Tuning Structural Topologies of a Series of MetalâOrganic

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Tuning Structural Topologies of Series of Metal -Organic Frameworks: Different Bent Dicarboxylates Ling Qin, Jinsong Hu, Ming-Dao Zhang, Qingxiang Yang, Yizhi Li, and Hegen Zheng Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400180j • Publication Date (Web): 01 Apr 2013 Downloaded from http://pubs.acs.org on April 11, 2013

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Crystal Growth & Design

Tuning

Structural

Topologies

of

Series

of

Metal−Organic

Frameworks: Different Bent Dicarboxylates

Ling Qin, Jinsong Hu, Mingdao Zhang, Qingxiang Yang, Yizhi Li, and Hegen Zheng∗

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China.

ABSTRACT: Five new metal-organic frameworks incorporating the angular tetratopic ligand with different transition metal ions and bent co-ligands have been synthesized: [Zn4(L)2(4,4'-sdb)4(H2O)2]·3H2O (1), [Zn2(L)2(hfipbb)2(H2O)3] (2), [Zn(L)(oba)]·H2O (3), [Cd2(L)2(4,4'-sdb)2]·2H2O (4), [Cd2(L)(hfipbb)(H2O)3]·2H2O (5), [L = 1,1'-oxybis[3,5-dipyridine-benzene, 4,4'-H2sdb = 4,4'-sulfonyldibenzoate, H2hfipbb

=

4,4'-(hexafluoroisopropylidene)bis(benzoic

acid),

H2oba

=

4,4'-

oxybis(benzoate)]. Structural analysis reveals that the mixed ligands display versatile coordination modes to manage the metal ions to form homochiral, inclined polycatenation (1D→2D), 3-fold interpenetrating nets. However, the different coordinated modes, geometry and flexibility of ligands around metal ions result in subtle differences in the final architecture. Bulk materials for 1 and 3 have a secondharmonic generation activity, approximately 0.4 and 0.8 times that of urea.

Introduction Metal-organic frameworks (MOFs) are a subset of new solid matierials, which

ACS Paragon Plus Environment


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proved to have many potential applications, such as, catalysis, optical, ferroelectricity, magnetic, solvatochromic, and separations.1 Previously, numerous metal-organic networks based on rigid organic linkers are reported.2 The assemblies of coordination polymers from flexible linkers are considerably attracting the attention of chemists, which is attributed to that they would likely offer new structures and consequently some potential for the design and synthesis of functional materials.3 The structures of coordination polymers are dependent upon a variety of factors such as the geometrical and electronic properties of the metal centers, solvent, the coordinative abilities of the ligands, the ligand-to-metal stoichiometry, and the synthesis methods of crystal growth.4 In particular, different conformations of the ligand often play an important role in the self-assembly processes to form metalorganic coordination polymers with different structures. Recently, we reported a neutral tetradentate non-rigid ligand, 1,1'-oxybis[3,5-dipyridine-benzene] (L) (Scheme

1).5

By

introduction

sulfonyldibenzoate(4,4'-H2sdb),6

of

different

bent

co-ligands,

4,4'-

4,4'-(hexafluoroisopropylidene)bis-(benzoic

acid)(H2hfipbb),7 4,4'-oxybis(benzoate)(H2oba),

8

a remarkable range of materials

containing various architectures can be prepared. Compared to the reported terephthalic, 1,4-cyclohexanedicarboxylic and 1,3,5trimesic acid as co-ligands, the V-shaped ligands (in which the two benzene rings are not coplanar) may induce the helicity or flexuousity of the polymeric chains, which may generate chiral compounds.9 Although some 3D chiral framework materials in the past several decades have been reported,10 homochiral MOFs with bulk homochirality are not many. 11 The synthesis method for homochiral MOFs prepared from achiral raw materials would offer some benefits since chiral raw materials are expensive. Homochiral materials are useful for many important applications as


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enantioselective separation, nonlinear optics, catalysis, and sensor technology.12

