Supramolecular Network of Triaminotriptycene and Its Water Cluster

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Supramolecular Network of Triaminotriptycene and Its Water Cluster Guest: Synthesis, Structure, and Characterization of [(tatp)4•17H2O]n Li Liu, Yun Zhang, Xiao-Li Wang, Geng-Geng Luo, Zi-Jing Xiao, Lin Cheng, and Jing-Cao Dai Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 29 Jan 2018 Downloaded from http://pubs.acs.org on January 29, 2018

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Crystal Growth & Design

Supramolecular Network of Triaminotriptycene and Its Water Cluster Guest: Synthesis, Structure, and Characterization of [(tatp)4·17H2O]n † Li Liu, Yun Zhang, Xiao-Li Wang, Geng-Geng Luo*, Zi-Jing Xiao, Lin Cheng* and Jing-Cao Dai* Institute of Materials Physical Chemistry, Huaqiao University, Xiamen, Fujian 361021, China

Abstract ： Hydrated triaminotriptycene solid, [(tatp)4·17H2O]n (1) (tatp = 2,6,12triaminotriptycene), has been obtained by the solution phase crystal growth techniques. The structure established through X-ray structural analysis shows that this hydrated solid, ascribed to cubic F3-d space group, Z = 8 (a = 25.56(2) Å, V =16699(3) Å3), crystallizes in a sodalite-like tatp porous supramolecular architecture that captures a bigger-sized heptadecameric water cluster guest. This hydrated solid is rather stable even removal of its guest waters in ambient temperature and exhibits an interesting light response behavior with the crystal color conversion from pale yellow to brown under the xenon lamp or sunlight irradiation. Keywords: supramolecular solids, water cluster, porous network, photocoloration, sodalite-like structure

--------------† This article is dedicated to Professor Xin-Tao Wu on the occasion of his 80th birthday. * Corresponding author, Email: [email protected]; Phone/Fax: +86-595-22690569.

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1. Introduction Rapid advances and widespread interest in the molecule-base materials is a recent phenomenon.1-7 In the search for new molecule-base functional materials, attention is being turned to explorations of the supramolecular solids exhibiting higher ordered structures because they may provide much opportunity for recognizing the intricate structural diversities associated with novel functionality.8-20 These supramolecular solids are defined by the multifunctional molecular components via their interactions with respect to each other in the crystalline phase. Some very interesting examples have been reported based on such supramolecular solids established in the noncovalent interactions, as to coordination bonding,14-25 hydrogen bonding,26-31 π−π stacking32-34 and electrostatic interactions,35-37 etc. In these supramolecular solids, the modularized multifunctional molecular components play an important role in the fabrication of a wide range of supramolecular architectures. Thus, selection of building blocks having suitable geometries is crucial with respect to overall shapes and properties of supramolecular solids. Because porous framework materials have been found a wide range of technological applications in all aspects of human activity, as to gas storage, small molecule separation, and catalysis and so on, there are many efforts devote to the designed construction of zeolite-like porous frameworks.7-20 A literature search shows that, some multifunctional organic molecules, such as terephthalate,4,14,22 trimesate,17-21 bipyridine,38-41 pyrazine,42,43 cyclodextrin,44 cucurbiturils,45 calixarenes,46 and pillarenes,47 have been successfully employed as building blocks to construct a large number of supramolecular solids with ordered porous or cyclic structures. However, as building blocks, the triptycene and its derivatives48-51 are not abundant used in the fabrication of supramolecular architectures in comparison with the great amount of multifunctional organic molecules mentioned above. Although several triptycene-based porous frameworks are established,50,51 their use to develop ordered porous architectures have not been well explored so far. 2,6,12- triaminotriptycene (tatp) is also a multifunctional organic molecule exhibiting unique star-shaped and branched molecular structure. This triptycene derivatives has three hydrophilic amino groups at their star-shaped and branched aromatic rings that may give the possibility for serving as hydrogen bond donors or acceptors. Thus, the unique geometric feature and amino functional group may be favorable to tatp molecule served as an adequately 2


