Syntheses and Characterizations of Zinc (II) Compounds Containing

May 22, 2004 - assembly of OH-H2BDC, ZnII with bpe, dpe, and bpp, respectively ... 1,2-bis(4-pyridyl)ethane, dpe ) 1,2-di(4-pyridyl)ethylene, and bpp ...
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Syntheses and Characterizations of Zinc(II) Compounds Containing Three-Dimensional Interpenetrating Diamondoid Networks Constructed by Mixed Ligands Xiaoju Li, Rong Cao,* Daofeng Sun, Wenhua Bi, Yanqin Wang, Xing Li, and Maochun Hong

CRYSTAL GROWTH & DESIGN 2004 VOL. 4, NO. 4 775-780

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China Received February 1, 2004;

Revised Manuscript Received April 1, 2004

ABSTRACT: Three three-dimensional interpenetrating diamondoid zinc(II) compounds, [Zn(bpe)(OH-BDC)]n (1), {[Zn(dpe)(OH-BDC)](dpe)0.5}n (2), and {[Zn(bpp)(OH-BDC)](H2O)}n (3), have been prepared solvothermally by assembly of OH-H2BDC, ZnII with bpe, dpe, and bpp, respectively [OH-H2BDC ) 5-hydroxyisophthalic acid, bpe ) 1,2-bis(4-pyridyl)ethane, dpe ) 1,2-di(4-pyridyl)ethylene, and bpp ) 1,3-bi(4-pyridyl)propane]. Single-crystal X-ray diffraction analyses reveal that 1 is a 5-fold interpenetrating diamondoid network, and 2 and 3 are 4-fold interpenetrating diamondoid structures with dpe guest molecules and water molecules, respectively. Introduction The designed construction of metal-organic complexes from various molecular building blocks connected by coordination bond, supramolecular contacts (hydrogen bond, π‚‚‚π stacking, etc.), or their combination, is an interesting research area. To date, it has made considerable progress in supramolecular chemistry and material chemistry.1-4 In this area, the metal-organic complexes exhibiting diamondoid networks have attracted great attention from chemists due to their robust structural topologies and potential applications in functional materials.4-9 Much effort has been devoted to their controllable construction since Ermer reported several hydrogen-bonded diamondoid organic compounds in 1988.4 Hence, a number of diamondoid compounds based on covalent and/or hydrogen bonds have been constructed from elaborately selective ligand linkers and appropriate transition-metal ion nodes. A conceivable and remarkable characterization in diamondoid frameworks is that the interpenetration phenomena is easily formed, and the degree of interpenetration mainly depends on the length and steric interactions of the bridging ligands.4-9 In the view of development of synthetic strategies and functional materials, it will be valuable to construct diamondoid architectures based on mixed bridging ligands because the combination of different ligands can result in greater tunability of structural frameworks than single ligands.10,11 However, owing to the difficult prediction of either composition or structure of the final product, the diamondoid metal-organic architectures with mixed bridging ligands are much less investigated.10 Benzenedicarboxylate ligands and their derivatives have been extensively employed to link metal ions to produce high dimensional frameworks containing channels or cavities.12 On the other hand, flexible dipyridyl ligands with certain spacers, such as 1,2-bis(4-pyridyl)ethane (bpe),13 1,2-di(4-pyridyl)ethylene (dpe),14 and 1,3bi(4-pyridyl)propane (bpp),15 can freely rotate to meet * To whom correspondence should be addressed. Tel: +86-5913796710. Fax: +86-591-3714946. E-mail: [email protected].

Scheme 1. Three Different Dipyridyl Ligands

the requirement of coordination geometries of metal ions in the assembly process. These ligands are good candidates to produce unique structural motifs with beautiful aesthetics and useful functional properties. Although the combination of dicarboxylate and dipyridyl ligands with metal ions has resulted in various supramolecular complexes with different structures and functions, complexes containing diamondoid networks have seldom been reported.10 In this work, mixed bridging ligands of 5-hydroxyisophthalic acid (OH-H2BDC) and flexible dipyridyl ligands (Scheme 1) were employed to react with ZnII to produce coordination polymers with diamondoid frameworks. Herein, we wish to report the syntheses and characterizations of three diamondoid compounds, [Zn(bpe)(OH-BDC)]n (1), {[Zn(dpe)(OHBDC)](dpe)0.5}n (2), and {[Zn (bpp)(OH-BDC)](H2O)}n (3). Experimental Section Materials and General Methods. 5-Hydroxyisophthalic acid, 1,2-bis(4-pyridyl)ethane, 1,2-di(4-pyridyl)ethylene, and 1,3-bi(4-pyridyl)propane were purchased from Aldrich and used without further purification; all the other reagents were commercially available and used as purchased. Thermogravimetric experiments were performed using a TGA/SDTA851

