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Directed Molecular Structure Variations of ThreeDimensional Halogen-Bonded Organic Frameworks (XBOFs) Sreejith Shankar, Olga Chovnik, Linda J. W. Shimon, Michal Lahav, and Milko E. van der Boom Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01163 • Publication Date (Web): 16 Jan 2018 Downloaded from http://pubs.acs.org on January 16, 2018
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Directed Molecular Structure Variations of ThreeDimensional Halogen-Bonded Organic Frameworks (XBOFs) Sreejith Shankar,a, † ,‡ Olga Chovnik,a, ‡ Linda J. W. Shimon,b Michal Lahav,a and Milko E. van der Boom*,a a
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 7610001, Israel Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 7610001, Israel. b
KEYWORDS halogen bonding • co-crystal • X-ray diffraction • non-covalent interactions • extended channels ABSTRACT. In this study we have used a tetrahedral oligopyridine and four different fluoroiodides to obtain 3D-nanoporous halogen-bonded co-crystals. Many of the halogen-bonded co-crystals reported to date are 1D chains or 2D sheet-like structures; these new co-crystals possess multiple channels of 300-800 Å3 volume per unit cell. The extended 3D channels can be designed by varying the molecular structure of the halogen bond donor and were found to occupy 20-40% of the unit cell volume. The N⋯I distances in our co-crystals are ~80% of the sum of the van der Waals radii of the nitrogen and iodine atoms, and the N⋯I-C angles are nearly linear. Non-covalent stacking (π-π) interactions as well as H-bonding to solvents were also observed in some of the co-crystals. The supramolecular structures obtained in this study are effectively derived out of different donor-acceptor XB interactions, solvent interactions, and various other tandem, but complementary non-covalent interactions. The weak nature of halogen
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bonds as well as the existence of multiple interactions make these co-crystal structures and their supramolecular organization difficult to predict. Even though this work does not attempt to single out the individual contributions of different factors affecting the supramolecular assemblies, we show here how the structure and hence the potential porosity of the XBOFs can be varied via careful design and combination of structurally different donors and acceptors.
INTRODUCTION Porous crystalline materials, such as Metal Organic Frameworks (MOFs)1-3 and Covalent Organic Frameworks (COFs)4-6 can be used in diverse applications, including separation and storage of gases, sensing, heterogeneous catalysis, and photovoltaics. Conventional inorganic porous materials such as zeolites are used extensively in industry, organic or hybrid porous materials have multiple advantages. However, organic components provide opportunities for the functionalization of the channels and tuning of the pore/channel dimensions.7-12 Although the constituents of MOFs and COFs interact via strong metal-ligand coordination or covalent bonds, the use of other supramolecular interactions can lead to the generation of new materials.7-12 Individually, weak non-covalent supramolecular interactions are collectively strong and are known to form well-defined and stable molecular architectures.13-18 For example, despite the hydrogen bond being a rather weak interaction, stable Hydrogen-Bonded Organic Frameworks (HBOFs) do exist and exhibit potency in the reversible adsorption of CO2, hydrocarbons and other gases,19,20 and alcohols.21 Among the various weak intermolecular forces, such as van der Waals, π-π interactions, and hydrogen bonding, halogen bonding (XB)22-27 is particularly interesting due to its directionality, bond strength (up to 43 kcal/mol), and structure-directing capabilities.24,28 In the 1970s Schmidt
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and Green already demonstrated how Cl⋯Cl interactions could be used to facilitate photodimerization.29 Research pertaining to halogen bonding now spans over a wide range of fundamental and applied sciences,30 including crystal engineering,31-33 nanochemistry and materials science,26,34-36 and medicinal chemistry.37-40 The construction of highly porous materials, based on halogen bonding, can result in the formation of flexible, dynamic voids41-43 and opens up an opportunity to develop new and adaptable materials.34 The formation of threedimensional halogen-bonded organic frameworks (XBOFs) having extended channels is less common.22,43-46 Hydrogen and halogen-bonded co-crystals have been reported to have channels occupying 19-40% of the unit cell volume.42,47-49 For instance, charge-assisted hydrogen bonding was found to result in porous crystals with 1D channels amounting to almost 21% of the total cell volume. These crystals are large enough to accommodate spheres having a 0.5 nm radius, and are among the highest reported for H-bonded networks.47 Halogen-bonded porous inclusion complexes are also found with channels occupying up to 40% of the unit cell volume.49 In this context, Metrangolo and Resnati reported the self-assembly of α,ω-diiodoperfluoroalkanes with 3D XB-acceptors, used to form networks with channels, cavities, and voids.45 However, studies related to porosity of extended supramolecular structures formed via halogen bonding are rather rarely found in literature. In this study, we report on the formation of a series of five XBOFs from solutions of individual halogen bonding acceptor and donor components leading to extended supramolecular systems. We show how the number of coordination sites, ring electronics, and the geometry of the XB donors affect halogen-bond formation. The structure-directing capabilities have been demonstrated by using a tetrahedral ligand A (XB acceptor) with Td symmetry possessing four pyridyl binding sites and four different iodide-based XB donors (D1–D4; Figure 1).