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tritopic building block in construction of supramolecular solids with variety of architectures. Recognizing the potential of this multifunctional organic molecule, as a part of our continuing interest on the exploratory design and synthesis of functional crystalline solids with the mineralominetic architectures as well as expected properties, we have embarked on a program for using tatp molecule to prepare supramolecular solids and wished to get the supramolecular architectures related to porous zeolite-like frameworks. Our initiated explorations have led to an interesting hydrated triaminotriptycene solid, [(tatp)4·17H2O]n (1), of which we herein report its synthesis, structure, characteristics, and photocoloration. 2. Experimental Section General remarks. Infrared spectra were recorded on a Shimadzu FTIR-8400S spectrometer in the range of 4000–400 cm–1 using KBr pellets. 1H-NMR spectra was obtained from a Bruker Avance III HD 400M Spectrometer. The elemental microanalyses were carried out with a Carlo-Erba EA1110 elemental analyzer. Fluorescent data were collected on an Edinburgh FL-FS920 TCSPC system, and TGA (thermal gravimetric analysis) were performed on a TA DSC2910/SDT2960 instrument at a heating rate of 5 ºC·min-1 under N2 atmosphere. PXRD (Powder X-ray diffraction) investigation was carried out on polycrystalline samples in the 2θ range of 3-50° using a Philip Panalytical Xpert Powder diffractometer at 40 kV, 30 mA or a Rigaku MiniFlex 600 diffractometer at 40 kV, 15 mA with Cu Kα radiation (λ = 1.5406 Å) with a scan speed of 5°·min–1 and a step size of 0.1° in 2θ. Solid state absorption spectra were collected on a Shimadzu UV2550 spectrometer equipped with a solid state sample holder for polycrystallines at room temperature. The XPS (X-ray photoelectron spectroscopy) spectra were measured on a Thermol scientific Escalab 250Xi system equipped with Al Kα as X-ray source. Photoirradiation was carried out using a 300 W AuLight Company Model CEL-HXUV300 Xe lamp at room temperature, and monochromic light was obtained by passing the light through monochromator. All the reagents and solvents for synthesis were purchased from commercial sources and used as received without further purification. 2,6,12-triaminotriptycene (tatp) was obtained by customary procedures described previously48,49 in the yield of 77.3%. IR (KBr pellet, cm-1) for tatp: v = 3421(s), 3352(br), 3220(br), 3003(w), 2949(w), 1620(vs), 1480(vs), 1449(vw), 3



