ARTICLE pubs.acs.org/crystal
Three 3D LanthanideOrganic Frameworks Based on Novel Flexible Multicarboxylates: From ssa to rtl Topologies Fangna Dai,† Di Sun,† and Daofeng Sun* Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong 250100, China
bS Supporting Information ABSTRACT: Three lanthanideorganic frameworks have been solvothermally synthesized and characterized. Complex 1 {[Pr2(bbda)(OH)2(H2O)6] 3 12H2O}n (H4bbda = 5,50 -(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(oxy)diisophthalic acid) is a 3D porous framework belonging to a 2-nodal net with the ssa topology. The coordinated formate ligand from in situ hydrolyzation of dmf binds metal centers to generate rigid rod-shaped SBUs (secondary building units) in both complexes 2 and 3, [Ln(HCOO)(L1)(dmf)]n (Ln = Er (2), Tm (3), H2L1 = 2,20 -(2,3,5,6-tetramethyl-1,4-phenylene) bis(methylene)bis(sulfanediyl)dibenzoic acid, dmf = N,N0 -dimethylformamide). The flexible ligand H4bbda in complex 1 exhibits syn conformation, while the flexible ligand H2L1 in complexes 2 and 3 adopts anti conformation. The anti L1 ligand links the rod-shaped SBUs to give 2 and 3 3D network with the rtl topology.
’ INTRODUCTION Porous metalorganic frameworks (MOFs) have attracted greater attention due to their fascinating structures and intriguing applications such as in catalysis, separation, and gas storage, etc.1,2 To construct MOFs with high stability is a tough but appealing work as almost all of the applications are highly determined by the stability of the porous MOFs.3 Recently, construction of MOFs based on flexible carboxylic ligand has become a flourishing field; despite its fluctuating coordination modes, it will bring more opportunities for structural diversity with its flexible capabilities to meet the coordination requirements of diverse metals.4 Polyhedral and 2D/3D transition-metal organic frameworks based on flexible ligands with “CH2O” spacer have been documented by Hong and Zheng.5,6 Two MOFs of nanoscale cages built by conformationally flexible cyclohexanehexacarboxylate have been presented by Tong and co-workers.7 Luminescence MOFs by trans-stilbene and stress-induced chemical detection using flexible MOFs have also been reported by Allendorf et al.4a,b Most of the MOFs constructing from flexible ligands are based on transition metals, but are rare on rare earth metals.8 Recently, we have reported a series of metalorganic coordination cages constructed from flexible carboxylic ligands and transition metals;10 herein, we report three new lanthanide organic frameworks based on two flexible ligands, {[Pr2(bbda) (OH)2(H2O)6] 3 12H2O}n (1) (H4bbda = 5,50 -(2,4,6-trimethyl1,3-phenylene)bis(methylene)bis(oxy)diisophthalic acid) and [Ln(HCOO)(L1)(dmf)]n (Ln = Er (2), Tm (3); H2L1 = 2, 20 -(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid). There are binuclear paddlewheel SBUs (secondary building units) in complex 1; if there are no rigid r 2011 American Chemical Society
Scheme 1. (a and c) syn-H4bbda and anti-H2L1 Ligands; (b) Binuclear SBUs for Complex 1, Yellow Balls for Coordinated Water Molecules; and (d) the 1D Rod-Shaped SBUs in Complex 2
