Supramolecular Organic Frameworks of Brominated Bisphenol

ARTICLE pubs.acs.org/crystal

Supramolecular Organic Frameworks of Brominated Bisphenol Derivatives with Organoamines Jian L€u,† Li-Wei Han,†,‡ Jing-Xiang Lin,† and Rong Cao*,† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002, P. R. China ‡ Graduate School, Chinese Academy of Sciences, Beijing 100039, P. R. China

bS Supporting Information ABSTRACT: Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF2 )2 3 (HPZ+)2 3 (H2PZ2+) (1), (TBBPF )2 3 (H2PZ2+) 3 2H2O 3 2MeOH (2), (TBBPF) 3 (TBBPF ) 3 (HDABCO+) 3 H2O (3), (TBBPF) 3 (HMTA) (4), (TBBPA) 3 (HMTA) (5), and (TBBPA)3 3 (HMTA)3 3 H2O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1 6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1 6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 44-sql layer structure built by the four-connected {H2PZ2+} moieties and {TBBPF2 }. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/PZ in 2:1 ratio with the presence of solvent H2O and MeOH molecules, in which two identical pcu topological nets are recognized by choosing a decamer synthons as nodes. Compound 3 displays H-bonded 44-sql layer structure built by 2:1 TBBPF and DABCO, as well as one H2O per formula unit. Compounds 4 and 5 assemble into 1D (one-dimensional) H-bonded zigzag chains via the alternate linkage of HMTA with TBBPF/TBBPA in a similar fashion. Compound 6 generates an interesting hexamer subunit (HMTA 3 3 3 TBBPA 3 3 3 HMTA 3 3 3 TBBPA 3 3 3 HMTA 3 3 3 TBBPA), which can be viewed as a fragment of three repeating units for a zigzag chain observed in compound 5. A pair of the hexamer subunits is further connected by two water molecules to form an H-bonded molecular oligomer. Importantly, halogen bonds (X-bonds) have been observed in compounds 4 6 that exhibit 1D and 0D H-bonded supramolecular structures.

’ INTRODUCTION Crystalline materials of supramolecular organic frameworks (SOFs) are notable representatives in supramolecular chemistry because of both their structural complexity and physical properties of interest, in which the role of hydrogen bonds (H-bonds), as predominant driving forces, has been well-established.1 Investigation on compounds of organic entities built by paradigms of supramolecular synthons is currently undergoing a burgeoning development taken full advantage of crystal engineering concepts.2 4 However, predetermination of even the simplest molecular structure is a daunting challenge because the intermolecular forces for upholding the molecules are poorly understood and difficult to predict, especially for organic solids.5 Any step taken into predictable molecular assemblies is thereby a practical impetus toward the ultimate goal of solid-based crystal engineering. Most H-bonds are primarily electrostatic in nature and flexible in strength according to the different electron donors and acceptors. At the same time, notwithstanding their weak bonding and angular spreading pattern, H-bonds have been approved as directional and predictive intermolecular cohesive forces in r 2011 American Chemical Society

molecular packing.6 Among others, H-bonds as main driving forces in supramolecular assemblies of organic modules featuring functional carboxyl, pyridyl, or a mixture of the two have been comprehensively explored.2d,f,h,3e,3f,3h,7,8 It should also be noted that phenol amine interplay has been confirmed to be a type of stable and robust driving forces for the exploitation of new solid materials, and the well-defined O H 3 3 3 N bonds furnished in molecular compounds have been found productive for the generation of a wide variety of supramolecular aggregates.9 During the course of our investigations in crystal engineering of phenol amine salts and adducts, we recently discovered that halogenations of bis(4 hydroxyphenyl)sulfone (BPS) would boost the abilities of the functional phenols to form H-bonds in directing molecular assembly and recognition.10 Moreover, the halogenated bisphenol molecules tetrabromobisphenol-S (TBBPS) and tetrachlorobisphenol-S (TCBPS) were capable of cocrystallization with organoamines and dramatically resulted in organic compounds with fascinating structures and interesting Received: April 24, 2011 Revised: June 23, 2011 Published: July 11, 2011 3551

