CRYSTAL GROWTH & DESIGN
Assembly of Large Aromatic Selenoether Ligands into Cubic and Non-interpenetrated (10, 3)-a Nets
2007 VOL. 7, NO. 12 2542–2547
Guo Huang,† Hanhui Xu,‡ Xiao-Ping Zhou,† Zhengtao Xu,*,† Kunhao Li,‡ Matthias Zeller,§ and Allen D. Hunter§ Department of Biology and Chemistry, City UniVersity of Hong Kong, 83 Tat Chee AVenue, Kowloon, Hong Kong, P. R. China, Department of Chemistry, the George Washington UniVersity, 725 21st Street NW, Washington, D.C. 20052, and Department of Chemistry, Youngstown State UniVersity, One UniVersity Plaza, Youngstown, Ohio 44555 ReceiVed May 15, 2007; ReVised Manuscript ReceiVed June 25, 2007
ABSTRACT: This paper reports on the strong tendency of a group of thioether and selenoether molecules to adopt non-centrosymmetric and non-interpenetrating features in forming 3D coordination networks with metal ions. We illustrate such tendency with the (10, 3)-a nets formed by Ag(I) ions and the large aromatic ligands of 1,3,6,8-tetrakis(phenylseleno)pyrene (TPhSeP) and 2,3,6,7,10,11-hexakis(phenylseleno)triphenylene (HPhSeT). In particular, TPhSeP interacts with AgSbF6 to provide a 3D chiral network based on trimeric coordination building blocks. Each trimeric building block is rather complex and consists of three pairs of TPhSeP molecules integrated through the Ag+ ions into a circular unit. The circular, trimeric units function as the three-connected nodes, which are further connected through the Ag+ ions to generate the (10, 3)-a topology. By comparison, the connectivity of the HPhSeT-based net is simpler, with the trigonal-shaped HPhSeT molecules acting as three-connected nodes that are integrated into a (10, 3)-a topology by means of the bridging Ag(I) ions. Other related networks are also briefly discussed to further illustrate the potential generality of the occurrence of non-centrosymmetric and non-interpenetrating features in networks formed by these molecules. Introduction The control of interpenetration is of fundamental interest in the field of coordination networks (i.e., metal–organic frameworks, MOF), largely because of the strong bearing on porosity, acentricity, and other technologically important solid state features.1–5 In general, interpenetration could prove unfavorable for the attainment of porous and acentric structures, because interpenetration effectively reduces the pore volume and often results in centrosymmetric alignment of the individual nets. Even though substantial porosity has been observed in the presence of extensive interpenetration6–10 and the study by Lin’s group has provided considerable insight into the control of interpenetration in relation to nonlinear optical properties,11–13 further studies on effective control or prevention of interpenetration remain a warranted exercise. In particular, the controlled formation of non-interpenetrated 3D nets should prove especially desirable for achieving porous and acentric features. Thioethers and selenoethers as organic building blocks14–24 provide unique advantages for the control of interpenetration in coordination networks. Unlike most organic ligands in coordination networks, where the coordinating sites (such as –COO-, –CN, and pyridinyl groups) are usually situated on the very periphery of the molecule, the sulfur atoms of the thioether molecules are bonded to two organic groups and are consequently embedded in the interior of the molecule. Thus in the formation of coordination networks, thioether and selenoether building blocks can be divided into two portions with distinct functions: the central core (such as the pyrene and triphenylene units in 1,3,6,8-tetrakis(phenylseleno)pyrene (TPhSeP) and 2,3,6,7,10,11-hexakis(phenylseleno)triphenylene (HPhSeT), see Scheme 1) and the pendant groups (e.g., the phenyl groups in TPhSeP and HPhSeT). Because the * To whom correspondence should be addressed. E-mail: zhengtao@ cityu.edu.hk. † City University of Hong Kong. ‡ George Washington University. § Youngstown State University.