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Figure 1. Molecular structure of the XB acceptor (A) and XB donors (D1–D4).
RESULTS AND DISCUSSION The tetrahedral carbon core, along with four terminal pyridine moieties, in XB acceptor A allows the formation of 3D halogen-bonded networks with XB donors D1–D4. Single crystals of XBOFs suitable for X-ray diffraction were obtained via two strategies: (a) mixing the components in solution, followed by slow evaporation over 1–2 weeks, and (b) layering the solutions, followed by diffusion of the solvents and slow evaporation. Subsequently, five cocrystals A•D1, A•D2, A•D3a, A•D3b, and A•D4 were isolated and characterized by single crystal X-ray analysis. All the co-crystals featured XB acceptor A in a slightly distorted Td geometry. The N⋯I distances were found to be ~80% of the sum of the van der Waals radii of the nitrogen and iodine atoms, and the N⋯I-C angles were nearly linear. The co-crystals A•D1–D4 reported here are spanned by extended 3D channels amounting to 20-40% of the unit cell volume. The results obtained are summarized in Tables 1 and 2. Others have observed isostructural topologies for halogen bonded co-crystals emanating from precursors with different supramolecular topologies,50 we demonstrate that the structures as well as the potential porosity of the co-crystals could be altered by using structurally different halogen bond donors. The
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combination of different non-covalent interactions such as metal coordination as well as halogen bonding has been shown to result in multi-dimensionality in halogen bonded frameworks.51
N/A
Observed Molar Ratio N/A
N/A
C-I···N angles Porositya (%) (deg) N/A 15
A, D1
1:4
A•D1, 1:2
2.755, 2.927
176.5, 177.1
25
A, D2
3:4
A•D2, 1:1
2.743, 2.763
176.0, 177.7
26
A, D3
1:1
A•D3a, 1:1
2.814, 2.836
176.1, 171.2
40
2.805, 2.812,
173.3, 176.9,
A, D3
1:2
A•D3b, 1:1
Compounds
Molar Ratio
A
A, D4
1:4
A•D4, 2:3
N···I dist (Å)
38 2.851, 2.901
172.0, 171.6
2.697, 2.732
175.9, 177.0
20
Table 1. Structural parameters observed for crystal A and co-crystals A•D1–A•D4 SQUEEZE protocol52 was used to remove disordered solvent and guest molecules present in the channels of the crystals. PLATON software53 (grid: 0.2 Å; probe radius: 1.2 Å) was used to calculate potential porosity of the structure that represents potential empty space present in a unit cell. Crystal A: Slow evaporation of a CHCl3 solution of acceptor A at room temperature resulted in the formation of colorless, needle-like crystals, suitable for single crystal X-ray diffraction analysis. The crystal structure of A (Figure 2) relates to a tetragonal P-4 space group, and contains two molecules of A in the unit cell with a slightly distorted Td geometry. The molecules are packed in an interlocking fashion along the b-axis (Figure 2B), generating continuous empty channels of 167 Å3 that occupy ~15% of the unit cell volume (Figure 2C, D). The crystal’s
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structure was analyzed with Mercury software, whereas the void’s volume was determined by PLATON sofware.53
V
Figure 2. (A) Mercury view (partial) of the crystal structure of A. Colors: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta; hydrogen atoms are omitted for clarity. (B) Spacefilling model representing the interlocking of A molecules along the b-axis. Each molecule in the packing arrangement is displayed in a different color; hydrogen atoms are omitted for clarity. (C) Ball-and-stick (left) and space-filling (right) representations of the lattice of crystal A, viewed along the c-axis. Continuous empty channels (V) of 167 Å3 are presented. (D) Side view of the channel as shown in (C).