dx.doi.org/10.1021/cg200520w | Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design Scheme 1. Structures of the Bisphenol Derivatives and Organoamines

physical properties.10 On the other hand, it is only recent that heuristic principles have been presented to develop a rational crystal engineering of organic complexes relying on halogen bonds as intermolecular cohesive interactions.11 As a matter of fact, halogen bonding was soon proven as an effective supramolecular interaction in self-assembly processes and inspired considerable research interest in many realms including molecular recognition, drug receptor interaction, supramolecular organic conductors, and liquid crystals.12 In order to enrich phenol amine-based organic solids as well as to study the rules of molecular assemblies in this system and related ones, we have developed two new bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), which hold similar sizes, shapes, and arrangements of functional groups as their precedents, TBBPS and TCBPS. In this study, the brominated TBBPF and TBBPA molecules have shown reliable ability, due to the significant enhancement of hydroxyl groups in forming H-bonds, to react with various organoamines having sp3 N donors (Scheme 1), including piperazine (PZ), diazabicyclo[2.2.2]octane (DABCO), and hexamethylenetetramine (HMTA).

’ EXPERIMENTAL SECTION General. Elemental analyses (C, H, and N) were carried out with an Elementar Vario EL III analyzer. Infrared (IR) spectra were recorded with a PerkinElmer Spectrum One with KBr pellets in the range 400 4000 cm 1. 1H NMR was performed on a 400 MHz AVANCE III nuclear magnetic resonance spectrometer (BRUKER BIOSPIN). Thermogravimetric (TG) analysis was recorded with a TA SDT Q600 unit at a heating rate of 10 °C min 1 under nitrogen flow. X-ray powder diffractions (XRPD) of all samples were recorded on a Rigaku DMAX 2500 diffractometer using Cu KR radiation (λ = 1.54056 Å) at 40 kV and 30 mA, and diffraction patterns were collected over a 2θ range of 5 35°. Single-crystal X-ray diffractions were performed on an Oxford Xcalibur Eos diffractometer. Synthesis. [(C6H2OHBr2)2CH2] (TBBPF, tetrabromobisphenol-F). Bis(4-hydroxyphenyl)methane (BPF) (0.02 mol, 5.01 g) was dissolved in glacial acetic acid, and Br2 (0.08 mol, 12.8 g) was added to the above solution with magnetic stirring for 2 h. CAUTION: liquid Br2 should be handled with care. White precipitate TBBPF was collected by filtration and washed several times with cold ethanol. Yield ca. 84% (8.65 g). Anal. Calcd for C13H8O2Br4 (%) (M = 515.82): C, 30.27; H, 1.56. Found (%): C, 31.36; H, 1.54. IR characteristics (KBr, cm 1): 1801w, 1763w, 1737w, 1600w, 1554m, 1471s, 1435w, 1410m, 1328s, 1298m, 1269m, 1247s,