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1331, 1297(w), 1261, 1187, 1184(w), 1142(w), 1117(w), 1088(w), 940(vw), 875(w), 841, 804(vw), 772, 709(w, br), 580(s), 504(vw), 454(vw) (also see Figure S1, Supporting Information); 1H-NMR (400 MHz, CDCl3, ppm): δ = 3.47 (brs, 6H, NH2), 4.99-5.06 (m, 2H, bridgehead), 6.24-6.25 (m, 3H, Ph), 6.71 (m, 3H, Ph), 7.04-7.06 (s, 3H, Ph) (Figure S2). Preparation of (tatp)4·17H2O (1). A typical prepared procedure of (tatp)4·17H2O (1) was given by tatp (59 mg, 0.2 mmol) stirred in CH3OH-H2O mixed solvent (9 mL, v/v: 1:2) under ultrasonic treatment (160 W, 40 KHz, 40°C) for getting a clear solution. The resultant filtrate was allowed to evaporate slowly at ambient temperature. After two weeks, pale yellow crystals of 1 were collected by filtrated isolation, whose phase purity was confirmed by PXRD patterns (Figure S3). Anal. Calcd. (found) for C80H102N12O17 (1): C 63.88 (64.10), H 6.84 (6.85), N 11.18 (11.17). IR (KBr pellet, cm-1) for 1: v = 3414(s), 3342(s), 3216, 3003, 2950, 1621(vs), 1480(vs), 1448(w), 1330(s), 1296, 1261(s), 1185(s), 1142, 1117, 1090(w), 942(w), 878, 840(s), 804, 775(s), 709(br), 582(vs), 504, 455. (Figure S1) Structure determinations. Blocklike single-crystal of the title compound with appropriate dimension 0.13 × 0.13 × 0.11 mm was chosen under an optical microscope and quickly coated with high vacuum grease (Dow Corning Corporation) before being mounted on a glass fiber for data collection. Data collection was performed on a Agilent Gemini/Xcalibur X-ray diffractometer equipped with a graphite monochromated Mo/Ka radiation (λ = 0.71073 Å) at 173 K. Data reductions were performed using CrysAlisPro program (Version 1.171.36.32), and empirical absorption corrections were applied for all of the data sets with the aid of MUTI-SCAN program. The systematic absences analyzed for 1 by the XPREP program in the SHELXL-2014 software package suggested Fd-3 (No 203) as the highest possible space group. The structures were solved by direct methods using SHELXS–2014 and refined on F2 by full-matrix least–squares techniques using SHELXL-2014. All non–hydrogen atoms were located from iterative examination of difference F-maps following least-squares refinements of the earlier models, and treated anisotropically. The positions of organic hydrogen atoms were generated geometrically and refined with isotropic temperature factors. Hydrogen atoms attached to lattice water molecules were located by difference F-maps, and then refined subject to the constraint O-H = 0.85 Å, and Uiso(H) = 1.5Ueq(O). Due to the face-centered cubic symmetrical operation, these water hydrogen atoms disordered more than three 4


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positions, in which two hydrogen atoms, H11 and H21, were symmetrical disordered over either 4 or 3 positions. All structures were examined using the Addsym subroutine PLATON to assure that no additional symmetry could be applied to the models. Final refinements converged at R1 = 0.096 for 1. Some crystallographic data are summarized in Table 1~2. More details on crystallographic information have been deposited as CCDC 1496656 in cif format that can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.ukf/data_request/cif. 3. Results and Discussion Structure. X-ray single-crystal diffraction analysis reveals that crystal structure of 1 crystallizes in a cubic space group Fd-3 and comprises well-separated tatp and lattice water molecules (Figure 1) that have been further interacted each other through various hydrogen bonds. In the star-shaped tatp molecule, each amino group is served as a 4-linking node and is connected to four different amino groups of three tatp neighbors via weak molecular N−H···N interactions in either 4.369 or 4.835 Å separations. Thus, one star-shaped tatp molecular spacer possesses multiple weak molecular N−H···N (4.369−4.835 Å) interactions with six different tatp neighbors. As a result, four tatp molecules are self-sorted into a sodalite-like cage (labeled as sod-cage latter) with a large host cavity of ~8.5 Å in diameter to accommodate a bigger-sized guest species (Figure 2a,b,c). Each sod-cage has eight 6-ring and six 4-ring windows, in which four windows of the former are acrossed by tatp molecules (Figure 2a) while six windows of the latter are further fused to six nearest neighboring sod-cages along three unit-cell axes directions to give a zeolite sodalite porous supramolecular networking host (Figure 2d). This is comparable to those super-sod frameworks in phosphate-based materials.52-54 It is noted that every acrossed tatp molecule has four C-H lipo-hydrogen atoms oriented vertically to the inner cavity of sod-cage, of which three lipo-hydrogen atoms come from branched aromatic rings, as discussed later, are found to be participated in the fabrication of guest hydrogen bonding and, therefore, are important for restraining and stabilizing the guest water cluster. On the other hand, the lattice water molecules are aggregated into an elegant (H2O)17 heptadecameric water cluster that is trapped inside the sod-cage (Figure 2c). The fascinating feature for present water cluster is that a 5