Co-crystal A•D1: Slow evaporation of a layered CHCl3/toluene solution containing compounds A and D1 in a 1:4 molar ratio resulted in the formation of colorless needle-like co-crystals (A•D1). Single crystal X-ray diffraction revealed the formation of an XBOF with A and D1 in a 1:2 ratio (Figure 3). The crystal structure of A•D1 relates to a monoclinic P2/c space group. Each pyridine moiety in A is involved in halogen bonding with D1 (Figure 3B); both of the iodine
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atoms of D1 are also involved (Figure 3A). The unit cell consists of two molecules of XB acceptor A and four molecules of XB donor D1 (Figure S1). Two N⋯I distances of 2.755 Å and 2.927 Å (~80% of the sum of the van der Waals radii of the nitrogen and iodine atoms) were observed with nearly linear N⋯I-C angles of 176.53° and 177.12°, respectively. The co-crystal also features a halogen-halogen interaction (F⋯F distance of 2.926 Å, type I, θ1 = 136.87° and θ2 = 136.29°) between the molecules of D1 and herringbone packing (Figure S2). The co-crystal’s structure was analyzed with PLATON software using a spherical probe of radius 1.2 Å. The analysis revealed continuous channels, filled with disordered solvent molecules, spanning the XBOF (Figure 3C). Two channels, 432 Å3 each, are present in a unit cell, and occupy ~25% of the unit cell volume.
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Figure 3. (A,B) Partial view of co-crystal A•D1. Each molecule of D1 has two asymmetric N⋯I interactions (a = 2.927 Å, b = 2.755 Å) with A (A) and each molecule of A has two sets of N⋯I interactions (two each of a = 2.927 Å, b = 2.755 Å) with D1 (B). The dotted lines show the nearly linear halogen bonds. (C) Ball-and-stick (left) and space-filling (right) representations of the crystal lattice of co-crystal A•D1 viewed through axis b showing continuous channels (voids) of 432 Å3 (V). Inset: Ball-and-stick representation of a unit cell of co-crystal A•D1. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta. Hydrogen atoms are omitted for clarity. The co-crystal A•D1 contains only one type of channel filled with two toluene molecules per unit cell stabilized via their interactions with the network (Figure 4). One such interaction occurs between the aromatic hydrogen atom of toluene and the fluorine atom of the XB donor molecule (A = 2.598 Å); another interaction was found to be between the aliphatic hydrogen atom of toluene and the pyridine ring of the XB acceptor (B = 2.882 Å).
Figure 4. (A) Zoomed in view on the channel of co-crystal A•D1 through axis b showing interactions between the trapped solvent molecules and the network (A = 2.598 Å; B = 2.882 Å).
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The size of the channel can be viewed as about 20 Å × 7 Å. (B) The channel viewed along a axis (toluene molecules are not shown in order to visualize the channel).
Co-crystal A•D2: Slow evaporation of a CHCl3/toluene solution containing compounds A and D2 in a 4:3 ratio resulted in the formation of colorless co-crystals of A•D2 (Figure 5). Single crystal X-ray analysis revealed an XBOF along with π-π stacking interactions. The stoichiometry of acceptor A and donor D2 in the co-crystal was found to be equimolar, which differs from that in solution. Only two out of the four pyridine moieties of A are involved in interactions with D2 (Figure 5B), and only two of the three iodine atoms of D2 are bound (Figure 5A). However, such an arrangement, where one or more of the binding units remain unbound, has been observed in other halogen and hydrogen-bonded systems. The unit cell consists of four molecules each, of XB acceptor A and XB donor D2 (Figure S3). The intermolecular N⋯I distances were found to be 2.743 Å and 2.763 Å (~80% of the sum of the van der Waals radii) and the corresponding N⋯I-C angles are nearly linear: 176.00° and 177.72°, respectively. Acceptor A is involved in π-π stacking interactions with D2 and another molecule of A (Figure 6A). Compound A forms stacking interactions with D2 either through the phenyl ring (3.396 Å) or the pyridine ring (3.149 Å). The distance between π-stacked A molecules is 3.362 Å; the π-π stacking interaction occurs between the pyridine ring and the double bond. Two continuous channels, ~817 Å3 each, are present in a unit cell, and occupy ~26% of the unit cell volume (Figure 4C). The co-crystal contains only one type of channel filled with disordered solvent molecules that were removed from the refinement models via SQUEEZE procedure (Figure 6B,C). The iodine atoms of D2 that do not participate in halogen bonding interactions with A were directed inwards into the
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channels (Figure 5C). This arrangement could possibly be employed for selective, halogen bondbased host-guest inclusion.
