Strong-Acid-Templated Construction of a Metallosupramolecular

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Strong-Acid-Templated Construction of a Metallosupramolecular Architecture: Reversible Ammonia Adsorption in Aqueous Media in a Single-Crystal-to-Single-Crystal Conversion Manner Takuma Itai, Nobuto Yoshinari, Tatsuhiro Kojima, and Takumi Konno Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01715 • Publication Date (Web): 15 Feb 2017 Downloaded from http://pubs.acs.org on February 19, 2017

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Crystal Growth & Design

Strong-Acid-Templated Construction of a Metallosupramolecular Architecture: Reversible Ammonia Adsorption in Aqueous Media in a SingleCrystal-to-Single-Crystal Conversion Manner Takuma Itai, Nobuto Yoshinari, Tatsuhiro Kojima, and Takumi Konno* Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 5600043 JAPAN

ABSTRACT: Creation of an acidic metallosupramolecular architecture templated by a strong Brønsted acid (HClO4) and its reversible adsorption/release of ammonia molecules in aqueous media are reported. The 1:1 reaction of a digold(I) metalloligand, [Au2(trans-dppee)(D-Hpen)2] ([H21]), with Ni(OAc)2 yielded an {AuI2NiII}n 1D coordination polymer ([2]). A similar reaction with Ni(ClO4)2 produced an AuI4NiII2 hexanuclear complex, which co-crystallized with HClO4 to form a metallosupramolecular structure in [3]·2HClO4; the metallosupramolecular structure consisted of {AuI4NiII2}6 octahedra and {ClO4–}10 adamantanes, together with H3O+ ions. Compound [3]·2HClO4 was single-crystal-to-single-crystal converted to [3]·2NH4ClO4 via treatment with aqueous ammonia; its reverse conversion was achieved via treatment with aqueous perchloric acid.

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Introduction Incorporation of target molecules/ions into host frameworks has received much attention in many research fields, including supramolecular chemistry and materials science. This attention is a consequence of the importance of this process not only for expanding fundamental understanding of host-guest interactions1,2 but also for producing functional materials for chemical sensing, molecular recognition, and catalysis.3–9 To date, a variety of guest species, such as inorganic anions,10 metal cations,11 organic molecules,12,13 and metal complexes,14,15 have been incorporated in host frameworks. In some cases, the constructed host frameworks are drastically transformed in response to the guest species; this phenomenon is referred to as the template effect. In addition, the encapsulation of functional guest species enables to provide new functionality (guest-induced functionality) for the host framework.16–18 Whereas acidincorporated materials have been proposed to be highly applicable as acid catalysts, baseresponsive sensors, and base scavengers,19–25 reported examples that introduce strong Brønsted acids as a template are limited in number; only weak acids, such as boronic acids and protonated nucleobases, have been used as a template.26–28 In this communication, we report a unique example of a strong-acid-templated construction of a metallosupramolecular structure based on a digold(I) metalloligand, [Au2(trans-dppee)(DHpen)2] ([H21], trans-dppee = trans-1,2-bis(diphenylphosphino)ethylene, D-H2pen = Dpenicillamine) (Scheme 1). Whereas the reaction of [H21] with basic Ni(OAc)2 in methanol yields an infinite {AuI2NiII}n 1D coordination polymer, i.e., [Ni{Au2(trans-dppee)(D-pen)2}]n ([2]), a similar reaction with acidic Ni(ClO4)2 produces a discrete hexanuclear AuI4NiII2 complex, i.e., [Ni2{Au2(trans-dppee)(D-pen)2}2] ([3]), which co-crystallizes with HClO4 to yield [3]·2HClO4 (Scheme 1). In [3]·2HClO4, six AuI4NiII2 hexanuclear molecules are self-assembled


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into a neutral {[AuI4NiII2]}6 supramolecular octahedron, and ten ClO4– ions are aggregated into an anionic {ClO4–}10 adamantane. Remarkably, [3]·2HClO4 was observed to adsorb NH3 molecules and to be converted into [3]·2NH4ClO4 when soaked in aqueous ammonia, with retention of its crystallinity (Scheme 1). Such a construction of an acidic supramolecular structure template using a strong Brønsted acid and its single-crystal-to-single-crystal conversion to a neutral structure via adsorption of base molecules are unprecedented.29 The reverse, singlecrystal-to-single-crystal conversion from [3]·2NH4ClO4 to [3]·2HClO4 also occurs when [3]·2NH4ClO4 is soaked in aqueous HClO4.