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central pivot lattice water molecule (O1) is tetrahedral surrounded by four water molecules (O2 and its three symmetric equivalents O2a-c) through intracluster hydrogen bonds (see Table 2) to form a centered tetrahedral (H2O)5 cluster core, a so-called ‘Walrafen pentamer’, 55,56

that is further spanned to six (H2O)2 dimeric fins by twelve lattice water molecules (O3

and its eleven symmetric equivalents O3a-k) on the six tetrahedral edges. This can be also structurally viewed as a condensed version of six pentagonal (H2O)5 pentamers that have been fused together by sharing one central pivot tetrahedral coordinated H2O molecule. To our best knowledge, the structural data for such water heptadecamer is still very scarce, only a similar water cluster captured in host MIL-74 zeolite material has been roughly described so far.53,54 An earlier theoretical prediction57 suggested that the higher stability for the (H2O)17 cluster structure should be an interior sphere array owing to it may have a possibility for the formation of a maximum number of hydrogen bonds. Obviously, present elegant (H2O)17 heptadecamer is considerably deviated from this expected ideal sphere geometry. Figure 2c gives a closer look at the connectivity of lattice water molecules for this rare water heptadecamer. Although X-ray crystallography suggests that it is hard to lock the precise positions of water hydrogen atoms because of symmetrical disorders, their hydrogen bond acceptors or donors can be distinguished well based on the analysis for the connectivity of these lattice water molecules. All lattice water molecules of Walrafen pentamer (O1, O2 and its symmetric equivalents O2a-c) are found to be tetrahedral coordinated and therefore served as the double hydrogen bond acceptors and double hydrogen bond donors whereas all fin water molecules (O3 and its symmetric relations O3a-k) are only µ2-bridged and thus just acted either as the single hydrogen bond donor or acceptor for matching else lattice water molecules within water heptadecamer. The O···O distances for this heptadecamer are in the ranges between 2.810 and 2.824 Å with an average value of 2.817 Å (Table 2), which is apparently longer than the expected ranges of 2.50-2.75 Å established from that similar water cluster squeezed in MIL-74 zeolite material53,54 and the values of either 2.75 Å in ice Ic or 2.759 Å in ice Ih58 but slightly shorter than those observed in liquid water (2.854 Å)59-61 and comparable to those in the ice II phase (2.77-2.84 Å).62 All intracluster O···O···O angles are fallen into the range of 105.7 to 113.0° (Table 2), an average value of 108.9°, considerably deviating from the 72° for a ideal pentagonal geometry of 5-ring. Moreover, the O···O···O 6


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angles around the central pivot water molecule are 109.5°, substantially closest to the expected typical tetrahedral geometry of water. These suggest the compactness of present water heptadecameric cluster is inferior to that of the similar water cluster in literature52-54 mentioned above and those known of ice Ic or Ih but close to that of liquid water. In additional, the separations of O3···N and O3···C4 are fallen on 2.88-3.31 Å and 3.37 Å (Table 2), respectively, implying hydrogen bond contact exist between the (H2O)2 dimeric fins and either the amino groups or the lipo-hydrogen atoms in the branched aromatic rings of tatp host, here the O3 lattice water molecule is observed to be served as the double weak hydrogen bond acceptor and the single strong hydrogen bond donor. This means that present water heptadecameric guest is actually anchored by host tatp molecules through the extensive hydrogen bond interactions and appears to be quite important for why this less stable water cluster does not aggregated into an interior sphere version as predicted theoretically. Characterizations and Properties. The IR spectrum of 1 exhibits the characteristic bands almost similar to that of its parent tatp molecule in the region 4000–400 cm–1. Their differences mainly occur in the region of 3421-3216 cm–1 that attributable to the O–H stretching vibrations. Three well-resolved peaks at 3415, 3342 and 3216 cm-1 in the hydrated solid vs three broad bands at 3421, 3352, and 3220 cm-1 in its parent tatp molecule reflect the presence of water aggregates in the former (Figure S1). It needs to be mentioned that the latter is also a blend of aqua molecules, this has been confirmed not only by above three broad IR bands at 3421, 3352 and 3220 cm-1 that attributed to the O–H stretching vibrations but by 1