SBUs, complex 1 should be sensitive and highly unstable as onehalf of the coordination sites of the praseodymium ion are occupied by water molecules (Scheme 1a and b). Complexes 2 and 3 are based on 1D rod-shaped SBUs involving formate ligands as the small bridging ligand, which are in situ generated from the hydrolyzation of dmf (Scheme 1c and d). The application of in situ generated rigid SBUs in the construction of porous MOFs has offered an efficient method for improving Received: September 15, 2011 Revised: November 1, 2011 Published: November 02, 2011 5670
dx.doi.org/10.1021/cg201210p | Cryst. Growth Des. 2011, 11, 5670–5675
Crystal Growth & Design
ARTICLE
Table 1. Crystal Data for 13
formula formula weight
1
2
3
C81H82O68Pr12
C30H32NO7S2Er
C30H32NO7S2Tm
2978.85
749.95
Complex 1a
751.62
i
Pr1O6
2.345(7)
Pr1O5
2.484(10)
2.373(7) 2.413(8)
Pr1O1 Pr1O2
2.519(10) 2.606(13)
Pr1O6iii
2.944(7)
temp (K)
298(2)
298(2)
298(2)
crystal system
hexagonal
monoclinic
monoclinic
Pr1O7 Pr1O8ii
space group
P63/m
P21/n
P21/c
Pr1O4iii
2.461(6) 2.465(11)
a (Å)
19.869(3)
9.0068(4)
9.0246(18)
Pr1O3
b (Å)
19.869(3)
22.9837(9)
23.061(4)
O6iPr1O7
c (Å) α (deg)
27.470(7) 90.000
14.8035(6) 90.00
77.4(3)
O4iiiPr1O1
138.1(4)
16.967(3) 90.00
O8 Pr1O4
76.4(3)
O8iiPr1O2
135.9(3)
O7Pr1O3
145.7(9)
O3Pr1O2
68.0(8)
58.3(8)
O3Pr1O6iii
120.6(6)
144.1(3)
O2Pr1O6iii
108.8(4)
ii
iii
β (deg)
90.000
92.787(1)
119.318(8)
O3Pr1O5
γ (deg)
120.000
90.00
90.00
O8iiPr1O1
3
V (Å )
9391(3)
3060.8(2)
3078.8(10)
Z
2
4
4
Complex 2b
1.029
1.627
1.622
F(000)
2870
1500
1500
data/params GOF on F2
5650/224 0.957
5383/370 1.001
5428/376 0.985
final R indices
R1 = 0.0738a
R1 = 0.0295a
R1 = 0.0349a
wR2 = 0.2368b
wR2 =0.0657b 2
Er1O2
2.301(3)
Er1O7
2.325(2)
Er1O1
2.306(3)
Er1O2iii
2.516(3)
2.309(3)
Er1O3iii
2 2 1/2
the stability of the final frameworks.11,12 As one of the porous neodymiumorganic framework we reported recently, it also involved small bridging ligand (formate) in situ generated from the hydrolyzation of dmf. That complex possesses high crystalline stability and can keep its diffraction pattern even after being heated to 200 °C.13 As presented by most reported MOFs containing 1D rod-shaped SBUs, complexes 2 and 3 can be stable up to 320 °C.
’ EXPERIMENTAL SECTION
2.516(4)
O4 Er1O5
83.23(10)
O2Er1O7
76.82(9)
O4iEr1O6iii
133.76(10)
O1Er1O2iii
138.95(10)
O5 Er1O2 O5iiEr1O7
109.71(10) 145.29(10)
O4iEr1O3iii O2Er1O3iii
74.00(11) 121.80(11)
ii
.
2.318(3)
ii
i
wR2 = 0.0848b 2 2
2.251(3)
Er1O5ii Er1O6iii
R1 = ∑| |Fo| |Fc| |/∑|Fo|. wR2 = [∑w(Fo Fc ) ]/∑w(Fo ) ] b
i
Er1O4
Fcalc (g/cm3)
[I > 2σ(I)] a
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 13
Complex 3c i
2.246(4)
Tm1O6iii
ii
Tm1O3
2.291(3)
Tm1O2iii
2.323(3)
Tm1O7
2.292(5)
Tm1O6
2.516(4)
2.298(4)
Tm1O5
Tm1O4
Tm1O1 O4iTm1O3ii
82.87(13)
O4iTm1O1 O3iiTm1O6iii
133.42(14) 110.04(13)
O6iiiTm1O2iii O7Tm1O6 O4iTm1O5
2.314(4)
2.527(5) 76.95(12) 138.86(14) 73.88(15)
Symmetry codes: (i) x + y + 1, x + 1, z; (ii) x + 2, y + 1, z + 1; (iii) x y + 1, x, z + 1. b Symmetry codes: (i) x + 1/2, y 1/2, z + 3/2; (ii) x + 1/2, y + 1/2, z + 1/2; (iii) x + 2, y, z + 2. c Symmetry codes: (i) x + 1, y + 1/2, z 1/2; (ii) x + 2, y 1/2, z + 1/2; (iii) x + 2, y, z. a
1