Scheme 1. Schematic of the formation of the 1D structure in [2] and the acidic supramolecular structure in [3]·2HClO4, showing reversible conversion to [3]·2NH4ClO4 in aqueous media. Results and Discussion The digold(I) metalloligand, [H21], was newly prepared via the reaction of [Au2Cl2(transdppee)] 30 with D-H2pen in a 1:2 ratio in ethanol/water, according to the procedure used for other


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[Au2(diphosphine)(D-Hpen)2]-type metalloligands.31–33 Compound [H21] was confidently assigned to [Au2(trans-dppee)(D-Hpen)2] on the basis of the IR (Figure S1) and 1H NMR spectroscopy results (Figure S2), together with the results of the X-ray fluorescence and elemental analyses.34 The molecular structure of [H21] was determined via single-crystal X-ray analysis. As shown in Figure 1a, [H21] has a linear-type digold(I) structure in which two {Au(DHpen)} moieties are linked by trans-dppee such that each AuI ion has a linear geometry bound by P and S donors (Figure 1a).

Figure 1. Perspective views of (a) [H21] and (b) [2]. Color code: Au, red; Ni, blue; P, orange; S, yellow; O, pink; N, pale blue; C, gray; H, light gray. H atoms in [2] are omitted for clarity. For the [Au2(diphosphine)(D-Hpen)2]-type metalloligand, three coordination modes, i.e., chelating, closed-bridging, and extended-bridging, are possible (Chart S1).31,34 When [H21] was reacted with Ni(OAc)2·4H2O at a 1:1 ratio in MeOH, a green solution was obtained. From this reaction solution, green platelet crystals ([2]) were isolated via vapor diffusion of CH3CN. Subsequent elemental and X-ray fluorescence spectroscopic analyses implied that [2] contains [Au2(trans-dppee)(D-pen)2]2– and Ni2+ in a 1:1 ratio. Its IR spectrum showed an intense C=O


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stretching band at 1593 cm–1, indicative of the presence of deprotonated COO– groups (Figure S1).34,35 The purity and crystallinity of the bulk sample of [2] were confirmed by the powder Xray diffraction results (Figure S3).34 Single-crystal X-ray analysis revealed that [2] has an infinite [AuI2NiII]n 1D chain structure in [Ni{Au2(trans-dppee)(D-pen)2}]n, in which [1]2– has an extended-bridging mode to NiII (Figure 1b). In [2], each NiII ion has a trans(O)-N2O2S2 octahedral geometry, coordinated by two tridentate-N,O,S D-pen ligands (Figure S4a). This infinite structure in [2] is in sharp contrast to that in the corresponding dppe (1,2-bis(diphenylphosphino)ethane) system, in which the [Au2(dppe)(D-pen)2]2– metalloligand has a closed-bridging mode, thus forming an AuI4NiII2 hexanuclear structure in [Ni2{Au2(dppe)(D-pen)2}2] (Figure S5a).34,36 In these complexes, AuI and NiII centers are bridged by thiolate S atoms from D-pen. Similar Ni-S-Au structures have been widely observed in gold(I)-nickel(II) complexes having square-planar or octahedral nickel(II) dithiolate species.37–39 Treatment of [H21] with Ni(ClO4)2·6H2O instead of Ni(OAc)2·4H2O under otherwise identical conditions yielded a pale-yellow solution, from which green crystals with a trigonalpyramid shape ([3]·2HClO4) were isolated after the addition of a small amount of base.34 The elemental analytical results for this compound were consistent with the formula ([3]·2HClO4·6H2O) containing [1]2–, NiII, and HClO4 in a 1:1:1 ratio. Its IR spectrum showed an intense C=O stretching band due to deprotonated COO– groups at 1591 cm–1, with a shoulder at the higher-energy side. This IR spectral feature suggests that H+ ions exist near the COO– groups. The IR spectrum also indicated the presence of ClO4– ions. On the basis of these results, we assumed that HClO4 was incorporated into the green crystals because of the acidic nature of the solution containing Ni(ClO4)2.