Figure 5. (A,B) Partial view of co-crystal A•D2. Each molecule of D1 has two asymmetric N⋯I (a = 2.763 Å, b = 2.743 Å) interactions with A (A) and each molecule of A has two asymmetric N⋯I interactions (a = 2.763 Å, b = 2.743 Å) with D2 (B). The third iodine of D2 does not participate in halogen-bonding or halogen-halogen interactions. The dotted lines show the nearly linear halogen bonds. (C) Ball-and-stick (left) and space-filling (right) representations of the crystal lattice of co-crystal A•D2 viewed through axis b showing continuous channels of 817 Å3 (V). Inset: Ball-and-stick representation of a unit cell of co-crystal A•D1 with the unbound iodine atoms pointing into the voids. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta. Hydrogen atoms are omitted for clarity.
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Figure 6. (A) Presentation of the intermolecular π-π stacking interactions present in co-crystal A•D2. The dotted lines (a = 2.763 Å, b = 2.743 Å) show the nearly linear halogen bonds. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta. Hydrogen atoms were omitted for clarity. (B) Zoomed in view on the channel of co-crystal A•D2 through axis b. The size of the channel is ~14 Å × 11 Å. (C) The channel viewed along a axis (disordered solvent molecules are not shown for clarity). Co-crystal A•D3a: Slow evaporation of a CHCl3/toluene solution containing compounds A and D3 in a 1:1 ratio resulted in the formation of co-crystal A•D3a (Figure 7). Single crystal X-ray diffraction showed the formation of a 3D halogen-bonded network with both of the compounds (A, D3) and solvent molecules (toluene) in a 1:1:4 ratio. Each pyridine of A is involved in halogen bonding with D3 (Figure 7B); all four iodine atoms of D3 also participate in halogen bonding (Figure 6A). The unit cell consists of four molecules each: the XB acceptor A and the
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XB donor D3, along with sixteen toluene molecules (Figure S4). The intermolecular N⋯I interactions with distances of 2.814 Å and 2.836 Å (~80% of the sum of the van der Waals radii) are nearly linear (N⋯I-C angles of 176.10° and 171.23°, respectively). The 3D network obtained has continuous channels filled with molecules of toluene (Figure 7C). Eight channels, four each of volume 363 Å3 and another four channels of volume 368 Å3, are present in a unit cell, and occupy ~40% of the unit cell volume. The co-crystal contains two types of channels, α and β, per unit cell, each filled with two toluene molecules (Figure 8A). While there are no interactions between the individual toluene molecules, they are stabilized via interactions with the network (Figure 8B). In channel α, the interactions occur between the aromatic hydrogen atom of toluene and the delocalized electrons on the double bond of the XB acceptor (A = 2.890 Å). In channel β, the interactions between the aliphatic hydrogen atom of toluene and the delocalized electrons on the aromatic ring of the XB acceptor (A = 2.827 Å) stabilizes the channel (Figure 8).
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Figure 7. (A,B) Partial view of co-crystal A•D3a. Each molecule of D3 has two sets of asymmetric N⋯I interactions (two each of a = 2.836 Å and b = 2.814 Å) with A (A), and each molecule of A also has two sets of N⋯I interactions (two each of a = 2.836 Å and b = 2.814 Å) with D3 (B). The dotted lines show the nearly linear halogen bonds. (C) Ball-and-stick (left) and space-filling (right) representations of the crystal lattice of co-crystal A•D3a viewed through axis b showing continuous channels of 363 Å3 (V1) and 368 Å3 (V2). Inset: Ball-and-stick representation of unit cells of co-crystal A•D3a with toluene molecules residing in each void. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta. Hydrogen atoms and solvent molecules were omitted for clarity.