10.1021/cg049949d CCC: $27.50 © 2004 American Chemical Society Published on Web 05/22/2004

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instrument (heating rate of 15 °C/min, nitrogen stream). IR spectra as KBr pallets were recorded on a Magna 750 FT-IR spectrophotometer. Elemental analysis of C, H, and N were determined using a Perkin-Elmer 240C elemental analyzer. Fluorescence spectroscopy was performed on an Edinburgh Analytical instrument FLS920. Synthesis of [Zn(bpe)(OH-BDC)]n 1. A mixture of OHH2BDC (0.045 g, 0.25 mmol), NaOH (0.020 g, 0.50 mmol), and bpe (0.044 g, 0.25 mmol) was dissolved in CH3OH (5 mL) and transferred to a 25-mL stainless steel reactor with Teflon liner. Zn(NO3)2‚6H2O (0.075 g, 0.25 mmol) in distilled water (15 mL) was added, and the mixture was heated to 170 °C automatically. The temperature was kept at 170 °C for 4 days and cooled to room temperature. Yellow block crystals of 1 were obtained. Yield: 72%. Elemental analysis (%): calcd. for C20H16ZnN2O5: C 55.90, H 3.75, N 6.52; found: C 55.81, H 3.82, N 6.48. IR (KBr, cm-1): 3070 (w), 1622 (vs), 1567 (vs), 1508 (m), 1434 (s), 1380 (vs), 1284 (s), 1216 (s), 1072 (s), 1033 (s), 829 (m), 800 (s), 781 (vs), 723 (vs), 559 (m). Synthesis of {[Zn(dpe)(OH-BDC)](dpe)0.5}n 2. The procedure is similar to the synthesis of 1 except that bpe was replaced by dpe. Yellow needle crystals of 2 were obtained. Yield: 55%. Elemental analysis (%): calcd. for C26H19ZnN3O5: C 60.19, H 3.69, N 8.10; found: C 60.24, H 3.55, N 8.12. IR (KBr, cm-1): 3359 (m), 3106 (m), 1621 (vs), 1565 (vs), 1434 (s), 1375 (vs), 1355 (s) 1298 (s), 1216 (m), 1028 (s), 975 (m), 829 (m), 802 (s), 777 (s), 722 (s), 566 (m), 547 (s). Synthesis of {[Zn(bpp)(OH-BDC)](H2O)}n 3. The procedure is similar to the synthesis of 1 except that bpp was used instead of bpe. Yellow needle crystals of 3 were obtained. Yield: 67%. Elemental analysis (%): calcd. for C21H20ZnN2O6: C 54.62, H 4.36, N 6.07; found: C 54.60, H 4.32, N 6.10. IR (KBr, cm-1): 3197 (s), 3076 (m), 1567 (s), 1380 (vs), 1358 (m), 1296 (s), 1068 (m), 1032 (s), 974 (m), 779 (s), 731 (s), 488 (s), 426 (w). X-ray Crystallographic Studies. Intensity data for 1 and 3 were measured on a Siemens Smart CCD diffractometer with graphite-monochromated Mo-KR radiation (λ ) 0.71073 Å) at room temperature. All empirical absorption corrections were applied by using the SADABS program.19 Measurement of 2 was conducted on a Rigaku Mercury CCD diffractometer with graphite monochromated Mo-KR radiation (λ ) 0.71073 Å). Reflections (16981) were collected at -100 °C, of which 5041 reflections were unique.20 The structures for 1-3 were solved by direct methods21 and refined on F2 by full-matrix leastsquares using the SHELXL-97 program package.22 The positions of hydrogen atoms were generated geometrically (C-H bond fixed at 0.96 Å), assigned isotropic thermal parameters, and allowed to ride on their parent carbon atoms before the final cycle of refinement. Crystal data and structure determination summary for 1-3 are summarized in the Table 1. The selected bond lengths and angles for 1-3 are listed in Table 2. CCDC number for complexes 1-3 are 220650, 220651, and 220652, respectively.