Scheme 1. The Neutral Tetradentate N-containing Ligand and Bent Carboxylate Coligands

Experimental Section Materials and Methods. All chemicals and solvents used in the syntheses were of reagent grade and were used without further purification. H2hfipbb, 4,4'-H2sdb, and H2oba were used as commercially available. L ligand was prepared on the basis of palladium-catalyzed cross-coupling reactions. The IR absorption spectra of these complexes were recorded in the 400 – 4000 cm-1 range by means of a Nicolet (Impact 410) spectrometer with dry KBr pellets. C, H and N elemental analyses were performed on a Perkin Elmer 240C elemental analyzer. Powder X-ray diffraction (PXRD) measurements were carried out with a Bruker D8 Advance X-ray diffractometer using Cu-Kα radiation (1.5418 Å), and the X-ray tube was operated at 40 kV and 40 mA. Luminescent spectra were recorded with a SHIMAZU VF-320 X-



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ray fluorescence spectrophotometer at room temperature. A pulsed Q-switched Nd:YAG laser at a wavelength of 1064 nm was used to generate a SHG signal. The backscattered SHG light was collected by a spherical concave mirror and passed through a filter that transmits only 532 nm radiation. The circular dichroism (CD) spectra were recorded at room temperature with a Jasco J-810(S) spectropolarimeter (KBr pellets).

Syntheses of the compounds Synthesis of complex 1: Single crystals of 1 - 5 were prepared in the same hydrothermal procedure, and thus only the compound 1 will be discussed here, the others are listed in the Supporting Information. A mixture of DMF/H2O/CH3CN containing the L (47.8 mg, 0.1 mmol), 4,4'-H2sdb (30.6 mg, 0.1 mmol) and Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol) was placed in a Teflon vessel within the autoclave. The vessel was heated at 95 °C for 3 days and then cooled to room temperature. The colourless blocks crystals were obtained and crystals were filtered off, washed with quantities of distilled water and dried under ambient conditions. Yield of the reaction was caculated 55% based on the L ligand. Anal. Calcd for C120H86N8O31S4Zn4: C, 57.06%, H, 3.43%, N, 4.44%; found C, 56.98%, H, 3.44%, N, 4.40%. The IR spectra of the corresponding complexes are shown in the Supporting Information (Figures S1-S5).

X-ray Crystallography. Crystallographic data of 1-5 were collected on a Bruker Apex Smart CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) using the ω-scan technique. The diffraction data were integrated by using the SAINT program.13 Semiempirical absorption correction was carried by using the SADABS program.14 The structures were solved by direct methods and all non-


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hydrogen atoms were refined anisotropically on F2 by the full-matrix least-squares technique using the SHELXL-97 crystallographic software package. The positions of the non-hydrogen atoms were refined with anisotropic displacement factors. The hydrogen atoms were positioned geometrically by using a riding model. The contribution of the electron density by the remaining disorder solvent molecule in the channels of 1 and 4 was removed by the SQUEEZE routine in PLATON.

15

The

structures were examined using the Addsym subroutine of PLATON to ensure that no additional symmetry could be applied to the models. The numbers of solvent molecules in compounds 1 and 4 were obtained by element analyses. Details of the crystal parameters, data collection and refinements for 1-5 are summarized in Table 1. More details are provided in the Supporting Information.

Results and Discussion Crystal Structure of [Zn4(L)2(4,4'-sdb)4(H2O)2]·3H2O (1). Single-crystal X-ray structural analysis reveals that the structure of 1 crystallized in the monoclinic system with the acentric space group Cc. In the crystal structure, the Flack parameter is 0.083 with esd 0.008. As shown in Figure 1a, the asymmetric unit contains four crystallographically unique Zn atoms, two L ligands, four 4,4'-sdb ligands, two coordinated water molecules, and three lattice water squeezed by PLATON. Zn2, Zn3 and Zn4 atoms are five coordinated. Zn1 displays a distorted octahedral coordination. Zn1 is bonded to four O atoms (three O from two carboxylate groups and one from water molecule) and two N atoms of L ligands. Zn3 ion is surrounded by three carboxylate O atoms from two carboxylate groups, one N atom from L ligand, and one water oxygen atom. The L ligands link the Zn cations to form a 1D chain with Zn2L1/2 ring staggering vertically (Figure 1b). Then the 4,4'-sdb ligands connect these 1D chains to generate a 3D framework (Figure 1c). Better insight into such an