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Figure 8. (A) Zoomed in view on the two types of channels, α and β, of co-crystal A•D3a through axis b showing interactions between the trapped solvent molecules and the network (α: A = 2.890 Å; β: A = 2.827 Å). The size of channels α and β are ~13 Å × 11 Å and ~13 Å × 14 Å, respectively. (B) Channels viewed along a and c axis (toluene molecules were are not shown for clarity). Co-crystal A•D3b: When a different ratio of A and D3 was used (as compared with that in A•D3a), a solvomorph was obtained. Slow evaporation of a layered CHCl3/toluene solution containing compounds A and D3 in a 1:2 ratio resulted in the formation of A•D3b (Figure 9). Single crystal X-ray diffraction revealed the formation of an XBOF with both of the compounds (A, D3) and solvent molecules (toluene, CHCl3) in a 1:1:1:1 ratio. Each pyridine of A is involved in halogen bonding with compound D3 (Figure 9B); all four iodine atoms of D3 also participate in halogen bonding (Figure 9A). The unit cell consists of four molecules each of XB acceptor A,
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the XB donor D3, toluene, and chloroform (Figure S5). The intermolecular N⋯I interaction with distances of 2.805 Å, 2.812 Å, 2.851 Å, and 2.901 Å (~80% of the sum of the van der Waals radii) are nearly linear with N⋯I-C angles of 173.25°, 176.94°, 171.98°, and 171.59°, respectively. The 3D network has continuous, alternating solvent (toluene or CHCl3)-filled channels (Figure 9C). Eight channels, four each of volume 300 Å3 and another four of volume 360Å3, are present in a unit cell and occupy ~38% of the unit cell volume.
Figure 9. (A,B) Partial view of co-crystal A•D3_b. Each molecule of D3 has four asymmetric N⋯I interactions (a = 2.805 Å, b = 2.812 Å, c = 2.851 Å, and d = 2.901 Å) with A (A) and each molecule of A also has four asymmetric N⋯I interactions (a = 2.805 Å, b = 2.812 Å, c = 2.851 Å, and d = 2.901 Å) with D3 (B). The dotted lines show the nearly linear halogen bonds. (C) Balland-stick (left) and space-filling (right) representations of the crystal lattice of co-crystal A•D3b
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viewed through axis b showing continuous channels of 360 Å3 (V1) and 300 Å3 (V2). Inset: Ball-and-stick representation of the unit cell of co-crystal A•D3b with alternating empty and solvent-occupied voids. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta. Hydrogen atoms and solvent molecules are omitted for clarity. Channels found in co-crystal A•D3b can be classified into four types: those with ordered (α, β) and those with disordered (γ, δ) solvent molecules. Channel α is enclosed within two molecules of A, and hosts two chloroform molecules per unit cell. Each of the chloroform molecules interacts with the network through weak H-bonding with an iodine atom of D3 (A = 3.009 Å; ∠C-H···I = 162.99°). Channel β hosts two toluene molecules per unit cell that interact neither with the network nor with themselves. Channel γ and δ are filled with disordered solvent molecules that were removed from the refinement models by the SQUEEZE procedure (Figure 10).
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Figure 10. (A) Zoomed in view on two types of channels, α and β, of co-crystal A•D3b through axis b showing the presence (α: A = 3.009 Å) or absence of interactions between the trapped solvent molecules and the network. The size of channels α and β are ~9 Å × 8 Å and ~10 Å × 16 Å, respectively; additional two types of channel, γ and δ, filled with disordered solvent molecules are estimated to be ~ 9 Å × 13 Å and ~7 Å × 14 Å, respectively. (B) Channels viewed along a and c axis (toluene molecules are not shown for clarity).
Co-crystal A•D4: Slow evaporation of a CHCl3 solution containing compounds A and D4 in a 1:4 ratio resulted in the formation of a co-crystal A•D4 (Figure 11). Single crystal X-ray diffraction revealed the formation of an XBOF with both of the compounds (A, D4) and solvent molecules (CHCl3) in a 2:3:4 ratio. Only two out of four pyridines of A are involved in halogen bonding with D4 (Figure 11B), whereas both of the iodine atoms of D4 are bound (Figure 11C).