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1200m, 1174s, 1145m, 1122s, 1064w, 1037w, 926w, 913w, 875m, 859w, 825w, 792w, 738s, 713m, 660w, 576w, 559w, 501w. 1H NMR (DMSO-d6): σ 9.773 (s, Ar OH) ppm, σ 7.461 (s, Ar H) ppm, σ 3.738 (s, Ar CH2 Ar) ppm. [(C6H2OHBr2)2C(CH3)2] (TBBPA, tetrabromobisphenol-A). Bis(4-hydroxyphenyl)propane (BPA) (0.02 mol, 5.01 g) was dissolved in glacial acetic acid and kept at about 45 °C until the white solid completely dissolved, and Br2 (0.08 mol, 12.8 g) was added to the solution with magnetic stirring for 2 h. White precipitate TBBPA was collected by filtration and washed several times with cold ethanol. Yield ca. 56% (6.1 g). Anal. Calcd for C15H12O2Br4 (%) (M = 543.88): C, 33.13; H, 2.22. Found (%): C, 33.42; H, 2.07. IR characteristics (KBr, cm 1): 1774w, 1753w, 1557m, 1474vs, 1398s, 1365m, 1323s, 1274s, 1241s, 1198m, 1176s, 1161s, 1132s, 939w, 868s, 780m, 733s, 713m, 706m, 650w, 616m, 574m, 563w, 540w, 484w. 1H NMR (DMSO-d6): σ 9.819 (s, Ar OH) ppm, σ 7.328 (s, Ar H) ppm, σ 1.562 (s, Ar C CH3) ppm. [(C6H2OBr2)2CH2]2 3 (C4H8N2H)2 3 (C4H8N2H2) (1). A mixture of 1:2 TBBPF and piperazine (PZ) was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 1 were obtained within a day with a yield of ca. 38% (24.5 mg). Anal. Calcd for C38H46N6O4Br8 (%) (M = 1290.09): C, 35.38; H, 3.59; N, 6.51. Found (%): C, 35.17; H, 3.53; N, 6.47. IR characteristics (KBr, cm 1): 1635w, 1533w, 1435m, 1013s, 922m, 811m, 737m, 600w. [(C6H2OHBr2)CH2(C6H2OBr2)]2 3 (C4H8N2H2) 3 (CH3OH)2 3 (H2O)2 (2). A mixture of 1:1 TBBPF and PZ was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 2 were obtained within 2 days with a yield of ca. 33% (20.1 mg). Anal. Calcd for C32H38N2O8Br8 (%) (M = 1217.92): C, 31.56; H, 3.14; N, 2.30. Found (%): C, 30.38; H, 3.09; N, 2.28. IR characteristics (KBr, cm 1): 1645w, 1433m, 1295w, 1238w, 1179w, 1095w, 1016w, 990m, 926w, 816m, 788w, 728m, 596m, 581w. [(C6H2OHBr2)2CH2] 3 [(C6H2OHBr2)CH2(C6H2OBr2)] 3 (C6H12N2H) 3 (H2O) (3). A mixture of 1:1 TBBPF and diazabicyclo[2.2.2]octane (DABCO) was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 3 were obtained within 2 days with a yield of ca. 25% (14.5 mg). Anal. Calcd for C32H30N2O5Br8 (%) (M = 1161.86): C, 33.08; H, 2.60; N, 2.41. Found (%): C, 32.55; H, 2.67; N, 2.44. IR characteristics (KBr, cm 1): 1782w, 1637w, 1555m, 1465s, 1394m, 1314s, 1232m, 1126s, 1052m, 995w, 896w, 869m, 792w, 740s, 655w, 601s, 527s. [(C6H2OHBr2)2CH2] 3 (C6H12N4) (4). A mixture of 1:2 TBBPF and hexamethylenetetramine (HMTA) was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 4 were obtained within a day with a yield of ca. 36% (23.6 mg). Anal. Calcd for C19H20N4O2Br4 (%) (M = 656.03): C, 34.79; H, 3.07; N, 8.54. Found (%): C, 35.72; H, 3.03; N, 8.48. IR characteristics (KBr, cm 1): 1633w, 1555m, 1511w, 1478s, 1326s, 1297m, 1178w, 1065w, 988m, 924w, 868w, 814m, 782w, 740m, 729m, 654m, 595m, 580m, 516m. [(C6H2OHBr2)2C(CH3)2] 3 (C6H12N4) (5). A mixture of 1:2 TBBPA and HMTA was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 110 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 5 were obtained within a day with a yield of ca. 22% (15.1 mg). Anal. Calcd for C21H24N4O2Br4 (%) (M = 684.08): C, 36.87; H, 3.54; N, 8.19. Found (%): C, 36.07; H, 3.42; N, 8.13. IR characteristics (KBr, cm 1): 1658w, 1526w, 3552

dx.doi.org/10.1021/cg200520w |Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design

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Table 1. Crystal Data and Structure Refinement for Complexes 1 6 complexes formula

