Layered 2D Sheetlike Supramolecular Polymers Formed by O–H

Article pubs.acs.org/crystal

Layered 2D Sheetlike Supramolecular Polymers Formed by O−H···Anion Hydrogen Bonds Nicholas G. White, Veronica Carta, and Mark J. MacLachlan* Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada S Supporting Information *

ABSTRACT: A hexahydroxyterphenyl was prepared in two steps and 77% overall yield. Co-crystallization of this ligand with a range of tetrabutylammonium salts gave [2 + 2] supramolecular macrocycles assembled through O−H··· anion hydrogen bonds. These macrocycles form 2D sheetlike architectures through intermolecular hydrogen bonds between phenol groups. Bulk samples of these structures were prepared in high yields (70−100%) and were characterized by X-ray crystallography, 1H NMR spectroscopy, IR spectroscopy, and elemental analysis. The relatively predictable organization of these molecules in the solid state may be exploited for crystal engineering.

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and a fluorinated diol (Figure 1c, d) have high anion binding affinities,29−33 and Gale’s group has shown that a fluorinated diol (Figure 1e) is isosteric to, and binds oxoanions more strongly than, archetypal isophthalamide.34 Despite these important advances, O−H based anion receptors remain rare, and we are unaware of any attempts to use O−H···anion interactions to template the formation of higher order structures.35−37 Here, we demonstrate that O− H···anion hydrogen bonds can be used to prepare complex molecular architectures, namely 2D sheetlike structures composed of anion-templated supramolecular macrocycles.

INTRODUCTION Considerable effort has been devoted to studying the solution phase chemistry of anions, inspired by their key role in a range of biological and environmental processes.1 Research has focused on the preparation of selective anion receptors1−5 and the design of systems for the transport of anions across membranes,6−8 and some work has investigated the use of anions as templates for extended structures.1,9−12 Typical hosts for anions use N−H hydrogen bond donors, 13−16 and more recently C−H hydrogen bond donors17,18 and halogen bond donors19−22 have been effectively integrated into a range of receptors. The use of O−H groups as hydrogen bonding motifs to complex anions has received far less attention, despite the fact that natural systems for anion recognition are known to use such interactions.23−25 Nevertheless, a handful of important receptors based on O− H···anion interactions have been reported. Notably, in 2001 Sessler demonstrated that alizarin (Figure 1a) could sense anions in CH2Cl2 colorimetrically,26 and shortly after Smith discovered that catechol (Figure 1b) exhibited respectable chloride binding in polar acetonitrile.27,28 More recently, Wang, Kass, and co-workers have demonstrated that flexible polyols

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RESULTS AND DISCUSSION Synthesis. Synthesis of 1. Hexahydroxyterphenyl 1 has been reported in a patent,38 but we could find no mention of it in the academic literature. It was readily prepared in two steps and 77% overall yield from commercially available starting materials by adapting the methods described in this patent (Scheme 1). Suzuki coupling of 5-bromo-1,2,3-trimethoxybenzene and benzene-1,4-diboronic acid gave hexamethoxyterphenyl 2 after purification by recrystallization (2 appeared to decompose during silica gel column chromatography). Subsequent demethylation with excess boron tribromide in dichloromethane gave 1 in 97% yield. Compound 1 was characterized by 1H and 13C NMR spectroscopies and highresolution ESI mass spectrometry, as well as by single-crystal Xray crystallography (see Supporting Information). We made several attempts to condense 1 with aldehydes (using acid catalysis)39 to prepare bridged “double” pyrogallolarene bicycles, but without success (see Supporting Information). We also investigated the reaction of 1 with transition metal cations in the presence of base, to see if we could form Received: January 14, 2015 Revised: February 2, 2015

Figure 1. Examples of receptors that bind anions using O−H···anion hydrogen bonds.26,27,30−32,34 © XXXX American Chemical Society