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Compound D4 alternates between its syn- and anti-conformers. The unit cell consists of two molecules: the XB acceptor A and two molecules of the XB donor D4 (two halves each of the anti and syn conformers), along with four chloroform molecules (Figure S6). Each conformer of the donor molecule is bound to the acceptor at two similar intermolecular N⋯I distances of 2.697 Å and 2.732 Å (~80% of the sum of the van der Waals radii), and two similar N⋯I–C angles of 175.87° and 176.98°, respectively. The two pyridines that do not participate in halogen bonding are capped by molecules of CHCl3 (Figure 11B,12A). The intermolecular N⋯C distances of 3.114 Å and 3.201 Å (N⋯H distances of 2.226 Å and 2.169 Å) are observed, indicating weak hydrogen bonds between A and CHCl3. Weak π-π interactions (3.395 Å) also exist between the acceptor molecules (Figure 12A). The co-crystal also features a halogen-halogen interaction (F–F distance of 2.910 Å, type II, θ1 = 161.98° and θ2 = 127.20°) between the anti-conformers of D4 (Figure S7). The co-crystal features four continuous channels per unit cell, each of volume 307 Å3, , occupying ~20% of the unit cell volume (Figure 11C). In the observed channels reside CHCl3 molecules, two per unit cell, that are stabilized via H-bonding (Figure 12B,C). Yet, each of the chloroform molecules has a diverse set of supplementary interactions resulting in a better stabilization of the arrangement (Figure 12B; C-Cl···F (A = 3.198 Å); C-Cl···π (B = 3.320 Å); CCl···π (C = 3.414 Å)).Metrangolo and Resnati have employed similar XB-directed crystal engineering principles to resolve mixtures of diiodoperfluoroalkanes using selective and reversible binding to bis(trimethylammonium) alkane-based organic ionic solids.54
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Figure 11. (A,B) Partial view of co-crystal A•D4. D4 alternates between syn- and anticonformers; each conformer has two symmetric N⋯I interactions (a = 2.697 Å for anti-D4, b = 2.732 Å for syn-D4) with A (A) and each molecule of A has two asymmetric interactions (a = 2.697 Å with anti-D4, b = 2.732 Å with syn-D4), one with each conformer of D4. The two unbound pyridines of A are hydrogen-bonded to CHCl3 (N⋯C distances of a = 3.201 Å, b = 3.114 Å; the corresponding N⋯H distances are 2.226 Å, b = 2.169 Å) (B). The dashed lines show the halogen and hydrogen bonds. (C) Ball-and-stick (left) and space-filling (right) representations of the crystal lattice of co-crystal A•D4 viewed through axis a showing continuous channels of 307 Å3 (V). Inset: Ball-and-stick representation of the unit cell of cocrystal A•D4 with chloroform molecules residing in each void. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta, chlorine, green. Hydrogen atoms and solvent molecules were omitted for clarity.
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Figure 12. (A) Partial view of the intermolecular interactions between A and D4 in co-crystal A•D4. The dashed lines show the halogen (a = 2.697 Å for anti-D4, b = 2.732 Å for syn-D4) and hydrogen bonds (N⋯C distances of a = 3.201 Å, b = 3.114 Å; the corresponding N⋯H distances are 2.226 Å, b = 2.169 Å). The arrows indicate π-π stacking interactions. Atomic color code: carbon, gray; nitrogen, blue; fluorine, light green; iodine, magenta, chlorine, green. Hydrogen atoms are omitted for clarity. (B) Zoomed in view on the channel of co-crystal A•D4 through axis a showing additional interactions between the trapped solvent molecules and the network (A = 3.198 Å; B = 3.320 Å; C = 3.414 Å). (C) Channels viewed along b axis (toluene molecules are not shown for clarity).
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We have previously shown that the formation of an N···I bond is accompanied by a charge transfer from pyridine units to the donors.55 The C−I bonds in the donors were found to be elongated after the formation of a new N···I bond, which could be attributed to the electron donation to the σ*(C−I) orbital. However, the elongation of a specific C−I bond may not be affected by the number of pyridines bound to the donor. The N···I distances, the C−I···N angles, as well as the void volume were found to be affected by the directional geometry of the components and hence, the number of donor and acceptor sites. The formation of only two halogen bonds instead of the expected three in co-crystal A•D2 is most likely due to the electronic factors involved and the geometry constraints of tetrahedral ligand A. In co-crystals A•D3, both the electronic factors and the Td geometry of A favor the formation of a network with four halogen bonds. We believe that the formation of these XBOFs balances at the border between the endergonic and exergonic parameters make the crystallization sensitive to the reaction conditions, as shown by the structures of co-crystals A•D3a and A•D3b.