H-NMR signal at 1.55 ppm of the water molecules (Figure S2). In additional, the sharped

peak at 1621 cm-1 for the former and 1620 cm-1 for the latter should be attributed to the N–H stretching vibrations, and the intensive characteristic band of O–H stretching vibrations at 3415 cm-1 seems the behavior of water cluster in 1 is more close to that of liquid water at 3490 cm-1 rather than ice at 3220 cm-1,58,63 which are consistent with the structure from the analysis results of the X–ray diffraction technique. The thermogravimetric (TG) trace for 1 reveals the weight loss of guest water molecules occurs in ca. 50–100 °C range with an approximately 19 % weight loss, corresponding to loss all of the water (calculated 20 %). The integrity for host organic molecules is found to be held up to ca. 300°C and the finally complete decomposition for host is finished at ca. 725 °C (Figure S4). Based upon above TG 7



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analysis, powder X–ray diffraction (PXRD) patterns were further used to explore the stability for guest water removal/readsorption, as shown in Figure 3. This hydrated triaminotriptycene solid is rather stable in darkness in ambient air (Figure 3b). Compared with the original crystals, the dehydrated solid obtained by heating crystals at either 50 °C (Figure 3c) or 100 °C (Figure 3d) shows a phase pattern with the line positions concerned but broadened peaks almost identical to original one, implying the integrity for host organic framework still kept. However, the host framework at 150 °C is found to have been fully destroyed (Figure 3e). In order to understand the stability of the host framework better, the polycrystalline sample of 1 was put into a desiccator with phosphorous pentaoxide for removal of guest water. The desiccated solid, ~13.8 % of weight loss, also gives a similar phase pattern as heated samples at either 50 °C or 100 °C (Figure 3g), suggesting the broad peaks should clearly be resulted from water molecules expulsion. Furthermore, almost identical patterns with both the sharp peaks and the intensities as the original one are observed for the water readsorbed solids that either dehydrated (Figure 3f) or desiccated sample (Figure 3h) is immersed in water for 2 days, indicating water removals is reversible for 1. This is important for present supramolecular framework because of the reversible dehydration and rehydration properties connecting the commercial applications. Photocoloration. Compound 1 exhibits an interesting light response behavior with the crystal color conversion from pale yellow to brown under the xenon lamp or sunlight irradiation. This color conversion also may be denied from the chemical reactions by tatp molecules because the IR spectra of 1 keep almost the same characteristic peaks during the photocoloration process (Figure S1) and, moreover, the crystalline phases for either the pale yellow or the brown are substantial equivalent, judging from their almost the same PXRD patterns (Figure S5). Although it is harder to judge the real mechanism for the photocoloration at this stage, the intramolecular conjugation effect between branched aromatic rings and their attached amino groups seems to be responsible for this interesting phenomenon. Note that the tatp molecule of 1 presents the average C-C distance of 1.386 Å (range 1.377(6)-1.401(6) Å) for the aromatic rings and the C-N distance of 1.399(5) Å for their grafted amino groups (also see Table 2), the latter is clearly shorter than a normal C-N single bond (~1.50 Å) and near a C-N double bond (~1.38 Å),64 suggesting the fact that double bonding effect appears in the 8