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The crystal structure of [3]·2HClO4 was precisely determined via synchrotron-radiation Xray analysis. As shown in Figure 2a, [3] has a discrete AuI4NiII2 hexanuclear structure in [Ni2{Au2(trans-dppee)(D-pen)2}2].34 In [3], each metalloligand adopts a closed-bridging mode such that two NiII ions are spanned by two metalloligands. As in [2], each NiII ion has a trans(O)N2O2S2 octahedral geometry, coordinated by two tridentate-N,O,S D-pen ligands (Figure S4b).34 The AuI4NiII2 hexanuclear structure in [3] is very similar to that observed in [Ni2{Au2(dppe)(Dpen)2}2].36 However, the aggregation mode of the AuI4NiII2 hexanuclear molecules in [3]·2HClO4 is differs substantially from that in [Ni2{Au2(dppe)(D-pen)2}2]. That is, the hexanuclear molecules in [3]·2HClO4 are self-assembled into a supramolecular octahedron of {[AuI4NiII2]}6 through CH···π and H2N···OCO hydrogen-bonding interactions, accommodating a ClO4– ion in the center (Figure 2b), whereas the AuI4NiII2 hexanuclear molecules in [Ni2{Au2(dppe)(Dpen)2}2] are connected with one another through intermolecular H2N···OCO hydrogen bonds, thus forming a 1D chain (Figure S5b). In [3]·2HClO4, the supramolecular octahedra are closely packed in a face-centered cubic (fcc) structure by forming intercluster CH···π interactions (Figure S6a).34 A similar fcc structure composed of {[AuI4CoIII2]2+}6 supramolecular octahedra has been observed in inorganic salts of the cationic AuI4CoIII2 complex, i.e., [Co2{Au2(dppe)(D-pen)2}2]2+ ([4]2+).32,33 The fcc structure involves a type of octahedral interstice and two types of larger tetrahedral interstices, with one being hydrophilic, surrounded by amine and carboxylate groups, and with the other being hydrophobic, surrounded by phenyl and methyl groups (Figure S6b).34 In [3]·2HClO4, each octahedral interstice, hydrophilic tetrahedral interstice, and hydrophobic tetrahedral interstice accommodates a ClO4– ion, ten ClO4– ions that form an adamantane-like arrangement, and a number of water molecules that form a large water cluster, respectively (Figures 3, S7).34,40


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Figure 2. Perspective views of (a) the AuI4NiII2 complex molecule of [3] and (b) the {[AuI4NiII2]}6 supramolecular octahedron, with a ClO4– ion in [3]·2HClO4. Color code: Au, red; Ni, blue; P, orange; S, yellow; O, pink; N, pale blue; C, gray; Cl, green. The ClO4– ion is represented in a space-filling model.

Figure 3. A perspective view of the packing structure in [3]·2HClO4. The ClO4– ions in the supramolecular octahedrons and the {ClO4–}10 adamantanes are represented in a space-filling model, with sky-blue color for O atoms. The O atoms in the water cluster are represented using a space-filling model with blue color. Color code: Au, red; Ni, blue; P, orange; S, yellow; O, pink; N, pale blue; C, gray; Cl, green.