Scheme 1
distance between neighboring nodes is largely determined by the distance between the coordinating site and the geometric center of the molecules, the size of the core unit effectively controls the metric length of the framework, whereas the pendant groups can be modified to control the overall volume of the molecules without affecting the length scale of the framework. Thus, with appropriately selected size of the pendant groups, interpenetration can be effectively controlled or prevented. As part of our effort to explore the versatility of thioethers and selenoethers in forming non-interpenetrated 3D networks, we here report the syntheses and crystal structures of two coordination networks (1 and 2) based on silver salts and the molecules of TPhSeP and HPhSeT (network composition for 1, 2TPhSeP · 3AgSbF6; for 2, 2HPhSeT · 3AgBF4). Despite the difference in the molecular geometries (of HPhSeP and HPhSeT) and the local coordination modes, the networks in both 1 and 2 adopt the non-interpenetrating (10, 3)-a topology with aesthetically appealing cubic symmetries. The (10, 3)-a topology presents the highest symmetry among three-connected nets, pertains to the famous gyroid surface, and is of particular interest in the construction of solid state networks.25 In spite of the increasing number of (10, 3)-a coordination networks reported in recent years,26–32 non-interpenetrating (10, 3)-a nets with cubic symmetry remain relatively rare.33–37 Besides the aesthetic
10.1021/cg070447k CCC: $37.00 2007 American Chemical Society Published on Web 11/07/2007
Assembly of Large Aromatic Selenoether Ligands
Crystal Growth & Design, Vol. 7, No. 12, 2007 2543
Table 1. Crystallographic Data for 1 and 2 compound
1
2
formula FW space group a, Å V, Å3 Z Fcalcd, g/cm3 wavelength, Å abs coeff (µ), cm-1 R 1a wR2b
C88H68Se8O2F18Sb3Ag3 2819.96 P4132 31.7406(7) 31977(1) 12 1.757 0.71073 (Mo KR) 40.93 5.85% [I > 2σ(I)] 17.11% [I > 2σ(I)]
C126H87Ag3B3F12N3O6Se12 3270.54 P213 24.1021(6) 14001.2(6) 4 1.551 0.71073 (Mo KR) 35.87 4.45% [I > 2σ(I)] 15.39% [I > 2σ(I)]
a
R1 ) ∑||Fo| – |Fc||/∑|Fo|. b wR2 ) {∑[w(Fo2 – Fc2)2]/∑w(Fo2)2]}1/2.
appeal, the interconnected channels in the cubic systems are generally useful for enhancing the absorption and transport properties in the solid state. Despite the large spacer length of TPhSeP and HPhSeT (and the large unit cell volumes as a result), no interpenetration occurs in either structure, and the non-centrosymmetric space groups are consequently imposed. Experimental Section Starting materials, reagents, and solvents were purchased from commercial sources (Aldrich) and used without further purification. Solution 1H and 13C NMR spectra were taken on a 200 or 300 MHz Varian Mercury spectrometer at room temperature with tetramethylsilane (TMS) as the internal standard. Powder X-ray diffraction patterns for the bulk samples were collected at room temperature on a Scintag XDS 2000 diffractometer (Cu KR, λ ) 1.5418 Å). The powder samples were pressed onto a glass slide for data collection (in air). A 2θ range of 3–40° was collected. The single crystal X-ray data sets of 1 and 2 were collected on a Bruker AXS SMART APEX CCD system using Mo KR (λ ) 0.710 73 Å) radiation. The structures were solved and refined by full-matrix leastsquares on Fo2 using Bruker Advanced X-ray Solutions SHELXTL (version 6.14), Bruker AXS Inc., Madison, Wisconsin. Selected crystallographic data are summarized in Table 1, with details of the X-ray diffraction studies on the single crystals provided in the Supporting Information. Thermogravimetric Analysis. Thermogravimetric analysis (TGA) was performed on a Pyris TGA-1 instrument under flowing N2 gas (20 mL/min), and the heating rate was 5 °C/min. The crystalline sample of 2 was suction-filtered from the mother liquor and rinsed briefly with 2 mL of hexane. After being left under suction for another 2 min to further dry the residual solvents, about 3.5 mg of the collected sample was loaded into the TGA sample holder, and the heating procedure for TGA was at once started. 