to ∼330 C without any weight loss. Decomposition of the organic components began at 330 C, in the temperature range 330650 C with a loss of 73.3 wt % (calcd 73.1 wt %). The decomposition process ended at about 650 C. It is found that the cavity of complex 2 is occupied by three DMF molecules per unit, as estimated by SQUEEZE and TGA.13 The TGA curve of complex 2 shows a one step weight loss of 13.6% between 30 and 210 C corresponding to the loss of the uncoordinated DMF molecules (calcd 14.0 wt %). The desolvated sample remained stable up to ∼320 C without any weight loss (Figure S2b in the Supporting Information). As for complexes 3 and 4, no weight losses are observed in the temperature range of 30240 C (Figure S2c in the Supporting Information) and 30330 C (Figure S2d in the Supporting Information), respectively, which is in good agreement with crystal structures of complexes 3 and 4, in which no solvent is included. Complex 3 shows three steps of weight losses when the temperature is above 240 C (Figure S2c in the Supporting Information), corresponding to the decomposition of the organic components. Complex 4 exhibits one step weight loss of 81.0 wt % (calcd 81.3 wt %) in the range of 330650 C, corresponding to the pyrolysis of organic ligands (Figure S2d in the Supporting Information). The decomposition process of complex 4 ended at about 650 C. As for complex 5, the first weight loss of 6.5 wt % (calcd 6.2 wt %) in the range of 30240 C corresponds to the loss of solvent DMF molecules (Figure S2e in the Supporting Information). The decomposition of the organic components occurred at about 280 C. Complex 6 easily loses its uncoordinated dimethyl amine molecules at room temperature (calcd, 9.7%; observed, 9.5%). The host framework of complex 6 starts to be decomposed when the temperature is higher than 170 C (Figure S2f in the Supporting Information). UVvis Absorption Spectra and Photoluminescence Property. The UVvis absorption spectra of the free organic ligands and complexes 16 at room temperature are shown in Figure S3 in the Supporting Information. As shown in Figure S3a and Table S2 in the Supporting Information, complex 1 displays a complex absorption in the range of 200400 nm, in which three maxima at 207, 268, and 320 nm are present. As for the free ligand 1,4-H2chdc, it exhibits a peak at 209 nm in the range of

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200250 nm, which probably corresponds to the electron transition of the CdO bond.21a A similar absorption peak around 210 nm is observed for all of the other free organic ligands and the other complexes due to the existence of the CdO in the structures. The absorption of 1,4-H2chdc in the range of 250400 is weak and can be neglected. The absorption band of L1 extends from 200 to 335 nm with three peaks at 207, 245, and 300 nm. The two absorption peaks at 268 and 320 nm for complex 1 show red shifts as compared with the peaks at 245 and 300 nm for L1, respectively, indicating that they may be ascribed to the intraligand (n-π* or ππ*) transition (ILCT) of L1 or metal-to-ligand charge-transfer transition (MLCT).21 As shown in Figure S3b and Table S2 in the Supporting Information, complex 2 shows a complex absorption in the range of 200400 nm with three intense peaks at 208, 265, and 320 nm. They show red shifts as compared with those of the pure L1 (207, 245, and 300 nm) and Hin (205, 243, and 294 nm), respectively, inferring that the absorption of complex 2 originate from the ILCT, ligand-to-ligand change transfer transition (LLCT), or LMCT.21 The absorption band of complex 3 extends from 200 to 450 nm with four intense peaks at 208, 268, 320, and 357 nm, as shown in Figure S3c and Table S2 in the Supporting Information. The pure L1 and 1,4-H2 bdc also display absorption bands in the similar region. The absorption peaks at 268 and 320 nm for complex 3 show red or blue shifts as compared with those of L1 (245 and 300 nm) and 1,4-H2bdc (320 nm), respectively, indicating that they may be ascribed to the ILCT, LLCT, or MLCT. 21 The new-originated absorption peak at 357 nm for complex 3 is probably assigned to the MLCT.21 As shown in Figure S3d and Table S2 in the Supporting Information, complex 4 exhibits two intense peaks at 268 and 321 nm in the range from 220 to 400 nm, which are red-shifted as compared with the peaks of 250 and 309 nm for the free L2, indicating that they may be assigned to the ILCT of L2 or MLCT.21 Complex 5 displays a complex absorption in the range of 200385 nm with three intense peaks at 206, 253, and 302 nm (Figure S3e and Table S2 in the Supporting Information). They show red or blue shifts as compared with those of the pure L2 (200, 250, and 309 nm) and H2tdc (200, 245, and 320 nm), respectively, inferring that the absorption of complex 5 may originate from the ILCT, LLCT, or MLCT.21 Complex 6 exhibits a complex absorption in the range of 200450 nm (Figure S3f and Table S2 in the Supporting Information). Three strong transition bands at 206, 268, and 346 nm and two weak shoulder bands at 320 and 369 nm are observed. As for the free L3, the main absorption is in the range of 200325 nm with three intense peaks at 200, 228, and 258 nm. As for 2,6-H2ndc, the strong absorption is in the range of 300425 nm with one intense peak at 377 nm and two weak shoulder peaks at 320 and 358 nm. The absorption of complex 6 shows red or blue shifts as compared with those of the pure L3 and 2,6-H2ndc, indicating that the absorption of complex 6 may be assigned to the ILCT, LLCT, or MLCT.21 Coordination polymers have been reported to have the ability to adjust the emission wavelength of organic materials through incorporation of metal centers, especially for the d10 metal centers.22 So, it gives us an impetus to make an investigation 1671