1 C38H46Br8N6O4

2 C32H38Br8N2O8

formula weight

1290.09

1217.92

temp (K)

a

3 C32H30Br8N2O5

4 C19H24Br4N4O2

5 C21H24Br4N4O2

6 C63H74Br12N12O7

1161.86

656.03

684 08

2070 26

293(2)

wavelength (A) cryst syst

monoclinic

monoclinic

0.71073 monoclinic

triclinic

triclinic

triclinic

space group

P21/c

P21/c

P21/c

P1

P1

P1

a (Å)

12.1305(4)

12.557(4)

13.9298(5)

8.0454(3)

7.3315(4)

13.5750(2)

b (Å)

12.3277(3)

19.349(5)

15.3719(5)

11.2431(6)

11.6404(8)

16.7167(2)

c (Å)

15.7747(5)

8.173(3)

17.7673(8)

12.4087(7)

14.9647(1)

18.585(3)

R (deg)

90

90

90

99 128(4)

103.659(6)

64.667(4)

β (deg)

106.318(4)

97.837(4)

105.553(4)

104.349(4)

102.636(5)

81.375(6)

γ (deg) vol (Å3)

90 2263.94(1)

90 1967.3(1)

90 3665.2(2)

91.335(4) 1071.34(9)

90.701(5) 1208.18(14)

72.956(6) 3643.1(8)

Z

2

2

4

2

2

2

GOF

0.858

1.095

0.574

0.902

0.908

0.809

R1a [I > 2σ(I)]

0.0416

0.0425

0.0323

0.0364

0.0452

0.0397

wR2a

0.0595

0.0973

0.0689

0.0698

0.0958

0.0774

R1 = ∑||Fo|

|Fc||/∑|Fo|; wR2 = {∑[w(Fo2

Fc2)2]/∑[w(Fo2)2]}1/2.

1472w, 1392w, 1274w, 1234m, 1173m, 1132m, 1051w, 1014s, 802m, 734w, 693w. [(C6H2OHBr2)2C(CH3)2]3 3 (C6H12N4)3 3 (H2O) (6). A mixture of 1:1 TBBPA and hexamethylenetetramine (HMTA) was added to 6 mL of methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at 110 °C for 3 days. After slow cooling to room temperature within 2 days, a clear solution formed and was allowed to evaporate in air. Colorless block crystals of 6 were obtained within 2 days with a yield of ca. 18% (12.4 mg). Anal. Calcd for C63H74N12O7Br12 (%) (M = 2070.26): C, 36.55; H, 3.60; N, 8.12. Found (%): C, 37.39; H, 3.53; N, 8.04. IR characteristics (KBr, cm 1): 1652w, 1536w, 1470w, 1393w, 1275w, 1230m, 1171m, 1132m, 1010s, 808m, 731w, 689w. X-ray Crystallography. Diffraction intensities for compounds 1 6 were collected on Oxford Xcalibur Eos diffractometer with graphite-monochromated Mo KR radiation (λ = 0.71073). Multiscan absorption corrections were performed with the CrysAlisPro program (Oxford Diffraction Ltd., Version 1.171.33.66). Empirical absorption corrections were carried out using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Structures were solved by direct methods and refined on F2 by full-matrix least-squares with the SHELXTL-97 program package.13 All the non-hydrogen atoms were refined anisotropically. CCDC 821470 821475 (1 6) contain the supplementary crystallographic data for this paper. Data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. A summary of the crystallographic data for compounds 1 6 is given in Table 1.

’ RESULTS AND DISCUSSION TBBPF and TBBPA were prepared from the reactions of bisphenol-F (BPF) and bisphenol-A (BPA) with bromine in glacial acetic acid, respectively. Cocrystallization of the bisphenol derivatives TBBPF and TBBPA with organoamines resulted in six organic compounds, formulated as (TBBPF2 )2 3 (HPZ+)2 3 (H2PZ2+) (1), (TBBPF )2 3 (H2PZ2+) 3 2H2O 3 2MeOH (2), (TBBPF) 3 (TBBPF ) 3 (HDABCO+) 3 H2O (3), (TBBPF) 3 (HMTA) (4), (TBBPA) 3 (HMTA) (5), and (TBBPA)3 3 (HMTA)3 3 H2O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine).