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intricate framework can be accessed by reducing multidimensional structures to simple node and connecting nets via TOPOS analysis software.16 One L connects to four Zn cations, the other only links three Zn cations. Besides, Zn3 is acted as a three connected node, Zn1, Zn2, Zn4 are all four connected. Accordingly, the 3D complex framework of 1 can be simplified to a 6-nodal 3,3,4,4,4,4-c topology (with the schläfli symbol {3.102.112.12}{3.102}{3.4.5.102.11}2{3.4.5.112.12}{3.4.5}).

(a)

(b)

Figure 1. (a) Coordination environment of 1 with 30% ellipsoid probability (hydrogen atoms and solvent molecules are omitted for clarity). Symmetry code: #1 = x, 1 - y, -0.5 + z.; #2 = -0.5 + x, 1.5 - y, -0.5 + z.; #3 = 0.5 + x, -1.5 - y, 0.5 + z.; (b)


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A view of 1D chain formed by Zn centers and L ligands; (c) Schematic representation of 3D framework of compound 1; (d) Schematic view of the topology of structure 1.

Crystal Structure of [Zn2(L)2(hfipbb)2(H2O)3] (2). X-ray diffraction analysis shows that complex 2 features an (1D + 1D→2D) inclined polycatenated framework with two sets of equivalent chains. Compound 2 crystallizes in a monoclinic system with space group C2/c. As shown in Figure 2a, the framework of 2 consists of one Zn2+ ion, one L ligand, one hfipbb ligand, and one and a half free water molecules. Zn1 cation is five-coordinated and coordinated by three carboxylate oxygen atoms from two different hfipbb ligands [Zn−O bond lengths varying from 1.998(4) to 2.425(3) Å], two N atoms from two L ligands [Zn−N bond lengths varying from 2.060(4) to 2.075(4) Å], the τ trigonality factor is 0.434, indicating that the geometry around the zinc is nearly in between the square pyramidal and trigonal bipyramidal geometry. The long bond (Zn1-O2) is included as a part of the coordination environment around Zn1 to achieve bond valence sums closer to the value of 2 expected for Zn2+. 17 The L and hfipbb ligands link Zn ions to form 1D chains. As shown in Figure 2b, the red chains lies at an inclined angle and interlocks with the blue one, to give an overall 2D entanglements, with an angle of 63.1°. 18 The 1D + 1D→2D polycatenated framework is further stabilized by hydrogen-bonding interactions.



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Figure 2. (a) Coordination environment of the Zn(II) ions in 2 (hydrogen atoms and solvated molecules are omitted for clarity), symmetry codes: #1 = -1/2 + x, -1/2 + y, z.; #2 = -x, -y, -z+1.; (b) Schematic view of 1D chain of 2; (c) 1D + 1D→2D inclined polycatenated framework of 2. Crystal Structure of [Zn(L)(oba)]·H2O (3). A single-crystal XRD study has revealed the 3D structure of 3 is built from homochiral helices and crystallizes in the P65 space group. The asymmetric unit consists of one Zn (II) cation, one L molecule, one oba ligand and one lattice water molecule (Figure 3a). The carboxylate groups of oba anions linked Zn centers to form one 65 helix. Besides, two coordinated pyridine groups of the L ligand also connected adjacent Zn cations to generate the other helical chain (Figure 3b). Each double-stranded 65 helices is further connected to six


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adjacent helix chains through the oba anions into a 3D framework (Figure 3c). As shown in Figure 3d, the helical channel was occupied by another two uncoordinated pyridyl groups of the L ligands. In addition, the water molecules in the channel also arranged in a helical chain, attributed to the H-bond interaction between the uncoordinated N atoms and the lattice water. The whole structure can be represented as a 4-c net qtz topology with the Schläfli symbol {64.82}. Because of the spacious nature of a single network, it allows another two independent identical networks to penetrate it in a normal mode, thus giving a three fold interpenetrated architecture (Figure 3e).