Materials and Physical Measurements. The H4bbda and H2L ligands were prepared according to the literature.14 All starting materials used were as purchased without further purification. C, H, N, and S microanalyses were carried out in the elementary analysis group of this department. Thermogravimetric experiments were performed using a TGA/SDT A851 instrument (heating rate of 10 °C/min, nitrogen stream). Preparation of Complexes 13. {[Pr2(bbda)(OH)2(H2O)6] 3 12H2O}n (1). Pr(NO3)3 3 4H2O (100 mg, 0.03 mmol), H4bbda
(100 mg, 0.02 mmol), and HClO4 (0.05 mL) were dissolved in 1 mL of mixed solvents of dmf, EtOH, and H2O (v/v/v = 5:2:1) and heated in a sealed Perex tube at 70 °C for 2 days. The light green crystalline block that formed was collected, washed with water, and dried in the air (yield: 40%). Anal. Calcd for 1: C, 28.33; H, 5.11. Found: C, 27.67; H, 4.58. [Er(HCOO)(L1)(dmf)]n (2). ErCl3 3 6H2O (15 mg), H2L1 (0.01 mg, 0.02 mmol), and HClO4 (0.05 mL) were dissolved in 1 mL of mixed solvents of dmf, EtOH, and H2O (v/v/v, 5:2:1) and heated in a sealed Perex tube at 95 °C for 4 days. Pink crystals suitable for X-ray analyses were collected from the walls of the tube (yield: 65%). Anal. Calcd for 2: C, 48.04; H, 4.30; N, 1.87; S, 8.55. Found: C, 46.99; H, 4.38; N, 1.95; S, 8.48. [Tm(HCOO)(L1)(dmf)]n (3). TmCl3 3 6H2O (15 mg), H2L1 (0.01 mg, 0.02 mmol), and HClO4 (0.05 mL) were dissolved in 1 mL of mixed solvents of dmf, EtOH, and H2O (v/v/v, 5:2:1) and heated in a sealed Perex tube at 95 °C for 4 days. Colorless crystals suitable for X-ray analyses were collected from the walls of the tube (yield: 43%). Anal.
Calcd for 3: C, 47.94; H, 4.29; N, 1.86; S, 8.53. Found: C, 47.02; H, 4.53; N, 1.91; S, 8.39. X-ray Crystallography. Crystals of 13 mounted on glass fiber were studied with a Bruker APEXII CCD detector single-crystal X-ray diffractometer with a graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) source at 25 °C. Absorption corrections were applied using the multiscan program SADABS. All structures were solved by the direct method using the SHELXS program of the SHELXTL package and refined by the full-matrix least-squares method with SHELXL.15 The metal atoms in each complex were located from the E-maps, and other non-hydrogen atoms were located in successive difference Fourier syntheses and refined with anisotropic thermal parameters on F2. The organic hydrogen atoms were generated geometrically (CH 0.96 Å). The free solvent molecules in complex 1 are highly disordered, and attempts to locate and refine were unsuccessful. The SQUEEZE program16 was used to remove scattering from the highly disordered solvent molecules, and a new .hkl file was generated. The structure was solved by using the new generated .hkl file. Pertinent crystallographic data collection and refinement parameters for 13 are collated in Table 1. Selected bond lengths and angles for 13 are collected in Table 2. 5671
dx.doi.org/10.1021/cg201210p |Cryst. Growth Des. 2011, 11, 5670–5675
Crystal Growth & Design
Figure 1. (a) Representation of 24-membered metallo-macrocycles in 1, (b) the large trigonal pore, (c) schematic illustration for striangular prism along the c axis, (d) representation of 48-membered metallomacrocycles, and (e) space filling of 48-membered metallo-macrocycles (Pr, cyan; O, red; C, gray).