1,3,6,8-Tetrakis(phenylseleno)pyrene (TPhSeP). In a nitrogenfilled glove box, diphenyl diselenide (anhydrous, 1.80 g, 99%, 5.80 mmol) and ethanol (anhydrous, 20 mL, 99.5+%) were loaded into a 100 mL two-neck round bottom flask equipped with a septum. After being taken out of the glove box, the flask was connected to a vacuum manifold under nitrogen protection, and sodium borohydride (anhydrous, 0.47 g, 98%, 12.40 mmol) was added to the stirred solution (whereupon the yellow solution changed to colorless). The ethanol was then evaporated, and the colorless residue was pumped to dryness. After 1,3-dimethyl-2-imidazolidinone (DMEU, 40 mL, 99%, anhydrous) was transferred into the flask via cannula and 1,3,6,8-tetrabromopyrene (TBP, 1.00 g, 1.90 mmol) was added under nitrogen protection, the reaction mixture was heated to 80 °C with stirring for 2 days. The resultant orange-colored reaction mixture was poured into 200 mL of water and extracted by toluene (50 mL × 4). The toluene solution was then washed with water (200 mL × 3) and brine (200 mL, saturated), dried over sodium sulfate, and evaporated in vacuo to afford a yellow solid (1.10 g, 76% based on TBP). The product thus obtained was shown to be practically pure by 1H NMR and 13C NMR and was used in subsequent experiments without further purification. 1H NMR (300 MHz, CDCl3): δ 7.18 (m, 12H), 7.31 (m, 8H), 8.34 (s, 2H). 8.57 (s, 4H). 13C NMR (75.5 MHz, CDCl3): δ 127.6, 128.1, 129.3, 129.7, 131.4,
131.8, 132.3, 132.7, 139.6. Chemical analysis of the product C40H26Se4 yields the following: calcd, C (58.41%), H (3.19%); found, C (57.22%), H (3.19%). 2,3,6,7,10,11-Hexakis(phenylseleno)triphenylene (HPhSeT). In an argon-filled glove box, diphenyl diselenide (anhydrous, 99%, 267 mg, 0.850 mmol) was loaded into a 25 mL two-neck round bottom flask equipped with a septum, and ethanol (anhydrous, 10 mL, 99.5+%) was added. After the flask was taken out of the glove box, it was connected to a vacuum manifold under nitrogen protection. Sodium borohydride (anhydrous, 98%, 70 mg, 1.8 mmol) was then added to the stirred solution at room temperature (rt), and the yellow solution became colorless. The ethanol was evaporated under an out-flowing nitrogen stream, and the colorless residue was evacuated to dryness. DMEU (15 mL) was then transferred into the flask via a cannula under nitrogen protection, followed by the addition of HBT (2,3,6,7,10,11hexabromotriphenylene, 100 mg, 0.14 mmol, prepared from a reported procedure38). The reaction mixture was heated and stirred at 70 °C until after 2 days TLC (thin layer chromatography) indicated the completion of reaction. The orange-colored solution was poured into 100 mL of water and extracted with toluene (50 mL × 4). The organic layers were then combined and washed with water (200 mL × 3) and brine (200 mL, saturated) and dried with anhydrous sodium sulfate. The solvent was removed in vacuo, and the crude product was purified by flash chromatography (silica gel, 1.5:8.5 dichloromethane/hexanes) to provide a yellow solid (117 mg, 71% based on HBT, mp 204–206 °C). 1H NMR (200 MHz, CDCl3): 7.18–7.43 (m, 30H), 7.86 (s, 6H). 13 C NMR (50 MHz, CDCl3): 128.2, 128.3, 128.9, 129.8, 131.2, 133.8, 136.2. X-ray Quality Single Crystals of 2TPhSeP · 3AgSbF6 (1). TPhSeP was dissolved in THF (9.1 mM, equivalent to 30 mg in 4.0 mL of THF) and placed at the bottom of a glass tube. A toluene solution of AgSbF6 (13.7 mM, equivalent to 37.6 mg in 8.0 mL of toluene) was then carefully layered on the top of the solution. The tube was sealed and was kept in a dark, quiet place. Yellow cube-like crystals suitable for X-ray studies were obtained over a period of 2 weeks (24.3 mg obtained, 50% yield based on TPhSeP). The crystals appear uniform in morphology, and the crystal growth procedure is highly reproducible with single crystal diffraction studies on different batches of the crystals all giving the same unit cell constant. Chemical analysis of the product (filtered, rinsed with hexanes, and dried in air for about 10 min) yields the following: found, C (35.67%), H (2.22%). This result closely matches the formula C80H52Ag3F18Sb3Se8 (equivalent to 2TPhSeP · 3AgSbF6): calcd, C (35.91%), H (1.96%), suggesting loss of the THF molecules during the sample preparation