Results and Discussion Syntheses. It is well-known that organic ligands play crucial roles in the design and construction of desirable frameworks. The change of flexibility, length, and symmetry of organic ligands can result in a remarkable class of materials containing diverse architectures and functions.16,17 Recently, Lin has reported a series of interpenetrating diamondoid ZnII and CdII complexes by using single multifunctional ligands with pyridyl and carboxylate groups. They demonstrated that the degree of interpenetration of diamondoid networks is heavily dependent on the length of spacer between pyridyl and carboxylate groups.5b We speculated that when using mixed multicarboxylate and pyridyl ligands to formulate interpenetrating diamondoid frameworks, the length of spacer in each ligand may also take an effective role on

Li et al. Table 1. Crystal Data and Structure Determination Summary for 1-3 formula Fw crystal size (mm) crystal system space group a/Å b/Å c/Å β/° V/Å3 Z Dc/g cm-3 µ/mm-1 T/K λ(Mo KR)/Å reflections collected unique reflections Rint parameters S on F2 R1 (I > 2σ(I))a wR2 (I > 2σ(I))b ∆Fmin and ∆Fmax [e/Å3] a

1

2

3

C20H16ZnN2O5 429.72 0.26 × 0.18 × 0.16 tetragonal P4(1) 8.1045(9) 8.1045(9) 29.953(5) 1967.4(4) 4 1.451 1.281 293(2) 0.71073 4870

C26H19ZnN3O5 518.81 0.30 × 0.10 × 0.10 monoclinic P2(1)/c 12.70(4) 12.198(17) 17.97(3) 125.75(11) 2259(9) 4 1.525 1.132 173(2) 0.71073 16981

C21H20ZnN2O6 461.76 0.74 × 0.24 × 0.10 monoclinic P2(1)/n 11.1365(2) 10.9605(4) 16.3438(7) 103.861(2) 1936.9(1) 4 1.584 1.311 293(2) 0.71073 5867

3037

5047

3359

0.0441 253 1.053 0.0623 0.1166 0.529 and -0.268

0.0362 316 0.961 0.0405 0.1227 0.469 and -0.372

0.0400 339 1.247 0.0570 0.1193 0.466 and -0.458

R ) ∑||F0| - |Fc||/∑|F0|. b wR ) [∑w(F02 - Fc2)2/∑w(F02)2]1/2.

Table 2. Selected Bond Lengths (Å) and Angles (°) for 1-3a Zn(1)-O(1) Zn(1)-N(2B) Zn(1)-N(1) O(1)-Zn(1)-N(2B) O(1)-Zn(1)-N(1) N(2B)-Zn(1)-N(1) O(1)-Zn(1)-O(3A) N(2B)-Zn(1)-O(3A)

Compound 1 1.932(6) Zn(1)-O(3A) 2.044(7) Zn(1)-O(4A) 2.051(7) 95.9(3) N(1)-Zn(1)-O(3A) 106.1(3) O(1)-Zn(1)-O(4A) 104.0(3) N(2B)-Zn(1)-O(4A) 143.0(4) N(1)-Zn(1)-O(4A) 109.4(3) O(3A)-Zn(1)-O(4A)

Zn(1)-O(1) Zn(1)-O(4A) Zn(1)-O(3A) O(1)-Zn(1)-N(2B) N(2B)-Zn(1)-N(1) O(1)-Zn(1)-O(4A) N(2B)-Zn(1)-O(4A) N(1)-Zn(1)-O(4A)

Compound 2 1.976(4) Zn(1)-N(2B) 2.137(3) Zn(1)-N(1) 2.173(4) 100.9(2) O(1)-Zn(1)-N(1) 107.1(2) O(1)-Zn(1)-O(3A) 103.24(13) N(2B)-Zn(1)-O(3A) 144.79(10) N(1)-Zn(1)-O(3A) 98.50(16) O(4A)-Zn(1)-O(3A)

89.1(2) 162.70(9) 91.0(2) 99.4(2) 60.81(14)

Zn(1)-O(1) Zn(1)-O(3A) O(1)-Zn(1)-O(3A) O(1)-Zn(1)-N(2B) O(3A)-Zn(1)-N(2B)