Figure 3. (a) Coordination environment of 3 with 30% ellipsoid probability (hydrogen atoms and water molecules are omitted for clarity). Symmetry code: #1 = - 1 + y, 1 - x + y, 1/6 + z.; (b) View of coaxial double-stranded helical chains along the b axis; (c) View of helical chains possessing 65 screw axis along the c axis; (d) A perspective of 3D framework along the c axis with 1D helical channels occupied by the uncoordinated pyridyl groups of the L ligands (guest H2O molecules are omitted); (e) Schematic representation of three fold interpenetrating framework with qtz topology.

Crystal Structure of [Cd2(L)2(4,4'-sdb)2] · 2H2O (4). The single-crystal X-ray diffraction study reveals that 4 have a 1D polymeric structure crystallizing in 1

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triclinic space group P . In the framework of 1, the asymmetric unit consists of one Cd(II) cation, one L1, one 4,4'-sdb ligand and two halves of solvent water (Figure 4a). Three pyridine groups of L ligand link three Cd ions to form a 1D chain. The 4,4'-sdb ligand also connect the Cd cations to generate a flexuous chain, however, the introduction of the 4,4'-sdb ligand does not increase the dimension of the structure (Figure 4b).


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Figure 4. (a) Coordination environment of 4 with 30% ellipsoid probability (hydrogen atoms and water molecules are omitted for clarity). Symmetry code: #1 = - x, 2 - y, - z.; #2 = - x, 2 - y, 1 - z.; #3 = 1.5 + x, 1.5 - y, 0.5 + z.; #4 = x, y, - 1 + z.; (b) Perspective of 1D chain. Crystal Structure of [Cd2(L)(hfipbb)2(H2O)3]·2H2O (5). X-ray analysis reveals that 5 crystallizes in a monoclinic system with a space group P21/n and is composed of two Cd cations, two L ligands, two hfipbb, three coordinated water, and two solvent water molecules (Figure 5a). Cd1 cation is seven-coordinated while Cd2 cation is six-coordinated. Cd1 is coordinated by four carboxylate oxygen atoms from two different hfipbb ligands, two N atoms from two L ligands, and one O atom from water molecule. The Cd2 center is six-coordinated in a distorted octahedral environment. The equatorial plane is defined by one monodentate carboxylate group, three water oxygen atoms; two N atoms occupy the axial positions of the octahedron. One carboxylate group of one hfipbb serving as terminal ligands takes µ3-chelatingbridging tridentate mode, and the other carboxylate anion does not coordinate. The other hfipbb is wholly deprotonated, and the carboxylate groups adopt chelating in a bidentate and monodetate mode, respectively. Two carboxylate groups from two symmetry-related hfipbb ligands connect two Cd (II) cations to a dinuclear [Cd2(CO2)4] subunit, and the Cd···Cd distance is 3.947 Å. The Cd-N and Cd-O bond lengths are all within the normal ranges. The potential voids are large enough to be



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filled via mutual interpenetration of two independent equivalent frameworks, generating a 3-fold interpenetrating 3D architecture. The interpenetration can be classified as type Class Ia, Z = 3 (Zt=3; Zn=1) (Figure 5c). To better understand the nature of this intricate framework, topology analysis is provided: the [Cd2(CO2)4] binuclear and Cd2 cations can be regarded as six and three connected nodes, respectively. And the L ligands act as a 4-connected node. Therefore, the whole structure can thus be represented as a 3, 4, 6-c net topology (with the Schläfli symbol {3.4.5.72.8}2{3.72}2{32.42.52.74.82.93}).