and measurement process. For comparison, formula C88H68Ag3F18O2Sb3Se8 (equivalent to 2TPhSeP · 3AgSbF6 · 2THF) gives the following calculated composition: C, 37.48%; H, 2.43%. X-ray Quality Single Crystals of 2HPhSeT · 3AgBF4(2). A nitrobenzene (NB) solution of HPhSeT (20.0 mg, 35 mM) was added to a NB solution of AgBF4 (5.0 mg, 52 mM) in a vial and filtered to obtain a light yellow solution. The vial containing this yellow solution (with the cap loosely on) was placed into a larger vial containing about 10 mL of hexanes. Yellow single crystals (24.0 mg obtained, 86% yield based on HPhSeT) suitable for single-crystal X-ray analysis formed after about 3 days. X-ray powder diffraction of the product indicated a dominant phase consistent with the single-crystal structure of 2 with a minor unknown phase (see Figure S1 in the Supporting Information). Chemical analysis of the evacuated product C108H71Ag3B3F12Se12 (equivalent to 2HPhSeT · 3AgBF4) yields the following: calcd, C (44.71%), H (2.50%), F (7.86%); found, C (43.98%), H (2.42%), F (7.70%). To help determine the chemical composition of the assynthesized crystals, freshly made crystals of 2 (6.4 mg) were dissolved in 0.5 mL of 1:1 DMSO/CD2Cl2 in a vial to form a solution (3.9 mM) for 1H NMR measurement. 1H NMR (200 MHz, DMSO/CD2Cl2): 7.27 (m, 18H), 7.40 (m, 12H), 7.54 (t, 6H), 7.75 (t, 6H), 7.86 (s, 6H), 8.16 (d, 3H). The 1H NMR spectra of (200 MHz, DMSO/CD2Cl2) for nitrobenzene: 7.58 (t, 2H), 7.74 (t, 2H), 8.20(d, 1H). Combined with the above NMR data of pure HPhSeT, the HPhSeT/NB ratio is thus established as 1:3 (i.e., 2HPhSeT · 3AgBF4 · 6C6H5NO2). This composi-
2544 Crystal Growth & Design, Vol. 7, No. 12, 2007
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Figure 1. A pair of π-stacked TPhSeP molecules and the coordinated Ag1 and Ag2 centers in the crystal structure of 1: red spheres, Ag; green spheres, Se; white spheres, C; yellow spheres, O. Figure 3. Projections along the 4-fold helices of a topological representation of the coordination net of 1.
Figure 2. (a) A fragment of the coordination net of 1 (red sphere, Ag; green spheres, Se; blue, a triangle-like circuit and (b) a topological representation of the π-centered TPhSeP pair as the four-connected node (red spheres, Ag; green spheres, π-stacked TPhSeP pair). tion is also supported by the TGA measurement (see Figure S2 in the Supporting Information).
Results and Discussion Synthesis and Crystallization. Molecules TPhSeP and HPhSeT were synthesized from reacting the phenylselenide anion (PhSe-, generated from PhSeSePh and NaBH4) and the aromatic bromides of 1,3,6,8-tetrabromopyrene and 2,3,6,7,10,11hexabromotriphenylene (see Experimental Section), while singlecrystal growth of the molecules with silver(I) salts was achieved in slow diffusion setups. Specifically, single crystals of 1 (network composition 2TPhSeP · 3AgSbF6) were prepared by slow diffusion between a THF solution of TPhSeP and a toluene solution of AgSbF6, and single-crystal samples of 2 (network composition 2HPhSeT · 3AgBF4) were prepared by diffusing hexanes vapor into a nitrobenzene solution of HPhSeT and AgBF4. The limited solubility of the TPhSeP molecule and the resultant small samples of 1 made it difficult to carry out more systematic characterization. By comparison, crystals of 2 could be readily obtained in larger amounts (e.g., over 50 mg), and more detailed characterization has been conducted. Besides the framework components, single-crystal X-ray diffraction studies on 2 located one third of BF4- anions and a certain fragment for the included nitrobenzene molecules. A composition of 2HPhSeT · 3AgBF4 · 3C6H5NO2 can thus be deduced, while about 24% of the total unit cell volume is made up by voids that seem to be at least partially filled with additional
Figure 4. A pair of π-stacked HPhSeT molecules and the coordinated Ag(I) centers in the crystal structure of 2: (a) a side view, with bonds of both triphenylene units shown in dark grey; (b) a top view, with bonds of the top triphenylene unit shown in dark grey; red spheres, Ag(I); green spheres, Se; white spheres, C. Disorder of the pendant phenyl groups is not shown.