’ RESULTS AND DISCUSSION Crystal Structures of Complex 1. Single-crystal X-ray diffraction reveals that complex 1 crystallizes in hexagonal P63/m space group and possesses a 2-nodal 3D porous framework based on binuclear SBUs with ssa topology. The asymmetric unit of 1 consists of one praseodymium ion, 1/2 bbda ligand, one coordinated hydroxyl group, and three water molecules. The mirror bisects the bbda ligand along C14, C16, and C17 atoms. As shown in Figure 1a, the central Pr(III) ion is eight-coordinated in a distorted bicapped trigonal prism coordination environment, completed by four oxygen atoms from four bbda4 ligands, one hydroxyl group, and three oxygen atoms from three water molecules. The O6 atom has a weak coordination to the central Pr(III) ion with the PrO distance of 2.944(7) Å; thus, two Pr(III) ions are engaged by four carboxyl groups from four bbda ligands to generate a binuclear paddlewheel SBU (Figure S1). The remaining coordination sites are occupied by coordinated water molecules. All carboxyl groups of bbda are deprotonated during the reaction, each one adopts bidentate bridging mode to connect two Pr(III) ions in one binuclear SBU, and every bbda4 ligand connects four binuclear SBUs. The bbda4 ligand adopting syn conformation is nonplanar, with the average dihedral angle between the carboxyl groups and the central benzene ring of 88.2°. If the bridging ligand of bbda4 can be considered as a 4-connected linker, the binuclear SBU is connected by four bbda ligands and can be simplified as a square planar 4-connected node (Figure S2). On the basis of the above analysis, the porous 3D framework is a (4,4)-connected 2-nodal net with a ssa topology (Figure S3). The Sch€afli notation is {42.64}{42.84} for this net, and the long symbol is [4.4.8(4).8(4).8(4).8(4)] [4.4.6(2).6(2). 6(2).6(2)] as indicated by the TOPOS software.17 Figure 1a and b shows that every three SBUs were connected by three carboxyl groups from three different bbda4 ligands (forming 24-membered metallo-macrocycles), and the other three arms of the bbda4 ligands coordinate to another three SBUs to form a cage that looks like a striangular prism (Figure 1c).
ARTICLE
Figure 2. (a) 3D framework after omitting the uncoordinated water molecules, showing the trigonal and hexagonal channels; (b) 3D porous framework of 1 with uncoordinated water molecules deleted shown in space filling; and (c) and (d) highlight representation of the large trigonal pore, manifesting three trigonal cages surrounding each trigonal cage (Pr, cyan; O, red; C, gray).
Figure 1d manifests a hexgonal plane formed by 48-membered metallo-macrocycles with six binuclear SBUs and six carboxylate benzene groups, as three interval carboxylate benzene groups point up of the hexagonal plane and the other three points down of the hexagonal plane; thus the hexgonal planes are connected by bbda4 ligands infinitely to form hexagonal channels. It is worth noting that the central benzene ring of bbda4 stretches into 48-membered metallo-macrocycles, and the inner surfaces of the hexagonal channels are bbda4decorated but chocked-full, leading to the small hexagonal channel (Figure 1e). Viewing along the c axis, complex 1 can be formed by infinitely sharing trigonal and hexgonal channels. Every hexgonal channel was surrounded by six trigonal channels (Figure 2a and b). Each binuclear SBU connects to two trigonal cages so that there exist three trigonal cages around each trigonal cage (Figure 2c and d). The dimensions of the large trigonal channel (Figure 2c) are 12.30 7.98 Å, in which the uncoordinated water molecules reside. The solvent-accessible volumes calculated from PLATON16 are 57.6% for 1. Crystal Structures of Complexes 2 and 3. Single-crystal diffraction analysis revealed that complexes 2 and 3 are isostructural; the following description of structural aspects will focus on complex 2. Complex 2 crystallizes in monoclinic P21/n space group and possesses a three-dimensional open framework based on 1D rod-shaped SBUs (Figure 3a and c). The asymmetric unit of 2 consists of one Er(III) ion, one L1 ligand, one formate ligand, and one coordinated dmf. The Er(III) ion is eight-coordinated by four oxygen atoms from four L1 ligands, three oxygen atoms from two formate ligands, and one coordinated dmf molecule, with the average ErO distance of 2.357 Å. The formate group comes from the hydrolysis of dmf molecule. As was found in our previous work,8b,9 the L1 ligand adopting anti conformation is nonplanar, with the average dihedral angles 5672
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Crystal Growth & Design
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Figure 4. TGA curves for complexes 1 and 2.
Figure 3. (a and c) 1D rod-shaped SBUs in 2, (b) two carboxyl groups in one L1 ligand, (d) the “hourglass” channel in 2, and (e) 3D open framework along the a axis; the coordinated dmf molecules were omitted for clarity.