Figure 5. (a) Coordination environment of the Cd (II) ions in 5 (hydrogen atoms and sovent molecules are omitted for clarity, 30% ellipsoid probability), symmetry codes: #1 = - x, 2 - y, - z.; #2 = - x, 2 - y, 1 - z.; #3 = 1.5 + x, 1.5 - y, 0.5 + z.; #4 = x, y, -1 + z.


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(b) Schematic view of 3D framework. (c) Toplogically schematic representation of three fold interpenetrating 3D structure.

Structural Discussion. It is noteworthy that various dimensional architectures can be achieved on the basis of the choice of the bent dicarboxylate as spacers and the metal ions. The coordination with V-shaped dicarboxylates and metal centers can furnish one-dimensional nonlinear flexuous chains in 1, 2, 4 or helical chains such as in 3 (Scheme S1). The most critical factor for the formation of chains is presumed to be the geometry and flexibility of the dicarboxylate ligand (Table S1). Considering the MOFs 1-3, in this series of nets, along with the variation of the V-shape ligand, their network arrays are changed from a 3D 6-nodal topology to an inclined polycatenation (1D→2D) and a 3-fold interpenetrating homochiral net. In addition, the choice of metal centers also plays a significant role on the binding fashions of the carboxylate as well as the resultant networks of MOFs.

Second Harmonic Generation Response and Circular dichroism Spectrum Since complexes 1 and 3 crystallize in the acentric or chiral space groups, the optical properties were investigated. Preliminary studies of a powdered samples for 1 and 3 indicate that they are SHG active, with the SHG efficiencies are approximately 0.4 and 0.8 times that of urea. Furthermore, the solid-state CD spectrum of 3 exhibits an obvious positive Cotton effect (Figure 6), suggesting the entire bulk samples are the same handed conformation. 19



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Figure 6. The solid-state CD spectra of bulk samples of 3.

Luminescent Properties and PXRD analyses. The coordination polymers with d10 metal centers have been investigated for fluorescence properties with many potential applications. The photoluminescence spectra of complexes 1-5 and the L ligand were examined in the solid state at room temperature (Figure S6). Emissions of the ligand were observed with wavelength at 393 nm in L (λex= 356 nm), which could be attributed to the π*–π transitions. The emission peaks at 410 nm in 1 (λex= 350 nm), 370 nm in 2 (λex= 350 nm), 460 nm in 3 (λex= 380 nm), 367 nm in 4 (λex= 330 nm), and 393 nm in 5 (λex= 340 nm). All complexes are similar to that of the ligand, assigned to the intraligand fluorescent emissions. 20 The emission bands of complexes 2 and 4 are blue-shifted as compared with that of the ligand, which can be attributed to the reduced degree of π electron overlap of the organic linkers. The differences in the band positions of these coordination polymers might be related to the differences in the metal centers and coordination environments. The PXRD experimental and computer-simulated patterns of the corresponding complexes 1-5 are shown the Supporting Information (Figures S7-S11). The results demonstrate that the experimental PXRD patterns match the simulated one based on the single-crystal Xray data. The thermal decompositions of these compounds were also carried out to examine the thermal stabilities (Figure S12).


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Conclusion In this paper, we present a new family of metal-organic frameworks generated from mixed-ligand systems of N-donor tetratopic ligand and various bent co-ligands. The different coordination modes and different disposition of the ligands result in subtle differences in the final architecture. The bent ligand has the potential of generating homochiral metal-carboxylate helical chains when it reacts with metal ions. Furthermore, both 1 and 3 are NLO-active materials. Further studies are directed toward the design of other MOFs.