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A detailed inspection of the structure of [3]·2HClO4 revealed the presence of a water molecule on each of the four trigonal faces of the {[AuI4NiII2]}6 octahedron, forming strong hydrogen bonds (O··O = 2.69 Å) with three D-pen carboxylate groups from three different AuI4NiII2 complex molecules (Figure S8a).34 Because of the strong hydrogen bond, each carboxylate group has asymmetric C-O bonds (1.23 Å, 1.27 Å), consistently with the IR spectral features. Moreover, four water molecules were observed inside each {ClO4–}10 adamantane (Figures 4a, 4b), each of which are hydrogen-bonded (O··O = 2.71 Å) with three oxygen atoms from three different ClO4– ions located at the octahedral site (site A) of the adamantane (Figure S9a), rather than from those located at its tetrahedral site (site B).34 The aforementioned water molecules that form hydrogen bonds with three adjacent O atoms are assumed to be protonated to form H3O+ ions. The existence of additional four protons is required to compensate for the negative charge of the ClO4– ions in [3]·2HClO4. We speculate that these protons are involved in the water cluster.


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Figure 4. Perspective views of (a) the {ClO4–}10 adamantane (space-filling and stick models) and (b) the {ClO4–}10 adamantane with H3O+ ions (pink balls) in [3]·2HClO4. Perspective views of (c) the {ClO4–}10 adamantane (space-filling and stick models) and (d) the {ClO4–}10 adamantane with NH4+ ions (blue balls) in [3]·2NH4ClO4. The Cl atoms of ClO4– ions at site A and site B are green and orange, respectively. To investigate whether [3]·2HClO4 exhibits adsorption capability with respect to base molecules, green single crystals of [3]·2HClO4 were soaked in a 0.1 M aqueous solution of NH3 overnight. The shapes of the crystals remained unchanged, and the PXRD pattern of the crystals after this treatment were essentially the same as those of [3]·2HClO4. Although the presence of ClO4– ions in [3]·2NH4ClO4 was confirmed by its IR spectrum, the C=O stretching shoulder observed in the spectrum of [3]·2HClO4 nearly disappeared. Moreover, the elemental analysis results for [3]·2NH4ClO4 were consistent with the formula ([3]·2NH4ClO4·6H2O) containing NH4ClO4, instead of HClO4 in [3]·2HClO4, thus suggesting the incorporation of NH3 molecules during the treatment with aqueous NH3. Synchrotron-radiation X-ray analysis was also carried out for [3]·2NH4ClO4 and demonstrated the single-crystal-to-single-crystal conversion from [3]·2HClO4 to [3]·2NH4ClO4 (Figure S10).34 The overall structure in [3]·2NH4ClO4 is very similar to that in [3]·2HClO4, having an fcc structure comprising the {[AuI4NiII2]}6 supramolecular octahedra (Figure S11).34 Moreover, the octahedral interstices, the hydrophilic tetrahedral interstices, and the hydrophobic tetrahedral interstices in [3]·2NH4ClO4 each accommodate one ClO4– ion, ten ClO4– ions with an adamantane-like arrangement, and a water cluster, respectively.40 However, in [3]·2NH4ClO4, the orientation of four ClO4– anions located at site B of the {ClO4–}10 adamantane appears to be opposite that in [3]·2HClO4 (Figure 4c). The four small molecules inside the {ClO4–}10


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adamantane are each hydrogen-bonded not only with the ClO4– ions at site A (N··O = 2.95 Å) but also with those at site B (N··O = 2.77 Å) (Figures 4d, S9b).34 This structural feature is rationalized by the replacement of the H3O+ ions inside the {ClO4–}10 adamantane with symmetrical NH4+ ions, which allows for the formation of flexible hydrogen-bonding interactions with all of the surrounding ClO4– ions. A detailed structural comparison between [3]·2HClO4 and [3]·2NH4ClO4 also revealed that the hydrogen-bond distances between the H3O+ ion and the three D-pen carboxylate groups in [3]·2HClO4 (O··O = 2.69 Å) are elongated in [3]·2NH4ClO4 (N··O = 2.81 Å) (Figure S8b).34 This elongation suggests that H3O+ was replaced with NH4+ given that N-H···O hydrogen bonds are commonly weaker than O-H···O bonds.41 The disappearance of the C=O stretching shoulder in the IR spectrum of [3]·2NH4ClO4 is consistent with this possibility. On the basis of the elemental analysis results, [2] with a 1D chain structure was confirmed not to adsorb NH3 molecules during treatment with aqueous NH3 under the same conditions, although its crystallinity was retained during the treatment. The same result was also obtained when [4](ClO4)2 was treated with aqueous NH3, although [3]·2HClO4 and [4](ClO4)2 have nearly the same fcc structure. Thus, the presence of H3O+ ions is essential for the adsorption of NH3 molecules in [3]·2HClO4 from aqueous ammonia. Notably, [3]·2NH4ClO4 easily reverted back to [3]·2HClO4, with retention of the crystallinity, when immersed in an aqueous solution of HClO4 (0.01 M) overnight. The [3]·2HClO4 thus obtained was characterized by IR spectroscopy, elemental analysis, and single-crystal and powder X-ray analyses (Figures S3, S12).34 Finally, [3]·2HClO4 was exposed to ammonia gas to verify the conversion to [3]·2NH4ClO4. The analytical data showed that this treatment also produced [3]·2NH4ClO4 after a few hours in a single-crystal-to-single-crystal conversion manner. The reverse conversion was partially