Crystal Structures of the Brominated Bisphenol Derivatives with Organoamines. (TBBPF2 )2 3 (HPZ+)2 3 (H2PZ2+) (1).

In the structure of compound 1, the ratio of TBBPF and PZ is 2:3 and the asymmetric unit contains one TBBPF and one and a half PZ moieties (Figure 1a). The crystallographically independent TBBPF molecule is fully deprotonated with its two hydroxyl protons transferred to the one and a half PZ moieties, respectively. Thus, there are both singly and doubly protonated PZ (HPZ+ and H2PZ2+) molecules in 1. Each TBBPF connects four PZ molecules (including two HPZ+ and two H2PZ2+), and each H2PZ2+ interacts with four TBBPF molecules via Ohydroxyl 3 3 3 H N hydrogen bonds (2.634 2.831 Å; Figure 2a,b),14 whereas the HPZ+ molecule connects to TBBPF with one N donor in an endon fashion (Figure 2c). In such a way, compound 1 is extended by H-bonds into a 2D supramolecular 44-sql layer in which the H2PZ2+ moieties act as nodes and TBBPF as linkers (Figure 2c). (TBBPF )2 3 (H2PZ2+) 3 2H2O 3 2MeOH (2). The asymmetric unit of compound 2 includes one TBBPF, one half of a PZ moiety, one methanol, and one water molecule (Figure 1b). The TBBPF molecule is singly deprotonated with one hydroxyl proton transferred to the half PZ moiety; thus the PZ molecules are doubly protonated (with a TBBPF/PZ ratio of 2:1). The hydrogen bonds (O 3 3 3 H 3 3 3 N and O 3 3 3 H 3 3 3 O) in compound 2 are somewhat intricate, in which a decamer supramolecular synthon built by four TBBPF, two PZ, two methanol, and two water molecules has been identified (Figure 3a). The decamer supramolecular synthon contains two 4-rings and four 5-rings comprising a double-corner-on cube. The network can be simplified as a six-connected uninodal (412 3 63)-pcu net (R-Po)15,16 by considering the decamer synthons as nodes (Figure 3b,c). Notably, the overall framework of compound 2 shows 2-fold interpenetration of two identical pcu nets (Figure 3c). (TBBPF) 3 (TBBPF ) 3 (HDABCO+) 3 H2O (3). The asymmetric unit of compound 3 contains two TBBPF, one DABCO, and a water molecule (Figure 1c). One of the two TBBPF molecules is singly deprotonated with one proton transferred to the DABCO molecule. The water molecules act as bridges to connect the TBBPF and TBBPF molecules via Ow 3 3 3 H 3 3 3 Ophenol interacttions (2.684 2.897 Å) and result in a double-chain subunit 3553

dx.doi.org/10.1021/cg200520w |Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design

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Figure 1. ORTEP drawing of the basic building units in compounds 1 6 (a f) with thermal ellipsoids at 30% probability.

Figure 2. View of the hydrogen bonds between TBBPF and PZ (a, b) and the 2D supramolecular 44-sql layer of compound 1 (c, the end-on PZ molecules are highlighted in green).

Figure 3. View of the interconnection between the decamer synthon (a), the 3D supramolecular structure of compound 2 (b), and the topological pcu net simplified from 2 (c).

(Figure 4a), which is further linked by HDABCO+ into a 44-sql layer through Ohydroxyl 3 3 3 H 3 3 3 N interactions (2.552 and 2.677 Å) (Figure 4b). Furthermore, the 2D structure is reinforced by halogen bonds (X-bonds) with Br 3 3 3 N distance of (3.478 Å).

(TBBPF) 3 (HMTA) (4) and (TBBPA) 3 (HMTA) (5). Cocrystallization of HMTA with TBBPF and TBBPA resulted in 1:1 adducts of 4 and 5, respectively (Figure 1d,e). Structures of 4 and 5 contain similar zigzag chain subunits built by alternate 3554

dx.doi.org/10.1021/cg200520w |Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design

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Figure 6. View of the 1D supramolecular zigzag chain (a) and the 1D supramolecular zigzag ladder of compound 5 (b). Figure 4. View of the 1D supramolecular ribbon (a) and the 2D supramolecular 44-sql layer of compound 3 (b).