A

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MS to probe the nuclearity of the complexes in solution or the gas phase were also unsuccessful. Solid-State Structures of 3·X. As discussed above, diffusion of diethyl ether vapor into an acetone solution containing a 1:1 mixture of 1 and TBA·X gave single crystals of 3·X (we were also able to obtain single crystals of [1·(TBA· Br)2]; see Supporting Information). In all cases, the structures of 3·X crystallize in noncentrosymmetric space groups (P21 when X = Cl, Br, I, and NO3; Pna21 when X = HSO4) and contain two molecules of 1, two anions, and two TBA cations in the asymmetric unit cell. In the structures of 3·Cl, 3·Br, 3·I, and 3·NO3 the two ligands are in different environments, with the twists between the aromatic rings in one ligand in the same direction but in alternate directions in the other ligand (such that the two pyrogallol moieties are close to coplanar, see Supporting Information Table S1). In the structure of 3·HSO4, both ligands feature alternating twists, giving approximately coplanar pyrogallol rings. The two molecules of 1 and two anions form a supramolecular macrocycle, with the anions forming strong hydrogen bonds to two OH groups from one end of 1 and a hydrogen bond from one OH group from the other end of the molecule (Figure 3). The two TBA cations sit above and below this supramolecular macrocycle. Notably, significant changes in the size and shape of the anion do not affect the structure of these supramolecular macrocycles. Even when using HSO4−, an anion which contains a hydrogen bond donor group, the same structure forms. Hydrogen bonding parameters for the O−H···X− hydrogen bonds are collated in Supporting Information Table S2. These hydrogen bonds are consistently very short and quite directional. For structures containing oxoanions the H···X distance ranges between 69 and 75% of the sum of the van der Waals radii40 (%vdWH,X),41 while with the halide anions, these distances increase slightly following anion basicity trends (less basic anions giving longer hydrogen bonds, in terms of % vdWH,X). Comparison with the Cambridge Structural Database42 shows that these parameters are quite typical and that phenol···halide anion hydrogen bonds are generally very short (see Supporting Information Figure S16). Three of the phenol groups from each molecule of 1 are involved in hydrogen bonding to the anions; each of the remaining three phenol groups form a “triangular” arrangement of hydrogen bonds to two phenol groups from adjacent molecules of 1. These intermolecular triangular hydrogen bonds assemble the [2 + 2] supramolecular macrocycles into approximately planar 2D sheets (Figure 4 shows this arrangement in the structures of 3·Cl and 3·NO3). These O−H···O hydrogen bonds are again short, although significantly less directional than the O−H···X hydrogen bonds (Supporting Information Table S3). There is no noticeable difference in the intermolecular hydrogen bonds between the five 3·X structures. The overall architecture of the crystal structures is of alternating layers: one layer consisting of hydrogen-bonded 2D sheets of supramolecular macrocycles, themselves consisting of anions and 1. These anionic layers are separated by cationic layers consisting of TBA cations and solvent molecules (Figure 5). As well as forming polymeric supramolecular frameworks through anion coordination, preliminary investigations revealed that 1 could be used to form neutral hydrogen-bonded frameworks.43−45 While we have not undertaken a compre-

Scheme 1. Synthesis of 1

two-dimensional sheet architectures. However, in our initial studies we obtained deeply colored solutions, which rapidly precipitated highly insoluble brown powders that we were not able to characterize. Synthesis of 3·X. Initial qualitative 1H NMR experiments suggested that 1 binds anions in d6-acetone, as evidenced by downfield shifts of the phenol protons upon addition of TBA·X salts (X = Cl−, Br−, I−, NO3−, and HSO4−; addition of TBA· OAc and TBA·BzO caused immediate precipitation). Diffusion of diethyl ether vapor into these NMR samples gave single crystals, which were shown by X-ray crystallography (vide infra) to be 1:1 co-crystals of 1 and TBA·X, henceforth referred to as 3·X [i.e., ternary co-crystals (1·X·TBA)n]. Subsequently, we prepared “bulk” crystalline samples of 3·Cl, 3·Br, 3·I, 3·NO3, and 3·HSO4 by diffusing diethyl ether vapor into 1:1 stoichiometric mixtures of 1 and TBA·X in acetone. The samples were isolated in good yields (70−100%), and their composition was confirmed by 1H NMR spectroscopy, IR spectroscopy, and elemental analysis. We attempted to determine quantitative association constants for the binding of anions to 1. Unfortunately, in the presence of anions the phenol (OH) resonances of 1 become extremely broad, precluding quantitative binding studies (see Figure 2 for 1H NMR spectra of 1 and 3·Cl and Supporting Information for more details). Attempts to use DOSY NMR or MALDI-TOF