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achieved when [3]·2NH4ClO4 was stored under vacuum at room temperature for 2 days. The reversible inclusion of polar solvent molecules, such as water and alcohols, in the non-porous crystal lattice through the single-crystal-to-single-crystal fashion have been reported in several diphosphine based discrete coordination systems.42–44 In these systems, the formation of hydrogen bonds and/or CH···π interactions between host framework and guest solvent molecules promotes the inclusion reaction. On the other hand, the reversible ammonia adsorption in the present system is induced by the unprecedented acid-base neutralization between template acid (HClO4) and guest base (NH3) molecules. Conclusion In summary, we showed an unprecedented template effect due to HClO4, which led to the formation of acidic crystals of [3]·2HClO4. Its molecular and supramolecular structures differ completely from those of neutral crystals of [2], which are formed under neutral conditions. Importantly, [3]·2HClO4 adsorbs NH3 molecules from aqueous ammonia and produces [3]·2NH4ClO4, which is easily reverted back to [3]·2HClO4 in a single-crystal-to-single-crystal conversion manner. Although the removal of ammonia from aqueous media is an important issue in environmental and biological sciences,45,46 to our knowledge, this system represents the first example of a coordination system that exhibits reversible adsorption of NH3 molecules in aqueous media; the incorporation of NH3 molecules into metal-organic frameworks has been reported, but this incorporation has been achieved only through the use of gaseous ammonia.47–50 The results obtained in the present study should provide substantial insight into the design and creation of metallosupramolecular systems using strong Brønsted acids as templates that can potentially adsorb target base molecules from aqueous media.


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ACKNOWLEDGMENT This work was supported by CREST, JST and Grants-in-Aids for Science Research (No. 15K21127) from the Ministry of Education, Culture Sports, Science and Technology of Japan. The synchrotron radiation experiments were performed at the BL02B1 and BL02B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2013B1036, 2014B1391, 2014B1021, 2014B1022) and at the 2D beam-line in the Pohang Accelerator Laboratory supported by POSTECH.

ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Experimental procedures and spectral data (PDF) Crystallographic data for [H21] (CIF) Crystallographic data for [2] (CIF) Crystallographic data for [3]·2HClO4 (CIF) Crystallographic data for [3]·2NH4ClO4 (CIF)

AUTHOR INFORMATION Corresponding Author *[email protected] Notes The authors declare no competing financial interests.


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(28) Feng, X.; Chen, K.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.; Tao, Z.; Day, A. I. CrystEngComm, 2011, 13, 5049–5051. (29) Single-crystal-to-single-crystal transformations are normally induced by solvent, temperature, light, and mechanical force, etc.51 The present study reports an unprecedented single-crystal-to-single-crystal transformations driven by adsorption of ammonia in reversible fashion. (30) Mirabelli, C. K.; Hill, D. T.; Faucette, L. F.; McCabe, F. L.; Girard, G. R.; Bryan, D. B.; Sutton, B. M.; Bartus, J. O. L.; Crooke, S. T.; Johnson, R. K. J. Med. Chem. 1987, 30, 2181– 2190. (31) Yoshinari, N.; Kakuya, A.; Lee, R.; Konno, T. Bull. Chem. Soc. Jpn. 2015, 88, 59–68. (32) Lee, R.; Igashira-Kamiyama, A.; Okumura, M.; Konno, T. Bull. Chem. Soc. Jpn. 2013, 86, 908–920. (33) Yoshinari, N.; Konno, T. Chem. Rec. 2016, 16, 1647–1663. (34) For detailed information on preparation procedures and characterization data, please see the Supporting Information. (35) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley, New York, 1997. (36) Igashira-Kamiyama, A.; Matsushita, N.; Lee, R.; Tsuge, K.; Konno, T. Bull. Chem. Soc. Jpn. 2012, 85, 706–708. (37) Denny, J. A.; Darensbourg, M. Y. Chem. Rev. 2015, 115, 5248–5273.