Figure 5. View of the 1D supramolecular zigzag chain (a) and the 2D supramolecular 44-sql layer of compound 4 (b).

connection of TBBPF/TBBPA and HMTA via Ohydroxyl 3 3 3 H 3 3 3 N (O 3 3 3 H 3 3 3 N of 2.736 and 2.964 Å for 4; 2.676 and 2.709 Å for 5) hydrogen bonds (Figure 5a and 6a). The remaining two N donors of HMTA in 4 are involved in strong Br 3 3 3 N halogen bonding interactions (Br 3 3 3 N of 3.201 and 3.431 Å) and result in a wavy 44-sql layer structure built by mixed hydrogen and halogen bonds (Figure 5b). However, only one of the remaining two N donors of HMTA in 5 is involved in strong Br 3 3 3 N halogen bonding interactions (Br 3 3 3 N of 3.446 Å) and this results in the formation of a zigzag ladder structure (Figure 6b). (TBBPA)3 3 (HMTA)3 3 H2O (6). There are three TBBPA, three HMTA, and a water molecule in the asymmetric unit of compound 6 (Figure 1f). The six crystallographically independent modules (three TBBPA and three HMTA) form a hexamer subunit through Ohydroxyl 3 3 3 H 3 3 3 N hydrogen bonds (2.683 2.738 Å) (Figure 7a). Interestingly, the hexamer subunits in 6 can be viewed as a fragment of three repeating units for a zigzag chain observed in compound 5. Two such hexamer subunits are connected by a pair of water molecules (Ow 3 3 3 H 3 3 3 N of 2.853 Å and Ohydroxyl 3 3 3 H 3 3 3 Ow of 2.665 Å) and give birth to a molecular oligomer, as shown in Figure 7b, which is further extended into a 1D ribbon by Br 3 3 3 N X-bonds (3.267 and 3.318 Å) (Figure 7c). Proton transfer from TBBPF to PZ/DABCO was observed in compounds 1 3; therefore they are organic salts. Proton

Figure 7. View of the hexamer subunit (a), the connection between hexamer subunits and water molecules (b), and the 1D supramolecular ribbon of compound 6 (c).

transfer was determined from the Fourier difference map of electron density as well as from the C Ophenol bond lengths (Table S1, Supporting Information). Generally speaking, the bisphenol molecules exhibit shorter bonds (1.299 1.309 Å) for the ionized phenol groups than the nonionized ones (1.338 1.363 Å). Furthermore, the distances of Ohydroxyl 3 3 3 H 3 3 3 N hydrogen bonds17 (Table S2, Supporting Information) in compounds 1 3 (salts) are shorter than the ordinary H-bond (2.8/ 2.9 Å, minimum/average distances), and they are thus considered as double charge-assisted H-bonds comprised by strong 1/2 D 3 3 3 H+ 3 3 3 A1/2 interactions (D = H-bond donor; A = H-bond acceptor).18 However, in the cases of compounds 4 6, which are built by TBBPF/TBBPA with HMTA, no proton transfer from TBBPF/TBBPA to HMTA has been observed, which is also in agreement with the judgment of C Ophenol bond lengths (Table S1, Supporting Information); thus compounds 4 6 are cocrystals. The H-bond dominated structural dimensionalities of compounds 1 6 decrease from 3D and 2D (compounds 2, 1, and 3) to 1D (4 and 5) and 0D (6) with the varieties of organoamines. It is not intricate to understand: In compounds 1 and 2, each N atom on PZ has two lone pair electrons; therefore PZ molecules provide four possibilities of connections, which is a potential factor to generate 2D and 3D nets when TBBPF behaves as 3555