between the carboxyl groups and the central benzene ring of 82.9° and 87.9°. Both carboxyl groups of L1 are deprotonated during the reaction and adopt a bidentate bridging mode to connect two Er(III) ions. It is notable that, although each of the two carboxyl groups in the L1 ligand connects two Er(III) ions, the roles for carboxyl groups are obviously different: the first carboxyl group (O6 C1O7) links Er1A and Er1B through a bridging mode, and the two erbium ions are further bridged by the other two formate groups and one carboxyl groups with a ErA 3 3 3 ErB distance of 3.875 Å and O6C1O7 angle of 126.52° (Figure 3b), and ErA and ErB form a binuclear SBU first; the second carboxyl group (O4C22O5) links ErA0 and ErB0 through a bridging mode, but the two Er(III) ions are not connected by any bridging formate ligands but only another carboxyl group of L1 ligand with a ErA0 3 3 3 ErB0 distance of 5.296 Å and O4C22O5 angle of 124.14° (Figure 3b); this carboxylate takes responsibility for connecting two Er(III) ions to from two binuclear SBUs. The isolated Er(III) ions can be conjointed infinitely by the alternate two kinds of carboxyl groups to form 1D rod-shaped SBUs along the a axis, and the remaining coordination sites are occupied by coordinated dmf molecules. The 1D rod-shaped SBU is further connected with four neighboring SBUs through the bridging L1 groups to form a 3D network, with “hourglass” channels along the a axis (Figure 3d). The dimensions of the large “hourglass” channel are 22.98 14.80 Å, in which the coordinated dmf molecules reside leading to nonporous 3D architecture. In the 3D open framework, each “hourglass” channel is surrounded by six “hourglass” channels by sharing SBUs and ligands (Figure 3e). Thus, complex 2 can be considered as formed by infinitely sharing “hourglass” channels. From the topology view, each binuclear SBU in 2 was linked by six neighboring L1 ligands, and each L1 ligand binds three neighboring binuclear SBU, so the whole 3D framework is a (3,6)-connected net and belongs to rtl topology (Figure S6) with the Sch€afli notation of {4.62}2{42.610.83}. Thermal Stabilities for 1 and 2. TGA measurement revealed that complex 1 is instable in air (Figure 4). The first gradual
Figure 5. Comparison of the PXRD patterns of 2.
weight loss of 18.7% from 50 to 160 °C corresponds to the loss of 12 uncoordinated water molecules (calcd: 18.7%). The second rapid weight loss of 9.3% from 160 to 310 °C is in accordance with the loss of six coordinated water molecules (calcd: 9.4%). A gradual weight loss was found before complex 1 starts to decompose at 310 °C. Complex 2 can be stable up to 310 °C. The first gradual weight loss of 14.9% from 50 to 220 °C corresponds to the loss of one coordinated dmf molecule and one formate (calcd: 15.7%). There is no weight loss between 220 and 310 °C; after that, complex 2 starts to decompose. To further investigate the heat resistance of 2, several freshly ground samples were placed inside a crucible of thermogravimetric analyzer upon heating treatment in air at 150 and 200 °C, respectively. As shown in Figure 5, the XRPD pattern of 2 treated at 150 °C shows no obvious change in comparison with that of 2 in room temperature, indicating the maintenance of periodicity of the crystalline lattice at 150 °C, which is consistent with the TG curve of 2. However, the XRPD pattern of 2 treated at 200 °C shows an obvious change in comparison with that of 2 at room temperature, indicating the collapse of the framework 2. 5673
dx.doi.org/10.1021/cg201210p |Cryst. Growth Des. 2011, 11, 5670–5675
Crystal Growth & Design
’ CONCLUSIONS By using different conformation flexible carboxylate ligands, three 3D porous lanthanideorganic frameworks have been solvothermally synthesized. The participation of formate ligand from the hydrolyzation of dmf molecule plays an important role in the formation of the rigid SBU as well as the 3D porous framework. Although many transition metalorganic frameworks containing in situ generated formate have been widely reported, the examples that the in situ generated formate directly coordinate to lanthanide ion to form rigid SBU are quite rare in porous lanthanideorganic frameworks. Further studies will focus on the synthesis of lanthanideorganic frameworks with permanent porosity by taking advantage of the hydrolyzation of dmf molecule to generate formate ion. ’ ASSOCIATED CONTENT
bS
Supporting Information. Three X-ray crystallographic files in CIF format, and structural figures for complexes 13. This material is available free of charge via the Internet at http:// pubs.acs.org. Crystallographic data (excluding structure factors) for the structures reported in this Article have been deposited in the Cambridge Crystallographic Data Center with CCDC nos. 7583675838 for complexes 13.
’ AUTHOR INFORMATION Corresponding Author
*Fax: +86-531-88364218. E-mail:
[email protected]. Author Contributions †
These authors contributed equally to this work.
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