Compound 3 1.971(3) Zn(1)-N(2B) 1.971(3) Zn(1)-N(1) 103.0(1) O(1)-Zn(1)-N(1) 111.2(2) O(3A)-Zn(1)-N(1) 116.4(2) N(2B)-Zn(1)-N(1)

2.042(4) 2.050(4) 100.6(1) 110.1(1) 113.9(2)

2.165(9) 2.193(9) 93.8(3) 95.3(3) 91.9(3) 151.6(4) 58.4(4) 2.065(5) 2.088(5)

a Symmetry code: for 1: (A) y + 1, -x + 2, z - 1/4; (B) -y + 3, x + 1, z + 1/4; for 2: (A) x, -y + 3/2, z + 1/2; (B) x - 1, -y + 1/2, z - 1/2; for 3: (A) x + 1/2, -y + 3/2, z + 1/2; (B) x + 1/2, -y + 5/2, z - 1/2.

constructing different degrees of interpenetration. The solvothermal reactions of OH-H2BDC, Zn(NO3)2‚6H2O with bpe, dpe, and bpp at 170 °C have afforded yellow crystals of complexes 1, 2, and 3, respectively. It is noteworthy that the hydroxyl group (-OH) in OH-BDC is not involved in coordination to ZnII center. The successful syntheses of the three compounds prompt us to investigate whether similar results can be observed by using 1,3-benzendicarboxylic acid (H2BDC) instead of OH-H2BDC under the same conditions. Unfortunately, uncharacterized precipitates insoluble in any common solvents have been generated. It can be pre-

Interpenetrating Diamondoid Zinc(II) Compounds

Crystal Growth & Design, Vol. 4, No. 4, 2004 777 Scheme 2. Coordination Modes of OH-BDC in the Three Compoundsa

a (a) OH-BDC adopts one chelating and one monodentate coordination mode in 1 and 2. (b) OH-BDC adopts a bis-monodentate coordination mode in 3.

Figure 1. (a) The coordination environment around ZnII in 1 with the thermal ellipsoids at 50% probability level. (b) View of a single diamondoid cage generated through six OH-BDC and six bpe bridging ten ZnII centers with the thermal ellipsoids at 50% probability level. (c) Five-fold interpenetrating diamondoid network in 1 with bridging ligands omitted for clarity.

sumed that the presence of a hydroxyl group in OH-H2BDC may be helpful for the formation of the three compounds as crystalline form under the solvothermal conditions, although a detailed mechanism is still unclear.

Description of Crystal Structures. [Zn(bpe)(OHBDC)]n 1. Single-crystal X-ray diffraction analysis reveals that 1 is a three-dimensional 5-fold interpenetrating diamondoid network and crystallizes in the chiral space group P4(1) with the flack parameter being 0.07(3). As shown in Figure 1a, each ZnII center is coordinated by two nitrogen atoms from different bpe and three carboxylate oxygen atoms from different OH-BDC in a distorted trigonal bipyramidal geometry. The bond distances of Zn1-N1 (2.051(7) Å) and Zn1-N2B (2.044(7) Å) are typical for Zn-Npy coordination. The bond distance between monodentate carboxylate oxygen atom and ZnII [1.932(6) Å] is much shorter than those between chelating carboxylate oxygen atoms and ZnII [2.165(9) and 2.193(9) Å]. Each OH-BDC ligand bridges two ZnII centers through its chelating and monodentate carboxylate groups (Scheme 2a), the hydroxyl group (-OH) neither takes part in coordination nor is involved in weak interactions to metal centers or other ligands. Bpe adopts an anti-conformation with the dihedral angle between two pyridine rings being 52.2°. Thus, 10 ZnII centers are connected by 12 bridging ligands, namely, six bpe and six OH-BDC, generating a diamondoid cage. The separation of the adjacent Zn‚‚‚Zn bridged by OHBDC and bpe are 10.302 and 13.390 Å, respectively (Figure 1b). The long spacers between coordination sites of bpe and OH-BDC result in large cavities within the diamondoid cages. However, due to the absence of large guest molecules to fill the void space, the potential voids are filled via mutual interpenetration of four independent equivalent frameworks, generating a 5-fold interpenetrating three-dimensional architecture (Figure 1c). {[Zn(dpe)(OH-BDC)](dpe)0.5}n 2. Different from 1, 2 is a three-dimensional 4-fold interpenetrating diamondoid network with dpe guest molecules and crystallizes in the monoclinic space group P2(1)/c. As shown in Figure 2a, each ZnII is coordinated by two nitrogen atoms from different dpe, a monodentate and a chelating carboxylate group from different OH-BDC. Hence, the

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Figure 2. (a) The coordination environment around ZnII in 2 with the thermal ellipsoids at 50% probability level. (b) Fourfold interpenetrating diamondoid network with dpe guest molecules in 2; bridging ligands are omitted for clarity.