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C-N contact. This means the conjugation effect between branched aromatic rings and their attached amino groups occurs, which is available for electron delocalizing. The XPS measurements support the conjugation changes of tatp arisen from the photoirradiation. An energy shift appears in the shake satellite,65 corresponding to the π → π* transitions of aromatic rings, of the C 1s state in the tatp molecule during photoirradiation: an energy signal at 290.5 eV in the pale phase vs signals at both 290.4 and 288 eV in the brown phase (Figure S6), approved the conjugation changes of tatp. The UV-VIS spectrum of 1 for the initial pale phase shows three well-resolved high-energy intensive absorption peaks at 213 nm, 262 nm and 317 nm as well as a less-obvious weak broad absorption band in visible region (Figure 4a), in which three high-energy absorptions should be, respectively, arisen from the σ → σ*, π → π* and n → π* transitions of the branched aromatic rings of tatp molecule. After photoirradiation, accompanying the crystal color from pale yellow to brown, that less-obvious weak broad absorption band range from ~350 nm of UV to ~500 nm of visible region now becomes quite remarkable and the corresponding absorption intensities obviously increase with the extension of irradiation time (Figure 4a). This process is also tightly coupled with fluorescence changes. The strong emission band is observed to be from 340 to 380 nm with the strongest emission at ~350 nm (Figure 4b), a clearly blueshift as compared to the fluorescent peak at ~360 nm for its parent tatp (Figure S7). This blueshift phenomenon should be recognized as a result of the electron delocalization effect inhibited by the hydrogen bonds from guest water cluster. The fluorescent intensities now decrease with the irradiation time and are inversely proportional to their UV absorptions, implying the fluorescence has been overlapped with the activated wavelength band of photocoloration. 4. Conclusion Herein, we have presented a good example of 2,6,12-triaminotriptycene as building block in the fabrication of supramolecular porous solids. A novel supramolecular porous material, [(tatp)4·17H2O]n,

was

successfully

prepared

and

characterized.

This

hydrated

triaminotriptycene solid possesses a sodalite-like porous supramolecular framework with an interesting heptadecameric water aggregrates and is rather stable even removal of the guest waters in ambient environment. The experimental observations also reveal this supramolecular porous solid is an optical-active material that exhibits an interesting light 9



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response behavior with the crystal color conversion from pale yellow to brown under the xenon lamp or sunlight irradiation. These results will be important for expanding the chemical horizons on the fabrication of functional supramolecular porous materials and their applications. Acknowledgments. This work was financially supported by the Natural Science Foundation of Fujian Province (grant No. 2015J01202) and the Package Funding for the Distinguished Professorship of the Tong-Jiang Scholars. The authors are grateful to Mr. Zhenbo Du for the assistance with the X-ray single-crystal diffraction data collections; and Lin Cheng also thanks the National Natural Science Foundation of China (grant No. 51473055) for support. Supporting Information Available: Figure S1-S7 including the FT-IR spectra of 1 and tatp molecule, 1H-NMR spectra of tatp, powder X-ray diffraction patterns of 1 that illustrate the high quality crystalline phase and crystalline stability, TGA trace of 1, XPS spectra of C in 1, fluorescent property of tatp, and additional crystallographic data in Table S1-S2 (that have been also deposited in a CIF file as CCDC-1496656 for 1 in the Cambridge Crystallographic Data Centre). These materials are available free of charge via the Internet at http://pubs.acs.org.