ill-defined solvent molecules (see Table S7 in the Supporting Information for details). Thermogravimetric analysis (TGA) of the as-synthesized sample indicated a weight loss of 19.1% at relatively low temperature (i.e., 171 °C, see the TGA plot in Figure S2 of the Supporting Information), indicating the overall composition as 2HPhSeT · 3AgBF4 · 6C6H5NO2 (calculated weight percentage for nitrobenzene, 20.3%). The overall composition of 2 is also supported by NMR measurement on a solution of the as-synthesized sample (dissolved in 1:1 DMSO/CD2Cl2 mixture). Preliminary X-ray diffraction scans on the solid samples of 2 indicated that the crystalline framework is substantially stable to the loss of the nitrobenzene guests at room temperature, although evacuation of the guest molecules at higher temperature resulted in collapse of the crystalline network. Description of Structures. The crystal structure of 1 was solved in the cubic space group P4132, and the unit cell size is quite large (a ) 31.7452 Å). The asymmetric portion of the unit cell contains one TPhSeP molecule and two AgSbF6 units. The crystal structure features distinct pairs of the TPhSeP molecules stacked in a face-to-face fashion (interplanar distance 3.46 Å, with the pyrene units oriented at about 90° to each other). The two crystallographically inequivalent Ag+ atoms interact with the TPhSeP molecules rather differently. The Ag2 atom coordinates to one selenium atom from each of the π-stacked TPhSeP pairs, while two associated THF molecules provide additional coordination bonds (Ag–O distances 2.384 Å) to furnish a distorted coordination geometry; as a link, it is therefore confined within the π-stacked pair of TPhSeP mol-
Assembly of Large Aromatic Selenoether Ligands
Figure 5. (a) A fragment of the coordination net of 2 (red spheres, Ag; green spheres, Se; for clarity, the phenyl groups on the HPhSeT molecule are omitted) and (b) a topological representation of the same fragment (red spheres, Ag; white spheres, geometric center of the triphenylene unit).
ecules (see Figure 1). The Ag1 atom, by comparison, bonds to three selenium atoms, two from within a π-stacked pair and one from a neighboring pair of TPhSeP molecules, with a coordination geometry close to trigonal planar; it is the Ag1 atoms that serve to connect the TPhSeP pairs into a 3D network (see Figure S3 in the Supporting Information for an overview of the network). Topologically, the π-stacked TPhSeP pair as the basic building block can be simplified as a four-connected node, since it is associated with four interconnecting Ag1 atoms; the trigonally coordinated Ag1 atoms, notably, become single bridges across neighboring TPhSeP pairs, because two of the Ag1–Se bonds originate from a single TPhSeP pair and are merged into a linear connection when the latter is taken as a building unit. With Ag1 atoms acting as the slightly bent bridging units (Figure 2b), the resultant four-connected net features distinct trianglelike circuits, imagine the bent bridge as one side, with each
Crystal Growth & Design, Vol. 7, No. 12, 2007 2545
vertex being one four-connected node. Each triangle-like circuit is connected to three closest neighbors through sharing of the vertices. For illustration, the chemical constitution of the triangle-like circuit is highlighted in Figure 2a. Treating the triangle-like circuits as three-connected nodes, one obtains a single net of the familiar (10, 3)-a topology, as shown in Figure 3. In the context of this fully simplified net, let us take note of the chemical content represented by the individual nodes and rods so as to dissect the supramolecular assembly in a new light. Thus each node corresponds to the above triangle-like circuit (see Figure 2a), and represents a circular fragment comprising three TPhSeP molecules and three interconnecting Ag1 atoms. Each rod represents the complex chemical interconnect between the circular fragments, which features three Se–Ag–Se links (two from Ag1 and one from Ag2) straddled across the π-stacked TPhSeP pairs. By comparison, the coordination network in the crystal structure of 2 (2HPhSeT · 3AgBF4) is simple to dissect. This is a structure solved in the enantiomorphic cubic space group P213 (cell parameter a ) 24.1021 Å), with the HPhSeT molecule centered on the crystallographic 3-fold axis, adopting a C3 point group symmetry. Like in 1, distinct pairing of the HPhSeT molecules occurs through the aromatic–aromatic stacking between the triphenylene units (interplanar distance 