■ASSOCIATED CONTENT Supporting Information Crystallographic data in CIF format, selected bond lengths and angles, and patterns of photochemistry, IR and PXRD. This information is available free of charge via the Internet at http://pubs.acs.org. ■AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (H. Z.). Fax: 86-25-83314502. Nanjing University

■ ACKNOWLEDGMENTS This work was supported by grants from the Natural Science Foundation of China (Nos. 91022011; 20971065; 21021062), National Basic Research Program of China (2010CB923303). References (1) (a)Yu, J.; Cui, Y.; C.; Yang, Y.; Wang, Z.; O' Keeffe, M.; Chen, B.; Qian, G. Angew. Chem. Int. Ed. 2012, 51, 10542. (b) Ameloot, R.; Vermoortele, F.; Hofkens, J.; De Schryver, F. C.; De Vos, D. E.; Roeffaers, M. B. J. Angew. Chem.



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Table 1. Crystal data and structure refinements parameters of complexes 1-5 Complex

1[a]

2

3

4[a]

5

Formula

C98H66F12N8O13Z n 1922.33

C46H32N4O7Z n 818.13

C92H62Cd2N8O15 S 1808.42

C66H43Cd2F12N4O

Mr

C120H80N8O28S4Z n 2471.64

Cryst syst

monoclinic

monoclinic

hexagonal

triclinic

monoclinic

Space group

Cc

C2/c

P6(5)

a (Å)

23.6644(17)

14.754(2)

13.5717(12)

13.2457(8)

13.821(9)

b (Å)

14.9473(13)

24.039(3)

13.5717(12)

13.2560(7)

32.91(2)

c (Å)

32.9534(16)

25.304(3)

37.332(7)

15.0285(15)

14.903(10)

α (°)

90.00

90.00

90.00

91.851(1)

90.00

β (°)

93.185(3)

101.283(3)

90.00

102.530(1)

112.939(10)

γ (°)

90.00

90.00

120.00

119.010(1)

90.00

11638.2(14)

8801.1(19)

5955.0(13)

2223.3(3)

6243(7)

4

4

6

1

4

1552.84

1

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Page 20 of 21

3

V (Å ) Z -3

ρcaled (g cm )

P

P2(1)/n

1.411

1.451

1.369

1.351

1.652

-1

µ (mm )

0.965

0.640

0.677

0.592

0.786

F (000)

5056

3928

33536

918

3100

rflns collected Uniq. rflns

46912

24483

6991

13637

54876

18524

7746

2532

8729

14198

R(int)

0.0732

0.0631

0.0730

0.0260

0.0757

2

GOF(F ) R1[I>2σ(I)]

1.055

1.022

1.134

1.087

1.039

[b]

0.0544

0.0631

0.0455

0.0584

0.0639

[

0.1138

0.1654

0.0630

0.0988

0.1588

wR2[I>2σ(I)]

c]

[a] The residual electron densities were flattened by using the SQUEEZE option of PLATON. [b] R1=Σ||Fo|-|Fc||/|Σ|Fo|. [c] wR2={Σ[w(Fo2-Fc2)2]/Σ[w(Fo2)2]}1/2; where w=1/[σ2(Fo2)+(aP)2+bP],P=(Fo2+2Fc2)/3.


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For Table of Contents Use Only

Tuning

Structural

Topologies

of

Series

of

Metal−Organic

Frameworks: Different Bent Dicarboxylates

Ling Qin, Jinsong Hu, Mingdao Zhang, Qingxiang Yang, Yizhi Li, and Hegen Zheng*

We have synthesized five metal-organic frameworks incorporating the tetratopic ligand with different transition metal ions and bent co-ligands via solvothermal reactions. Structural analysis reveals that the mixed ligands display versatile coordination modes to manage the metal ions to form homochiral, inclined polycatenation, or 3-fold interpenetrating nets. Bulk materials for chiral compounds 1 and 3 have a second-harmonic generation activity.


Tuning Structural Topologies of a Series of MetalâOrganic

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Tuning Structural Topologies of a Series of MetalâOrganic