Crystal Growth & Design on the luminescence properties of coordination polymers in view of potential applications as photoactive materials. The photoluminescence properties of Zn(II) or Cd(II) complexes 16, together with the L1, L2, and L3 ligands and all of the carboxylic acids, were studied in the solid state at room temperature. The emission spectra of the free organic ligands (slit width = 5 nm) are depicted in Figure S4a in the Supporting Information. Strong photoluminescence emission bands at 500 (λex = 300 nm), 492 (λex = 360 nm), and 497 nm (λex = 370 nm) are observed for free L1, L2, and L3 ligands, respectively (Figure S4a in the Supporting Information). Weak emission bands at 460 (λex = 300 nm), 448 (λex = 350 nm), and 474 nm (λex = 370 nm) are observed for free 1,4-H2chdc, Hin, and H2tdc, respectively (Figure S4a in the Supporting Information), whereas for the free 1,4-H2bdc and 2,6-H2ndc, the emission bands are very strong and exceed the experimental range of the intensity under the similar conditions (slit width = 5 nm). When the slit width is adjusted to be 2.5 nm, free 1,4-H2bdc and 2,6-H2ndc show emission bands at 440 (λex = 350 nm) and 450 nm (λex = 390 nm), respectively. The emissions of the organic ligands may be ascribed to the π* f n or π f π* transitions.23 The emission spectra of complexes 2, 3, and 4 (slit width = 5 nm) are depicted in Figure S4b in the Supporting Information. An intense emission peak of complex 2 is found at 451 nm with an excitation band at 330 nm (Figure S4b in the Supporting Information), which is blue-shifted 49 nm and red-shifted 3 nm as compared with those of the pure L1 ligand (λem = 500 nm) and Hin (λem = 448 nm) (Figure S4a-b and Table S3 in the Supporting Information). The emission spectra of complexes 3 and 4 show the emission maxima at ca. 465 nm upon excitation at 340 and 380 nm, respectively (Figure S4b in the Supporting Information). The emission peak of complex 3 is blue-shifted 35 nm and red-shifted 25 nm as compared with those of the free L1 (λem = 500 nm) and 1,4-H2bdc (λem = 440 nm), respectively. As for complex 4, it is blue-shifted 27 nm and red-shifted 5 nm as compared with those of the uncoordinated L2 (λem = 492 nm) and 1,4-H2chdc (λem = 460 nm), respectively (Table S3 in the Supporting Information). Complexes 1, 5, and 6 display strong blue photoluminescence properties, and their emission bands exceed the experimental range of the intensity under the similar conditions (slit width = 5 nm). When the slit width is adjusted to be 2.5 nm, complexes 1, 5, and 6 exhibit emission bands at 450 (λex = 340 nm), 462 (λex = 350 nm), and 445 nm (λex = 350 nm), respectively (Figure S4c in the Supporting Information). They are blue- or red-shifted as compared with the pure organic ligands, as shown in Table S3 in the Supporting Information. As for the d10 valence electron configuration of the Zn(II) or Cd(II) ion, the emission band of the Zn(II) or Cd(II) complexes may be assigned to the LLCT, admixing with MLCT and LMCT.24 The results are in agreement with the absorption spectra of the complexes. The enhancement of luminescence in complexes 1, 5, and 6 may be attributed to the ligation of the ligand to the metal center, which enhances the rigidity of the ligand and reduces the loss of energy through a radiationless pathway.25 As described above, the emission spectra of complexes 16 are different from each other, which is due to the different coordination modes of organic ligands and their different structures. Among the six as-synthesized complexes, except complexes 3 and 4, the other four complexes all contain guest or lattice solvent molecules in the structures. To preliminarily investigate the effect