3.462 Å). The two π-stacked molecules are crystallographically inequivalent, and the asymmetric portion of the unit cell thus contains two thirds of an HPhSeT molecule, together with one AgBF4 unit (Figure 4). Each HPhSeT molecule takes on three Ag(I) atoms through the chelating ortho-bis(phenylseleno) groups, while each Ag(I) as a coordination center bears two HPhSeT ligands, with the surrounding Se atoms in a distorted tetrahedral configuration [Ag(I)-Se, 2.639-2.687 Å; Se-Ag(I)-Se, 80.86°–142.93°], as shown Figure 5a,b. Overall, the Ag(I) atoms serve as a slightly bent bridge across the trigonal HPhSeT molecules, forming the (10, 3)-a net with the triphenylene centers as the three-connected nodes (Figure 6a,b). Compared with the prototypical (10, 3)-a net in SrSi2 (Figure 6c), the net of 2 features closely paired nodes, as a result of the π-stacked pairing of the HPhSeT molecules (see Figure S4 in the Supporting Information for more comparison of the nets of 2 and SrSi2). No interpenetration is observed for the (10, 3)-a net in either 1 or 2, and both networks (i.e., networks and associated anions, excluding all solvent molecules) contain substantial voids, with Platon calculations indicating 19% and 41.2% of the unit cell volumes of 1 and 2, respectively, as the solvent accessible region (see Figure 7 for a projection of the channels in the crystal
Figure 6. Projections along the 4-fold helices of (a) a topological representation of the coordination net of 2 (red spheres, Ag; white spheres, geometric center of the triphenylene unit), (b) the same representation without the Ag centers, and (c) the Si net in SrSi2. The green portions highlight the neighboring 4-fold helices.
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Acknowledgment. This work is supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China [Project No. 9050198 (N_CityU 118/06)]. The diffractometer was funded by NSF Grant 0087210, by the Ohio Board of Regents grant CAP-491, and by Youngstown State University. Supporting Information Available: Full crystallographic data in CIF format for 1 and 2, a TGA plot for the solid sample of 2, additional figures of the crystal structures of 1 and 2, an X-ray powder diffraction pattern of 2, and UV–vis and emission spectra for TPhSeP and HPhSeT. This material is available free of charge via the Internet at http:// pubs.acs.org.
References
Figure 7. View of the crystal structure of 2 along the 3-fold axis (solvent molecules are omitted): red dots, Ag; green dots, Se. The BF4anion is colored orange.
Scheme 2
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15)
structure). Interestingly, the absence of interpenetration is also commonly observed in 3D coordination networks of similar aromatic thioether molecules. For example, HPhTB, HPhTT, and HMOPhTT (Scheme 2) all formed with silver(I) salts into 3D non-interpenetrating nets in acentric space groups (namely, j HMOPhTT · HPhTB · 2AgPF6, I212121; HPhTT · AgBF4, I4; AgSbF6, Cc).18,21 Apparently, the relatively large size and the large number of the aromatic pendant groups account for a substantial fraction (e.g, over 50%) of the volume of the entire molecule and thus contribute to the exclusion of additional nets in the solid state. By comparison, in coordination networks of thioether molecules with smaller pendant groups such the methyl group [e.g., tris(4-methythiophenyl)amine], interpenetration becomes more prone to occur.39 In a larger context, these thioether examples point to a general approach for the use of pendant groups to prevent interpenetration of 3D nets. To minimize the impact of the pendant groups on the bonding pattern between the organic molecule and the metal center, and thus to retain a persistent network topology, it is advisable to devise systems in which the pendant groups are spacially removed from the ligating groups. The retention of the network topology is well illustrated in the structures of the previously reported HPhTT · AgBF4 and HMOPhTT · AgSbF6, in which the 82.10-a topology was adopted in spite of the introduction of the methoxy groups. Similarly, the integration of spacially removed pendant groups into the commonly used building blocks (such as carboxylic acids and pyridines) may lead to robust frameworks with convenient and systematic control of interpenetration, noncentrosymmetry, and other structural characteristics in the solid state.
(16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34)
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CG070447K