ZnII center is in a distorted trigonal bipyramidal geometry. There are two kinds of dpe ligands: one acts as an exo-bidentate ligand in an anti-conformation, and the dihedral angle of 48.4° between two pyridyl rings is smaller than that in 1, probably due to the different twist between CdC in dpe and C-C in bpe; the other serves as a guest molecule and is not involved in any interactions with metal centers or other ligands. Similar to that in 1, each OH-BDC bridges two ZnII centers through its monodentate carboxylate oxygen atom and chelating carboxylate group, the hydroxyl group (-OH) is not involved in coordination (Scheme 2a). Thus, dpe and OH-BDC link ZnII into a three-dimensional diamondoid network, in which the separation of the adjacent Zn‚‚‚Zn bridged by OH-BDC and dpe are 9.732 and 13.425 Å, respectively. To minimize the big void cavities in the diamondoid cages and stabilize the whole framework, a 4-fold interpenetrating diamondoid framework is generated. Uncoordinated dpe molecules are accommodated inside the framework and further shrink the void space (Figure 2b).

Figure 3. (a) The coordination environment around ZnII in 3 with the thermal ellipsoids at 50% probability level. (b) Fourfold interpenetrating diamondoid network with water guest molecules in 3; bridging ligands are omitted for clarity.

{[Zn(bpp)(OH-BDC)](H2O)}n 3. 3 is a 4-fold interpenetrating diamondoid network with water guest molecules and crystallizes in the monoclinic space group P2(1)/n. As shown in Figure 3a, each ZnII is coordinated by two nitrogen atoms from different bpp and two monodentate carboxylate oxygen atoms from different OH-BDC in a distorted tetrahedral geometry. The average distances of Zn-N (2.046(4) Å) and Zn-O (1.971(3) Å) are similar to those in 1 and 2. Different from 1 and 2, OH-BDC behaves in a bis-monodentate bridging mode (Scheme 2c). Although the hydroxyl group (-OH) does not participate in coordination, it is involved in hydrogen bonding interaction with the adjacent uncoordinated water molecule (O5‚‚‚Ow1 ) 2.725 Å). Bis-monodentate OH-BDC and exo-bidentate bpp bridge four-coordinated ZnII to form a threedimensional diamondoid framework. Three identical frameworks fill its void space to generate a 4-fold interpenetrating network with water molecules as space fillers (Figure 3b). It should be emphasized that the separation of adjacent Zn‚‚‚Zn bridged by OH-BDC (9.784 Å) is approximately equal to that in 2; however, the separation of the adjacent Zn‚‚‚Zn bridged by bpp

Table 3. Comparison of Structural Data in the Three Compounds distance between distance between dipyridyl ligand Zn(II) centers Zn(II) centers angle of bridged by bridged by degree of spacer pyridyl rings (°) dipyridyl ligand (Å) OH-BDC (Å) interpenetration 1 2 3

bpe dpe bpp

CsC CdC CsCsC

52.2 48.4 81.5

13.390 13.425 12.772

10.302 9.732 9.784

5-fold 4-fold 4-fold

guest molecule dpe water

Interpenetrating Diamondoid Zinc(II) Compounds

Figure 4. Photoluminescence spectra and excitation spectra (inset) of the three compounds at room temperature: (a) compound 1; (b) compound 2; (c) compound 3.

(12.772 Å) is much shorter than those in 1 and 2 due to the great twist of C-C-C spacer in bpp. Two pyridyl rings in dpp are almost vertical with dihedral angle between them being 81.5°.