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(38) Pinder, T. A.; Montalvo, S. K.; Lunsford, A. M.; Hsieh, C.-H.; Reibenspies, J. H.; Darensbourg, M. Y. Dalton Trans. 2013, 43, 138–144. (39) Taguchi, M.; Igashira-Kamiyama, A.; Kajiwara, T.; Konno, T. Angew. Chem. Int. Ed. 2007, 46, 2422–2425. (40) [3]·2HClO4 and [3]·2NH4ClO4 were characterized by thermal gravity analyses, which showed the presence of water molecules (Figures S13, S14).34 (41) Steiner, T. Angew. Chem. Int. Ed. 2002, 41, 48–76. (42) Deák, A.; Tunyogi, T.; Károly, Z.; Klébert, S.; Pálinkás, G. J. Am. Chem. Soc. 2010, 132, 13627–13629. (43) Yoshinari, N.; Shimizu, T.; Nozaki, K.; Konno, T. Inorg. Chem. 2016, 55, 2030–2036. (44) Igawa, K.; Yoshinari, N.; Okumura, M.; Ohtsu, H.; Kawano, M.; Konno, T. Sci. Rep., 2016, 6, 26002. (45) Uğurlu, M.; Karaoğlu, M. H. Microporous Mesoporous Mater. 2011, 139, 173–178. (46) Lin, L.; Lei, Z.; Wang, L.; Liu, X.; Zhang, Y.; Wan, C.; Lee, D.-J.; Tay, J. H. Sep. Purif. Technol. 2013, 103, 15–20. (47) Britt, D.; Tranchemontagne, D.; Yaghi, O. M. P. Natl. Acad. Sci. U.S.A. 2008, 105, 11623– 11627. (48) Borfecchia, E.; Maurelli, S.; Gianolio, D.; Groppo, E.; Chiesa, M.; Bonino, F.; Lamberti, C. J. Phys. Chem. C 2012, 116, 19839–19850.


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(49) Spanopoulos, I.; Xydias, P.; Mal-liakas, C. D.; Trikalitis, P. N. Inorg. Chem. 2013, 52, 855– 862. (50) Wilcox, O. T.; Fateeva, A.; Katsoulidis, A. P.; Smith, M. W.; Stone, C. A.; Rosseinsky, M. J. Chem. Commun. 2015, 51, 14989–14991. (51) Li, C.-P.; Chen, J.; Liu, C.-S.; Du, M.; Chem. Commun. 2015, 51, 2768–2781.


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For Table of Contents Use Only Manuscript Title: Strong-Acid-Templated Construction of a Metallosupramolecular Architecture: Reversible Ammonia Adsorption in Aqueous Media in a Single-Crystal-to-SingleCrystal Conversion Manner Authors: Takuma Itai, Nobuto Yoshinari, Tatsuhiro Kojima, and Takumi Konno*

SYNOPSIS Creation of a metallosupramolecular system from a chiral digold(I) metalloligand and NiII, with a template of HClO4 is reported. This compound consists of neutral {AuI4NiII2}6 octahedra and anionic {ClO4–}10 adamantanes, together with H3O+ ions. This compound is demonstrated to reversibly adsorb NH3 molecules in aqueous media while retaining its crystallinity.


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Strong-Acid-Templated Construction of a Metallosupramolecular

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