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Crystal Growth & Design linkers. We would also expect that HMTA, comprising four N donors locating in a tetrahedral pattern, is sufficient to form 3D structures although HMTA has only one lone pair electron on each of its four N atoms. However, HMTA produces cocrystals with TBBPF/TBBPA primarily in 1:1 stoichiometric ratio; thus only two of its N donors are involved in Ohydroxyl 3 3 3 H 3 3 3 N H-bonds to reinforce the two O donors of TBBPF/TBBPA. In this way, both HMTA and TBBPF/TBBPA behave as linkers (geometrically) and lead to low-dimensional (1D) structures. Once 1D and 0D H-bonded structures are assembled, as in the case of compounds 4 6, auxiliary Br 3 3 3 N X-bonds (3.201 3.478 Å) have been extensively observed and found robust to direct the hierarchical molecular assemblies into higher dimensionalities. It is now clear that molecular design based on the assembly of comparable secondary building units may result in different architectures by virtue of the effect of molecular shape, size, and substituent. In this current system, for example, compounds 4 and 5 are built by similar organic modules, TBBPF/TBBPA, with the same organoamine HMTA. However, the overall packing diagrams of 4 and 5 differ from 44-sql layer to 1D zigzag ladder. A careful examination of the structures indicates that the Cbenzene Ccentral Cbenzene angle around the central sp3 carbon of the TBBPF is somewhat distorted (115.9°; 115.2° 117.7° in compounds 1 4), whereas the Cbenzene Ccentral Cbenzene angle around the central sp3 carbon of the TBBPA is standard (109.9°; 108.5° 110.2° in compounds 5 and 6). This means that TBBPF is somewhat flat, and thus the Ophenol 3 3 3 Ophenol distance of TBBPF (9.73 Å; 9.73 9.99 Å in compounds 1 4) is longer than the one in TBBPA (9.39 Å; 9.36 9.60 Å). Furthermore, the methyl on the central sp3 carbon of the TBBPA molecules leads to steric hindrance of the molecular packing. Indeed, the methyl points outward from the ladder structures in compound 5, which deters its further connection into layers. On the other hand, we notice that inclusion of solvent MeOH or H2O molecules (likely captured from air) would dramatically influence the molecular packing as in the cases of TBBPF/PZ (compounds 1 and 2) and TBBPA/HMTA (compounds 5 and 6). It is intelligible that time of crystallization, which is related to the concentration and mol ratio of starting materials, accounts for the inclusion of solvent molecules; that is, the higher the concentration and mol ratio of starting materials is (in compounds 1 and 5), the shorter the time needed for crystallization is and the less likely solvent molecules, especially H2O in atmosphere, will be present (in compounds 2 and 6). X-ray Powder Diffraction and Thermal Analysis. X-ray powder diffraction patterns of compounds 1 6 (Figure S3, Supporting Information) were recorded to confirm the polymorphic purity of the bulk materials. The experimental XRPD patterns match with the calculated lines from the crystal structures. TGA plots of compounds 1 6 are given in Figure S4, Supporting Information. In compounds 1, 4, and 5, which contain no solvent molecules in the crystal lattice, continuous weight losses were observed after 160 °C corresponding to the structural decompositions. For compound 2, the weight loss of 7.85% before 100 °C is assigned to the loss of solvent methanol and water molecules (calculated 8.22%), followed by a plateau between 100 and 160 °C and further decomposition thereafter. Similarly, for compound 3 and 6, the first weight loss of 1.48% (calculated 1.55% for 3) and 0.76% (calculated 0.87% for 6) before 120 °C are attributable to the release of water molecules, and the weight losses after 160 °C correspond to the further structural decompositions.