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Page 14 of 21

Figure captions 1) Figure 1. The ORTEP diagram of compound 1 (ellipsoids at 25 % probability) depicting the tatp molecule associated with its lattice water guests, the hydrogen atoms of lattice water are omitted for clarity. Symmetry key: (a) 1+z, -0.5+x, -0.5+y; (b) 0.5+y, 0.5+z, -1+x; (c) 1.25-y, 0.25-z, -1+x; (d) 1.25-y, 0.5+z, 0.75-x; (e) 0.5+y, 0.25-z, 0.75-x; (f) 1.75-x, y, -0.25-z; (g) 0.75-z, 1.25-x, -0.5+y; (h) 1.75-x, 0.75-y, z; (i) x, 0.75-y, -0.25-z; (j) 0.75-z, -0.5+x, 0.25-y; (k) 1+z, 1.25-x, 0.25-y. 2) Figure 2. (a) A view of a sod-cage possesses a large host cavity of ~8.5 Å in diameter in 1 generated by the self-sorting of four tatp molecules via weak molecular N−H···N (4.369−4.835 Å) interactions. (b) Schematic illustration showing the sod-cage with large host cavity accessible to a bigger (H2O)17 water cluster guest species based on 1. (c) A view showing how an elegant (H2O)17 heptadecameric water cluster guest assembled by the hydrogen-bonded network of the lattice water molecules in 1. Hydrogen bond lengths and angles are listed in Table 2. (d) Crystal packing of 1 showing how a sod-cage (highlight by red) fused to six nearest neighboring sod-cages through its 4-ring windows along three lattice axes to give a host zeolite-type porous supramolecular network. 3) Figure 3. Comparison of powder patterns of polycrystalline sample treated by different ways showing that crystalline phase of 1 kept after (a) calculation based on single crystal data, (b) exposured on air in darkness for 1 year, (c) dehydrated under vacuum at 60 °C, (d) dehydrated under vacuum at 100 °C, (e) dehydrated under vacuum at 150 °C, (f) the dehydrated sample of 150 °C dipped in water. (g) dehydrated (~13.8% weight loss) on a desiccator with phosphorous pentaoxide, and (h) the desiccated sample dipped in water. 4) Figure 4. Solid state UV-visible (a) and fluorescent spectra (b) for 1 upon the irradiation of UV-light at 300 nm.

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Table 1. Crystal data and structure refinement for 1

Empirical formula Formula weight Crystal size (mm) Crystal system Space group, Z a (Å) V (Å3)

ρcalcd (g·cm3) µ (mm-1) F(000) λ( Mo–Kα) (Å)

T (°K) θ Range (°) Collected reflections Unique reflections Observed reflections Rint GOF R indices (for obs.): R1 a, wR2b R indices (for all): R1, wR2 Largest diff. peak/hole (e.Å-3) a

1 (CCDC 1496656) C80H102N12O17 1503.73 0.13×0.13×0.11 Cubic Fd-3, 8 25.5160(3), 16612.6(6) 1.202 0.085 6416 0.71073 173(2) 2.77 – 24.99 27062 1234 1050 (>2σ (I)) 0.0702 1.007 0.0961, 0.2975 0.1089, 0.3111 0.41/ -0.39

R1 = ∑(||Fo|–|Fc||)/∑|Fo|, wR2 = {∑w[(Fo2–Fc2)2]/∑w[(Fo2)2]}1/2; bw = 1/[σ2(Fo2)+(aP)2+bP], where P =

(Fo2+2Fc2)/3].

15



Geometrical parameters for 1 [Å and º]. Hydrogen bond D-H...A d(D-H) d(H...A) N-H(0B)...O(3a) 0.88 2.52 C(4)-H(4A)...O(3a) 0.95 2.55 O(1)-H(11)...O(2b) 0.85 1.97 O(2)-H(22)...O(1) 0.85 1.98 O(2)-H(21)...O(3a) 0.85 1.97 O(3)-H(31)...N(c) 0.85 2.04 O(3)-H(32)...O(3d) 0.85 2.22 O(3)-H(33)...O(2) 0.85 2.03 Dimensions of water cluster O...O...O O...O...O ∠(OOO) O2...O1...O2 109.47 O3...O2...O3 O1...O2...O3 105.62 O3...O3...O2 Bond lengths of tatp N-C(5) 1.399(5) C(4)-C(5) C(1)-C(3) 1.534(4) C(5)-C(6) C(2)-C(8) 1.513(5) C(6)-C(7) C(3)-C(8) 1.377(6) C(7)-C(8) C(3)-C(4) 1.385(5)

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Table 2.