Figure 2. 1H NMR spectra of 1 and 3·Cl (10 mM in d6-acetone, 300 MHz). Peaks marked with asterisks correspond to residual NMR solvent and water resonances. B

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Figure 3. Supramolecular macrocycles in the solid state structures of (a) 3·Cl, (b) 3·Br, (c) 3·I, (d) 3·NO3, and (e) 3·HSO4. TBA cations, solvent molecules, and most hydrogen atoms are omitted for clarity.

Figure 5. Diagram showing alternating layers comprised of anions and 1 and TBA cations and solvents in the structure of 3·Cl (top) and 3· NO3 (bottom, the same arrangement is also seen in the structures of 3· Br, 3·I, and 3·HSO4). Figure 4. Diagram showing intermolecular hydrogen bonding leading to 2D sheet motifs in the structures of 3·Cl (top) and 3·NO3 (bottom, the same arrangement is also seen in the structures of 3·Br, 3·I, and 3· HSO4). The triangular hydrogen bonding motif is highlighted with a black oval.

solution of 1 and HMTA (HMTA = hexamethylenetetramine, see Supporting Information for further details).

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CONCLUSIONS A series of 2D sheetlike supramolecular polymers composed of supramolecular macrocycles were prepared by anion templation. Short hydrogen bonds between the anions and

hensive study, we obtained crystals of a framework of [1· (HMTA)2] by diffusing diethyl ether vapor into a DMF C

DOI: 10.1021/acs.cgd.5b00062 Cryst. Growth Des. XXXX, XXX, XXX−XXX

a

D

15290 27462 0.0300 0.0754

14105 42457 0.0327 0.0794

3·Br 2(C18H14O6)·2(C16H36N)·C3H6O·2 (Br) 1355.38 13.668(3) 19.384(4) 13.748(3) 90 106.219(3) 90 3497.3(12) 90 monoclinic P21 2 1.221

3·Cl

2(C18H14O6)·2(C16H36N)·C3H6O·2 (Cl) 1266.48 13.443(2) 19.383(3) 13.671(2) 90 105.615(3) 90 3430.6(9) 90 monoclinic P21 2 0.157

Platon-SQUEEZE47,48 applied, see Supporting Information for details.

formula weight a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) unit cell volume (Å3) temperature (K) crystal system space group Z absorption coefficient (μ/mm1) reflections (unique) reflections (all) R1 [I > 2σ(I)] wR2(F2) (all data)

chemical formula

Table 1. Selected Crystallographic Data for 3·X

16585 42825 0.0266 0.0682

1449.38 14.028(5) 19.233(6) 14.064(5) 90 107.618(6) 90 3616.4(20) 90 monoclinic P21 2 0.929

2(C18H14O6)·2(C16H36N)·C3H6O·2(I)

3·I

compound 3·NO3

8538 57077 0.0310 0.0792

2(C18H14O6)·2(C16H36N)·C3H6O·2 (NO3) 1319.60 13.963(4) 18.833(5) 14.460(4) 90 108.723(6) 90 3601.2(17) 90 monoclinic P21 2 0.088

3·HSO4

18914 98653 0.0588 0.1297

2(C18H14O6)·2(C16H36N)· 2(HO4S)a 1331.64 19.796(4) 17.583(4) 23.652(5) 90 90 90 8233(3) 90 orthorhombic Pna21 4 0.126

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hexahydroxyterphenyl 1 form a 2− supramolecular macrocycle. Intermolecular O−H···O hydrogen bonds link these macrocycles into 2D polymers, which stack into a layered structure with the sheets of supramolecular polymers alternating with cationic layers consisting of TBA cations and solvent molecules. This work demonstrates the utility of O−H···anion interactions for the preparation of supramolecular structures. Hexahydroxyterphenyl 1 forms supramolecular assemblies with anions with some predictability. We suggest that careful design of extended systems based on this motif may allow the deliberate synthesis of functional architectures assembled through O−H···anion hydrogen bonding.