Crystal Growth & Design, Vol. 4, No. 4, 2004 779

Although all the three compounds exhibit threedimensional interpenetrating diamondoid frameworks, they are quite different. 1 is a 5-fold interpenetrating network, and 2 and 3 are 4-fold interpenetrating frameworks with large dpe guest molecules and small water guest molecules, respectively. As shown in Table 3, the Zn‚‚‚Zn distances bridged by dipyridyl ligands are slightly different (13.390 Å for 1, 13.425 Å for 2, and 12.772 Å for 3). The twist of the spacer in the dipyridyl ligand increases from CdC in dpe, C-C in bpe, to C-C-C in bpp, resulting in obviously different twisting angles between two pyridyl rings (48.4° for 2, 52.2° for 1, and 81.5° for 3) to meet for the requirement of ZnII coordination geometry, and further influences the metalmetal distances. It should be emphasized that bpp in 3 possesses three carbon atoms between two pyridyl rings, but the great distortion of C-C-C results in a shortest metal-metal distance. On the other hand, due to the different bridging and/or chelating modes of OH-BDC, the distances of Zn‚‚‚Zn bridged by OH-BDC (10.302 Å in 1, 9.732 Å in 2, and 9.784 Å in 3) are also slightly different in the three compounds. Thus, the effective size of diamondoid cages is shrinked from 1, 2, to 3 and thereby results in a decrease of the degree of interpenetration or diminishment of guest molecules. IR Spectroscopy. The IR spectrum of 1 displays characteristic bands of the carboxylate groups (OHBDC) at 1622 and 1567 cm-1 for asymmetric vibrations and at 1434 and 1380 cm-1 for symmetric vibrations. The ∆ values, which represent the separation between νasym(-COO) and νsym(-COO), are 188 and 187 cm-1, respectively. For 2, the characteristic bands of the carboxylate groups are shown at 1621 and 1565 cm-1 for the asymmetric vibrations and 1434 and 1375 cm-1 for the symmetric vibrations. The ∆ values are 187 and 190 cm-1, respectively. For 3, the characteristic bands of the carboxylate groups are shown at 1567 cm-1 and 1380 cm-1 for asymmetric and symmetric vibrations, respectively, and the ∆ value is 187 cm-1. The similar splitting of νasym(-COO) in 1 and 2 reveals the presence of similar coordination fashion of carboxylate groups in OH-BDC;12b,18 the results are consistent with their crystal structures. Thermal and Fluorescent Properties. The thermal stability of compounds 1-3 has been determined on polycrystalline samples in a nitrogen atmosphere by thermogravimetric analysis (TGA). There was no chemical decomposition up to 379 °C in 1. For 2, TGA shows no weight loss up to 311 °C, lower than that in 1 owing to the presence of dpe guest molecules. For 3, the total weight loss of 3.96% from 158 to 276 °C corresponds to the loss of one uncoordinated water molecule per formula unit (ca. 3.90%), indicating the presence of hydrogen bonding interaction between water molecule and hydroxyl group (-OH) of OH-BDC. The compound starts decomposition after 321 °C. The emission spectra of compounds 1-3 have been shown in Figure 4. It can be seen that 1 exhibits an intense broad photoluminescence emission at 570 nm (λex ) 482 nm). The intense photoluminescence emissions for 2 and 3 are observed at 559 nm (λex ) 480 nm) and 505 nm (λex ) 426 nm), respectively. To ascertain the adscription of the emission bands, the photoluminescence of pure organic ligands is measured, and no

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emission is found in the range 500-600 nm. Thus, the emission of 1-3 may be assigned as ligand-to-metalcharge-transfer (LMCT). The similar emission of 1 and 2 may be due to the similar coordination environments around ZnII centers. The different emission for 3 results from the different coordination geometry of ZnII center in 3 as compared to those in 1 and 2.

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The solvothermal reactions of 5-hydroxyisophthalic acid (OH-H2BDC), Zn(NO3)2‚6H2O and flexible dipyridyl ligands with different spacers (bpe, dpe, and bpp) produced three different interpenetrating diamondoid networks. Different spacer and flexibility in dipyridyl ligands result in different Zn‚‚‚Zn distances and sizes of the diamondoid cage, which induce different degree of interpenetration and guest molecules in their frameworks. In summary, this research reveals that assembly of mixed bridging organic ligands and metal ions can afford a broader way to construct interpenetrating diamondoid networks than using single ligand, and the conformation of co-ligand plays an important role on the degree of interpenetration and inclusion of guest molecules. Acknowledgment. The authors are grateful to the financial support from NNSF of China (90206040, 20325106, 20333070), NSF of Fujian Province (B982003), and the key and the “One Hundred Talent” projects from CAS. Supporting Information Available: Crystallographic information files (CIF) of three compounds are available free of charge via the Internet at http://pubs.acs.org.

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