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of water on the photoluminescence property of MOF, complex 1 is dehydrated at 50 C for 56 h before the measurement of emission spectrum. According to the TG analysis of complex 1, partial uncoordinated water molecules can be removed from complex 1 at 50 C without destroying the host framework of the complex. It is observed that the emission band of dehydrated complex 1 becomes stronger than that of complex 1. Guestresponsive photoluminescent properties of some MOFs have ever been reported,26 the phenomenon in our experiment is in agreement with the previous work.26 In the further investigation, it is found if complexes 3 and 4 are kept in humid air for 23 days before the measurement of emission spectra, the emissions of the hydrated complexes 3 and 4 become weak. As we know, complexes 3 and 4 are nonporous, and water cannot enter the lattice of the complexes. It is expected that the water from the humid air can be adsorbed on the surface of complexes 3 and 4, which would lead to energy loss and reduce the emission intensities of the samples. After the hydrated complexes 3 and 4 are dried at 50 C for 56 h, the intensities of the emission bands of complexes 3 and 4 can be recovered. Similarly, when the other complexes are kept in humid air for several days, it is observed that the emissions of the complexes have been weakened to some extents.

’ CONCLUSION In conclusion, using bis-pyridyl-bis-amide ligands, L1, L2, L3, and carboxylates, six Cd(II) or Zn(II) complexes have been hydro(solvo)thermally synthesized and structurally characterized by single-crystal XRD. Complex 1 is a noninterpenetrated 3D network with {44.610.8}-mab topology, complex 2 exhibits a 2-fold interpenetrated 3D framework with {412.63}-pcu topology, complex 3 shows an 8-fold interpenetrated 3D diamondoid framework. Complexes 4 and 5 possess similar 2D layer with 44sql topology, and complex 6 shows a framework of 2D f 3D inclined polycatenation based on 44-sql layer. In complexes 1 and 2, L1 exhibits a similar trans-conformation, whereas in complex 3, it displays a cis-conformation. In complexes 4 and 5, L2 presents a cis- and trans-conformation, respectively. In complexes 1 and 4, 1,4-chdc2 exhibits a similar e,a-cis-conformation. The present work shows that subtle differences of the organic ligands have great influence on the topologies of the metal(II) complexes and their thermal stability and photoluminescence properties. The emission band of dehydrated complex 1 becomes strong than that of complex 1, and water can quench the emissions of the six complexes to some extents. ’ ASSOCIATED CONTENT

bS

Supporting Information. Crystallographic data and PXRD patterns and other supporting information. This material is available free of charge via the Internet at http://pubs.acs.org.

’ ACKNOWLEDGMENT Financial support from the 973 Program (2011CB932504 and 2007CB815303), NSFC (20731005, 20821061, and 91022007), the Chongqing University Postgraduate Science (No. CDJXS10 22 11 43), and the Fundamental Research Funds for the Central Universities (No. CDJZR10 22 00 09) are gratefully acknowledged. 1672



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