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General Procedure for the Synthesis of 3·X. A solution of 1 in acetone (10 mM) was added to the solid tetrabutylammonium salt of the appropriate anion. The resulting clear solution was subjected to diethyl ether vapor diffusion, which in each case yielded large yellow or yellow-orange X-ray quality single crystals. These were washed with diethyl ether (3 × 2 mL) and then dried in vacuo. Due to the small scale of the reactions, yields are given to the nearest 5%. 3·Cl. According to the general procedure, the reaction of a solution of 1 in acetone (3.2 mL, 0.032 mmol) and solid TBA·Cl·3H2O (11 mg, 0.032 mmol) gave yellow-orange crystals. Yield: 20 mg (100%). 1 H NMR (d6-Acetone). 8.32 (br. s, 6H, OH), 7.54 (s, 4H, Ar-H), 6.69 (s, 4H, Ar-H), 3.40−3.45 (m, 8H, N−CH2), 1.75−1.86 (m, 8H, N−CH2−CH2), 1.42 (sextet, 3J = 7.4 Hz, 8H, N−CH2−CH2−CH2), 0.97 (t, 3J = 7.4 Hz, 6H, CH3). EA, calcd for C34H50NO6Cl = C 67.59, H 8.34, N 2.32%; found C 67.25, H 8.66, N 2.28%. IR (inter alia, ν/ cm−1): ∼3150 (v. broad s, O−H stretch), 1177 (s, C−O stretch), 1028 (s, C−O stretch). MPt: 214.5−215.5 °C. 3·Br. According to the general procedure, the reaction of a solution of 1 in acetone (3.5 mL, 0.035 mmol) and solid TBA·Br (11 mg, 0.035 mmol) gave yellow-orange crystals. Yield: 18 mg (80%). 1 H NMR (d6-Acetone). 7.94 (br. s, 6H, OH), 7.55 (s, 4H, Ar-H), 6.72 (s, 4H, Ar-H), 3.40−3.45 (m, 8H, N−CH2), 1.75−1.86 (m, 8H, N−CH2−CH2), 1.42 (sextet, 3J = 7.4 Hz, 8H, N−CH2−CH2−CH2), 0.97 (t, 3J = 7.4 Hz, 6H, CH3). EA, calcd for C34H50NO6Br = C 62.95, H 7.77, N 2.16%; found C 62.77, H, 8.06, N 2.12%. IR (inter alia, ν/ cm−1): ∼ 3150 (v. broad s, O−H stretch), 1177 (s, C−O stretch), 1027 (s, C−O stretch). MPt: decomposes ∼230 °C. 3·I. According to the general procedure, the reaction of a solution of 1 in acetone (3.2 mL, 0.032 mmol) and solid TBA·I (12 mg, 0.032 mmol) gave yellow-orange crystals. Yield: 19 mg (85%). 1 H NMR (d6-Acetone). 