∠(DHA) 148.6 144.4 179.4 179.3 170.8 169.0 126.8 153.0

d(D...A) 3.307(6) 3.367(6) 2.824(6) 2.824(6) 2.810(4) 2.878(5) 2.815(8) 2.810(4)

∠(OOO) 113.03 107.39 1.401(6) 1.386(7) 1.383(6) 1.386(6)

Symmetry transformations used to generate equivalent atoms: (a) -z+3/4,-x+5/4,y-1/2; (b) x,-y+3/4,-z-1/4; (c) z+5/4,x-3/4,-y; (d) -x+7/4,y,-z-1/4

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Figure 1. The ORTEP diagram of compound 1 (ellipsoids at 25 % probability) depicting the tatp molecule associated with its lattice water guests, the hydrogen atoms of lattice water are omitted for clarity. Symmetry key: (a) 1+z, -0.5+x, -0.5+y; (b) 0.5+y, 0.5+z, -1+x; (c) 1.25-y, 0.25-z, -1+x; (d) 1.25-y, 0.5+z, 0.75-x; (e) 0.5+y, 0.25-z, 0.75-x; (f) 1.75-x, y, -0.25-z; (g) 0.75-z, 1.25-x, -0.5+y; (h) 1.75-x, 0.75-y, z; (i) x, 0.75-y, -0.25-z; (j) 0.75-z, -0.5+x, 0.25-y; (k) 1+z, 1.25-x, 0.25-y.

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(a)

(b)

(c)

(d)

Figure 2. (a) A view of a sod-cage possesses a large host cavity of ~8.5 Å in diameter in 1 generated by the self-sorting of four tatp molecules via weak molecular N−H···N (4.369−4.835 Å) interactions. (b) Schematic illustration showing the sod-cage with large host cavity accessible to a bigger (H2O)17 water cluster guest species based on 1. (c) A view showing how an elegant (H2O)17 heptadecameric water cluster guest assembled by the hydrogen-bonded network of the lattice water molecules in 1. Hydrogen bond lengths and angles are listed in Table 2. (d) Crystal packing of 1 showing how a sod-cage (highlight by red) fused to six nearest neighboring sod-cages through its 4-ring windows along three lattice axes to give a host zeolite-type porous supramolecular network.

18


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Figure 3. Comparison of powder patterns of polycrystalline sample treated by different ways showing that crystalline phase of 1 kept after (a) calculation based on single crystal data, (b) exposured on air in darkness for 1 year, (c) dehydrated under vacuum at 60 °C, (d) dehydrated under vacuum at 100 °C, (e) dehydrated under vacuum at 150 °C, (f) the dehydrated sample of 150 °C dipped in water. (g) dehydrated (~13.8% weight loss) on a desiccator with phosphorous pentaoxide, and (h) the desiccated sample dipped in water.

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hv

(a)

(b) Figure 4. Solid state UV-visible (a) and fluorescent spectra (b) for 1 upon the irradiation of UV-light at 300 nm.

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For Table of Contents Use Only

Supramolecular Network of Triaminotriptycene and Its Water Cluster Guest: Synthesis, Structure, and Characterization of [(tatp)4·17H2O]n Li Liu, Yun Zhang, Xiao-Li Wang, Geng-Geng Luo*, Zi-Jing Xiao, Lin Cheng* and Jing-Cao Dai*

hv

Four star-shaped triaminotriptycene molecules are self-sorted into a sodalite-like cage with a large host cavity of ~8.5 Å in diameter to capture a bigger-sized heptadecameric water cluster guest in the hydrated triaminotriptycene solid, [(tatp)4·17H2O]n (1) (tatp= 2,6,12triaminotriptycene), that exhibits an interesting light response behavior with the crystal color conversion from pale yellow to brown under the xenon lamp or sunlight irradiation.

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Supramolecular Network of Triaminotriptycene and Its Water Cluster

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