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’ CONCLUSION In summary, we have prepared two bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), by bromination reactions of bisphenol-F (BPF) and bisphenol-A (BPA), respectively. TBBPF and TBBPA were utilized to assemble with various organoamines and resulted in a series of six supramolecular organic frameworks (SOFs) with versatile topological structures, including three organic salts, (TBBPF2 )2 3 (HPZ+)2 3 (H2PZ2+) (1), (TBBPF )2 3 (H2PZ2+) 3 2H2O 3 2MeOH (2), and (TBBPF) 3 (TBBPF ) 3 (HDABCO+) 3 H2O (3), and three cocrystals, (TBBPF) 3 (HMTA) (4), (TBBPA) 3 (HMTA) (5), and (TBBPA)3 3 (HMTA)3 3 H2O (6). Structures of the six SOFs are defined by predominant hydrogen bonds (H-bonds). It is found that dimensionalities of the H-bonded structures vary based on the geometries as well as the different pattern of electron configurations of organoamines. Moreover, bromination on bisphenol molecules not only boosts the ability of hydroxyl O donors to form H-bonds but also introduces supportive X-bonds to direct the hierarchical molecular assemblies, which has been demonstrated as a successful synthetic strategy to build new supramolecular organic frameworks. ’ ASSOCIATED CONTENT

bS

Supporting Information. 1H NMR, IR, XRPD, TGA, and crystallographic data in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected].

’ ACKNOWLEDGMENT Financial support from the 973 Program (Grants 2011CB932504 and 2007CB815303), NSFC (Grants 20731005, 20821061, and 21001105), Fujian Key Laboratory of Nanomaterials (Grant 2006L2005), and Key Project from CAS are gratefully acknowledged. ’ REFERENCES (1) (a) Steed, J. W.; Atwood, J. L. Supramolecular Chemistry; John Wiley& Sons: New York, 2000. (b) Russell, V. A.; Evans, C. C.; Li, W.; Ward, M. D. Science 1997, 276, 575. (c) Holman, K. T.; Pivovar, A. M.; Ward, M. D. Science 2001, 294, 1907. (d) Horiuchi, S.; Ishii, F.; Kumai, R.; Okimoto, Y.; Tachibana, H.; Nagaosa, N.; Tokura, Y. Nat. Mater. 2005, 4, 163. (e) Sawada, T.; Yoshizawa, M.; Sato, S.; Fujita, M. Nat. Chem. 2009, 1, 53. (f) Yang, W.; Greenaway, A.; Lin, X.; Matsuda, R.; Blake, A. J.; Wilson, C.; Lewis, W.; Hubberstey, P.; Kitagawa, S.; Champness, N. R.; Schr€oder, M. J. Am. Chem. Soc. 2010, 132, 14457. (2) See, for example:(a) Remenar, J. F.; Morissette, S. L.; Peterson, € J. Am. M. L.; Moulton, B.; MacPhee, J. M.; Guzman, H. R.; Almarsson, O. Chem. Soc. 2003, 125, 8456. (b) Childs, S. L.; Chyall, L. J.; Dunlap, J. T.; Smolenskaya, V. N.; Stahly, B. C.; Stahly, P. G. J. Am. Chem. Soc. 2004, € Zaworotko, M. J. Chem. Commun. 126, 13335. (c) Almarsson, O.; 2004, 1889. (d) Vishweshwar, P.; McMahon, J. A.; Peterson, M. L.; Hickey, M. B.; Shattock, T. R.; Zaworotko, M. J. Chem. Commun. 2005, 4601. (e) Aaker€oy, C. B.; Desper, J.; Scott, B. M. T. Chem. Commun. 2006, 1445. (f) Bhogala, B. R.; Nangia, A. New J. Chem. 2008, 32, 800. (g) Thakuria, R.; Sarma, B.; Nangia, A. New J. Chem. 2010, 34, 623. (h) Khan, M.; Enkelmann, V.; Brunklaus, G. J. Am. Chem. Soc. 2010, 132, 5254. 3556

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(17) The only exception is N(2) 3 3 3 Ophenol(1) distance of 2.831 Å in compound 1. (18) (a) Gilli, P.; Bertolasi, V.; Pretto, L.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc. 2004, 126, 3845. (b) Gilli, P.; Bertolasi, V.; Pretto, L.; Lycka, A.; Gilli, G. J. Am. Chem. Soc. 2002, 124, 13554. (c) Gilli, P.; Bertolasi, V.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc. 2000, 122, 10405.

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