7.71 (br. s, 6H, OH), 7.54 (s, 4H, Ar-H), 6.75 (s, 4H, Ar-H), 3.44−3.49 (m, 8H, N−CH2), 1.78−1.88 (m, 8H, N−CH2−CH2), 1.44 (sextet, 3J = 7.4 Hz, 8H, N−CH2−CH2−CH2), 0.98 (t, 3J = 7.4 Hz, 6H, CH3). EA, calcd for C34H50NO6I = C 58.70, H 7.24, N 2.01%; found C 58.34, H 7.67, N 2.23%. IR (inter alia, ν/ cm−1): ∼ 3250 (v. broad s, O−H stretch), 1185 (s, C−O stretch), 1027 (s, C−O stretch). MPt: decomposes ∼230 °C. 3·NO3. According to the general procedure, the reaction of a solution of 1 in acetone (3.7 mL, 0.037 mmol) and solid TBA·NO3 (11 mg, 0.037 mmol) gave yellow-orange crystals. Yield: 16 mg (70%). 1 H NMR (d6-Acetone). 7.98 (br. s, 6H, OH), 7.55 (s, 4H, Ar-H), 6.74 (s, 4H, Ar-H), 3.40−3.46 (m, 8H, N−CH2), 1.76−1.86 (m, 8H, N−CH2−CH2), 1.42 (sextet, 3J = 7.4 Hz, 8H, N−CH2−CH2−CH2), 0.97 (t, 3J = 7.4 Hz, 6H, CH3). EA, calcd for C34H50N2O9 = C 64.74, H 7.99, N 4.44%; found C 64.71, H 8.31, N 4.17%. IR (inter alia, ν/ cm−1): ∼ 3250 (v. broad s, O−H stretch), 1183 (s, C−O stretch), 1034 (s, C−O stretch). MPt: decomposes ∼230 °C. 3·HSO4. According to the general procedure, the reaction of a solution of 1 in acetone (3.6 mL, 0.036 mmol) and solid TBA·HSO4 (12 mg, 0.036 mmol) gave yellow-orange crystals. Yield: 21 mg (85%). 1 H NMR (d6-Acetone). 7.55 (s, 4H, Ar-H), 6.74 (s, 4H, Ar-H), 3.39−3.45 (m, 8H, N−CH2), 1.74−1.84 (m, 8H, N−CH2−CH2), 1.42 (sextet, 3J = 7.4 Hz, 8H, N−CH2−CH2−CH2), 0.96 (t, 3J = 7.4 Hz, 6H, CH3) (OH peaks not visible). EA, calcd for C34H51NO10S = C 61.33, H 7.72, N 2.10%; found C 60.72, H 8.02, N 2.06%. IR (inter alia, ν/cm−1): ∼ 3300 (v. broad s, O−H stretch), 1179 (s, C−O stretch), 1153 (s, S−O stretch), 1029 (s, C−O stretch). MPt: 141− 142 °C. X-ray Crystallography. Single-crystal X-ray data were collected on a Bruker APEX DUO diffractometer using graphite monochromated Mo Kα radiation (λ = 0.71073 Å). All data were collected at 90 K to a resolution of 0.77 Å. Raw frame data (including data reduction, interframe scaling, unit cell refinement, and absorption corrections) for all structures were processed using APEX2.49 Structures were solved using SUPERFLIP50 and refined using full-matrix least-squares on F2 within the CRYSTALS suite.51 All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were generally visible in the Fourier difference map and were initially refined with restraints on bond lengths and angles, after which the positions were used as the basis for a riding model.52 Further refinement details