All the co-crystals were prepared in air. TGA analysis infers that the decomposition of A•D1–A•D4 co-crystals is most likely due to lower stability of the XB donor. The weight loss corresponding to the XB donor D1–D4 occurs in two steps rather in one direct sublimation event observed for the individual components. The decomposition temperature for the XB acceptor A (390-410o C) stays the same for all co-crystals, as expected. The weight loss corresponding to the loss of the donors also correlate well with those for the individual donors. A•D1 starts to decompose via the loss of the donor around 96o C, A•D2 and A•D4 are slightly more stable (lose
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donors at 132-144o C), while A•D3a-b start to decompose at a much higher temperature (170180o C). The co-crystals also exhibited loss of solvents (up to 6%) around 100o C. (Figure S8). The DSC thermograms (Figure S9) revealed the melting and phase transitions in the co-crystals along with some peaks associated with solvent loss. Co-crystal A•D1 was selected to determine its stability via single crystal XRD measurements. A single crystal of A•D1 was subjected to high vacuum for 5 h at a temperature of 60 ˚C and then its X-ray structure was determined. The halogen-bonded framework was found to be stable with only minor changes in its unit cell parameters (P 2/c, a = 20.3560(3) b = 7.79840(10) c = 22.0365(4), β = 95.3200(10)) as compared to the untreated co-crystal. Toluene molecules were not eliminated from the channels (Figure S10).
CONCLUSIONS The co-crystals are spanned with continuous channels of 300-800 Å3 volume per unit cell, occupying up to 40% of the unit cell volume. These extended 3D channels occupy volumes among the highest reported for halogen-bonded organic frameworks (XBOFs). Halogen bonded co-crystals obtained from tetrahaloethynyl cavitands and ditopic XB acceptors have recently been reported to possess medium (186 Å3) to large (683 Å3) cavities.56 Whereas all co-crystals featured characteristic and nearly linear N···I halogen bonds, co-crystals A•D1 and A•D4 also involved F···F halogen bonds between donor molecules. Weak π-π stacking interactions and hydrogen bonding with solvents were also observed in some of the co-crystals. The structure of the XB donors, the number of binding sites, the geometry and electronic factors, as well as the crystallization conditions were found to direct voids of the 3D nanoporous networks.
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Extrinsically porous crystal A increases its potential porosity significantly via the formation of halogen-bonded co-crystals A•D1- A•D4 with halogenated arenes D1-D3, and an aliphatic molecule D4. The volume of the formed channels is tuned by the type of the XB donor molecule (as observed in co-crystals A•D1, A•D2) and the type of the guest molecule serving as a growth template (toluene in co-crystal A•D3a, CHCl3 and toluene in co-crystal A•D3b, CHCl3 in cocrystal A•D4). In all of the above-mentioned co-crystals, interpenetration is avoided, and the energetic penalty for the presence of channels is paid by filling them either with disordered or ordered solvent molecules (A•D1-2; A•D3-D4, respectively). The presence of unbound C−I moieties suggests that such structures can be used for host-guest chemistry for halogen-bond acceptors.
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EXPERIMENTAL SECTION Materials and Methods 2,3,5,-Trifluoro-1,4-diiodobenzene (D1, Appolo Scientific Ltd.), hexadecafluoro-1,8diiodioctane (D4, Sigma Aldrich) and solvents were used as received. Tetrakis(4-pyridylethen-2yl)tetraphenylmethane (A),57 1,3,5-trifluoro-2,4,6-triiodobenzene (D2),58 and 1,4-difluoro2,3,5,6-tetra-iodobenzene (D3)59 were prepared according to literature procedures. Preparation of Crystal A and Co-crystals A•D1 - A•D4 Crystal A: Compound A (25 mg, 0. 0.034 mmol) was dissolved in CHCl3 (6.0 mL) in a screwcapped vial. The vial was loosely capped and the solution was kept in the dark. After a week, colorless needle-like crystals suitable for X-ray analysis were obtained. Co-crystal A•D1: Compound D1 (55 mg, 0.14 mmol) was dissolved in toluene (2.0 mL) and layered over a CHCl3 solution (4.0 mL) of compound A (25 mg, 0.034 mmol). The vial was loosely capped and the solution was kept without light. After a week, colorless needles suitable for X-ray analysis were obtained. Co-crystal A•D2: A 3.0 mL solution of compound D2 (9.7 mg, 0.019 mmol) and a 3.0 mL solution of compound A (10 mg, 0.014 mmol) in CHCl3/toluene (25:1 (v/v), 6.0 mL) were mixed in a vial. The vial was loosely capped and the solvent was allowed to evaporate slowly without light. Colorless needles suitable for X-ray analysis were obtained after two weeks at room temperature. Co-crystal A•D3a: A solution of compound D3 (8.4 mg, 0.014 mmol) in toluene (3.0 mL) was mixed with a CHCl3 solution (3.0 mL) of compound A (10 mg, 0.014 mmol). The vial was loosely capped and the solvent was allowed to evaporate slowly without light. Colorless needles suitable for X-ray analysis were obtained after two weeks at room temperature.