EXPERIMENTAL SECTION

Synthesis. General Comments. Dichloromethane was dried by storing it over 3 Å molecular sieves for at least 24 h before use. Otherwise, reagents and solvents were bought from commercial suppliers and used as received. 1 H and 13C NMR spectra were recorded on a Bruker AV-300 spectrometer and referenced to residual solvent signals.46 13C NMR spectra were recorded using a proton decoupled pulse sequence. Electrospray ionization mass spectra (ESI-MS) were obtained on a Bruker Esquire LC instrument. Melting points were recorded on a Stanford Research Systems Digimelt. Elemental analyses were performed at the UBC Microanalytical Services Laboratory. Hexamethoxyterphenyl 2. Benzene-1,4-diboronic acid (0.547 g, 3.30 mmol), 5-bromo-1,2,3-trimethoxybenzene (1.63 g, 6.60 mmol), Pd(PPh3)4 (0.17 g, 0.15 mmol), and Na2CO3 (3.5 g, 33 mmol) were placed in a flask. Ethanol (15 mL), dimethoxyethane (15 mL), and water (5 mL) were added, and the mixture was heated to 90 °C overnight under a nitrogen atmosphere. It was cooled to room temperature, and the organic solvents were removed under reduced pressure. The pale yellow suspension was diluted with 20 mL of additional water and extracted with DCM (3 × 30 mL). The combined organic layers were dried over MgSO4, filtered, and dried under reduced pressure. The pale yellow powder was dissolved in boiling toluene (60 mL), filtered hot to remove a small amount of insoluble brown solid, and then reduced in volume to 25 mL. Cooling gave the product as a slightly off-white feathery solid that was isolated by filtration, washed with cold toluene (3 × 3 mL), and dried in vacuo. Yield: 1.06 g (2.58 mmol, 79%). 1 H NMR (CDCl3): 7.64 (s, 4H, Ar-H), 6.82 (s, 4H, Ar-H), 3.95 (s, 12H, OCH3), 3.91 (s, 6H, OCH3). 13C NMR (CDCl3): 153.6, 140.4, 137.9, 136.8, 127.5, 104.5, 61.1, 56.3. HRESI-MS (pos.): 433.1628, calcd for [C24H26O6·Na]+ = 433.1627. IR (inter alia, ν/cm−1): 1237 (s, C−O stretch), 991 (s, C−O stretch). MPt: 211.0−211.5 °C. Note: this compound appears to decompose during chromatography on silica gel. Hexahydroxyterphenyl 1. Hexamethoxyterphenyl 2 (0.616 g, 1.50 mmol) was dissolved in dry CH2Cl2 (30 mL). The solution was cooled to −78 °C under a nitrogen atmosphere, and BBr3 (1.7 mL, 4.5 g, 18 mmol) was added dropwise. The reaction was stirred at −78 °C under nitrogen for an hour and then allowed to warm to room temperature under a nitrogen atmosphere overnight. It was again cooled to −78 °C, and water (30 mL) was cautiously added to quench the reagent. Organic solvents were removed under reduced pressure, and the graygreen aqueous suspension was extracted with EtOAc (60 mL, then 2 × 30 mL). The combined organic phases were washed with brine (60 mL), dried over Na2SO4, filtered, and dried under reduced pressure to give 1 as a sandy-brown powder. Yield: 0.476 g (1.46 mmol, 97%). 1 H NMR (d6-Acetone). 7.93* (s, 4H, OH), 7.54 (s, 4H, Ar-H), 7.40* (s, 2H, OH), 6.75 (s, 4H, Ar-H). 13C NMR (d6-acetone): 147.0, 140.2, 133.5, 132.9, 127.4, 106.6. HRESI-MS (neg.): 325.0714, calcd for [C18H13O6]− = 325.0712. IR (inter alia, ν/cm−1): 3449 (s, O−H stretch), 3392 (s, O−H stretch), 1183 (s, C−O stretch), 1019 (s, C− O stretch). MPt: >250 °C. *Peak disappears on addition of D2O. Note: the two OH resonances become broad and merge over time. See Supporting Information for more details. E

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are provided in the Supporting Information. Full crystallographic data in CIF format are provided as Supporting Information (CCDC numbers: 1043470−1043477).

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(22) Robinson, S. R.; Mustoe, C. L.; White, N. G.; Brown, A.; Thompson, A. L.; Kennepohl, P.; Beer, P. D. J. Am. Chem. Soc. 2015, 137, 499−507. (23) Pflugrath, J. W.; Quiocho, F. A. Nature 1985, 314, 257−260. (24) Luecke, H.; Quiocho, F. A. Nature 1990, 347, 402−406. (25) Dutzler, R.; Campbell, E. B.; Cadene, M.; Chait, B. T.; MacKinnon, R. Nature 2002, 415, 287−294. (26) Miyaji, H.; Sessler, J. L. Angew. Chem., Int. Ed. 2001, 40, 154− 157. (27) Smith, D. K. Org. Biomol. Chem. 2003, 1, 3874−3877. (28) Winstanley, K. J.; Sayer, A. M.; Smith, D. K. Org. Biomol. Chem. 2006, 4, 1760−1767. (29) Shokri, A.; Schmidt, J.; Wang, X.-B.; Kass, S. R. J. Am. Chem. Soc. 2012, 134, 2094−2099. (30) Shokri, A.; Schmidt, J.; Wang, X.-B.; Kass, S. R. J. Am. Chem. Soc. 2012, 134, 16944−16947. (31) Shokri, A.; Wang, X.-B.; Kass, S. R. J. Am. Chem. Soc. 2013, 135, 9525−9530. (32) Shokri, A.; Kass, S. R. Chem. Commun. 2013, 49, 11674−11676. (33) Wang and Kass’ group have also recently reported a tripodal alcohol-based anion receptor: Shokri, A.; Deng, S. H. M.; Wang, X.-B.; Kass, S. R. Org. Chem. Front. 2014, 1, 54−61. (34) Busschaert, N.; Jaramillo-Garcia, J.; Light, M. E.; Herniman, J.; Langley, G. J.; Gale, P. A. RSC Adv. 2014, 4, 5389−5393. (35) It should be noted that nearly 30 years ago Khan demonstrated that catechol formed discrete or 1D polymeric complexes with anions, with the nature of the complex dependent on the cation used (refs 36 and 37). (36) Khan, M. A.; McCulloch, A. W.; McInnes, G. A. Can. J. Chem. 1985, 63, 2119−2122. (37) Khan, M. A. J. Mol. Struct. 1986, 145, 203−218. (38) Yasuda, N.; Kakimoto, M.; Urushibata, H.; Hayakawa, T.; Maeda, R. Resin compositions and their cured products with good electrically insulating properties and thermal conductivity. Japanese Patent, JP2011153265, August 11, 2011. (39) Weinelt, F.; Schneider, H.-J. J. Org. Chem. 1991, 56, 5527−5535. (40) Alvarez, S. Dalton Trans. 2013, 42, 8617−8636. (41) See the Supporting Information for more details regarding the accuracy of these values. For a more detailed explanation of the advantages and disadvantages of using %vdWH,X to describe hydrogen bonding parameters, see: White, N. G.; Serpell, C. J.; Beer, P. D. Cryst. Growth Des. 2014, 14, 3472−3479. (42) Allen, F. H. Acta Crystallogr. 2002, B58, 380−388. (43) Yang, W.; Greenway, A.; Lin, X.; Matsuda, R.; Blake, A. J.; Wilson, C.; Lewis, W.; Hubberstey, P.; Kitagawa, S.; Champness, N. R.; Schröder, M. J. Am. Chem. Soc. 2010, 132, 14457−14469. (44) He, Y.; Xiang, S.; Chen, B. J. Am. Chem. Soc. 2011, 133, 14570− 14573. (45) Luo, X.-Z.; Jia, X.-J.; Deng, J.-H.; Zhong, J.-L.; Lui, H.-J.; Wang, K.-J.; Zhong, D.-C. J. Am. Chem. Soc. 2013, 135, 11684−11687. (46) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997, 62, 7512−7515. (47) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13. (48) van der Sluis, P.; Spek, A. L. Acta Crystallogr. 1990, A46, 194− 201. (49) APEX; Bruker AXS Inc.: Madison, WI, 2007. (50) Palatinus, L.; Chapuis, G. J. Appl. Crystallogr. 2007, 40, 786− 790. (51) Betteridge, P. W.; Carruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin, D. J. J. Appl. Crystallogr. 2003, 36, 1487. (52) Cooper, R. I.; Thompson, A. L.; Watkin, D. J. J. Appl. Crystallogr. 2010, 43, 1100−1107.

ASSOCIATED CONTENT

S Supporting Information *

1

H NMR spectra of new compounds and complexes, crystal structures of 1, 1·(TBA·Br)2, and 1·(HMTA)2, further crystallographic details including hydrogen bonding and ring twisting parameters for 3·X, full crystallographic information in CIF format, and details of attempts to prepare doubly bridged pyrogallolarene bicycles. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +1-604-822-3070. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank Hessam Mehr for assistance with DOSY NMR spectroscopy. N.G.W. thanks the Killam Foundation for a postdoctoral research fellowship and Drs. Brian Patrick, Christopher Serpell, and Amber Thompson for helpful discussions. We thank NSERC (Discovery Grant) for funding.

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DOI: 10.1021/acs.cgd.5b00062 Cryst. Growth Des. XXXX, XXX, XXX−XXX