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Co-crystal A•D3b: A 1.0 mL toluene solution containing compound D3 (68 mg, 0.11 mmol) was layered over a CHCl3 solution (2.0 mL) of compound A (40 mg, 0.055 mmol). The vial was sealed and kept without light. After 5 days, colorless needles suitable for X-ray analysis were obtained at room temperature. Co-crystal A•D4: A solution of compound D4 (35 mg, 0.054 mmol) in CHCl3 (3.0 mL) was mixed with a solution of compound A (10 mg, 0.014 mmol) in CHCl3 (3.0 mL). The vial was loosely capped and the solvent was allowed to evaporate slowly without light. Colorless needles suitable for X-ray analysis were obtained after one week at room temperature. Crystallographic Analyses of the Supramolecular Co-crystals All crystals were coated in Paratone oil (Hampton Research) and mounted on MiTeGen loops. They were flash frozen in the liquid nitrogen stream of the Oxford Cryostream. Diffraction data of the co-crystals A•D1, A•D3a, A•D3b were measured at a low temperature of 100(2) K using MoKα λ=0.71073 Å on a Bruker KappaApexII CCD system diffractometer. The data sets were reduced in Bruker Apex2. Multi-scan absorption corrections were applied with SADABS.60 Diffraction data for the complex A•D2 were measured with MoKα λ = 0.71073 Å on a Nonius Kappa CCD system with MiraCol optics. The data were processed with Denzo-Scalepack. The diffraction data for A•D4 were collected on a Rigaku XtaLabPro using CuKα λ = 1.54178 Å. The data were processed and reduced with CrysAlisPro. The structure solution of co-crystals A•D1, A•D2, A•D3a, and A•D3b was prepared using direct methods in SHELXS-2013.61 The structure solution of co-crystal A•D4 was prepared with SHELXT-2016.62 Full-matrix leastsquares refinement based on F2 was done with SHELXL-2016/4.63 Non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in calculated positions and refined in riding mode. The SQUEEZE protocol of PLATON was used to remove highly disordered
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solvent molecules from the refinement models of A, A•D1, A•D2, A•D3b.52 Crystallographic data are given in Table 2. Table 2. Crystallographic data of co-crystals A•D1–A•D4. Complex CCDC No.
A 1565667 C53H40N4
A••D1 1565668 C53H40N4 + 2(C6F4I2) + 2(C7H8)
A••D2 1565669 C53H40N4 + C 6 F 3 I3
A••D3_a 1565670 C53H40N4 + C 6 F 2 I4 + 4(C7H8)
A••D3_b 1565671 C53H40N4 + C 6 F 2 I4 + C 7 H8 + CHCl3
Formula
A••D4 1565672 C53H40N4 + C8F16I2 + CHCl3
Formula weight Crystal system
732.89
1720.87
1242.65
1626.95
1562.05
1625.51
tetragonal
monoclinic
monoclinic
monoclinic
monoclinic
triclinic
Space group Crystal size
P -4 0.50 0.05 0.05 Colorless needle 100
P 21/c 0.34 x0.22 x0.10 Colorless needle 120
C2/c 0.09x0.020x0.010
Crystal color and shape Temperature (K) wavelength (Å) a, (Å) b, (Å) c, (Å) α, (°°) β, (°°) γ, (°°) Volume (Å3) Z ρcalcd,(g cm-1) µ, mm-1 No. of reflection (unique) Rint Completeness to θ (%) data / restraints / parameters goodness-offit on F2 Final R1 and wR2 indices [I
P 2/c 0.35 x0.10 x 0.02 Colorless needle 100
Colorless needle 100
Colorless needle 100
Colorless needle 100
0.71073
0.71073
0.71073
0.71073
0.71073
1.54187
17.363(1) 17.363(1) 7.3086(4) 90 90 90 2203.4(3) 2 1.105 0.065 9981/4630
20.406(2) 7.8067(15) 22.050(2) 90 95.330(4) 90 3497.5(8) 2 1.634 1.850 84648(6896)
18.476(3) 15.240(2) 22.763(3) 90 101.582(6) 90 6279.0(15) 4 1.314 1.537 265154(6522)
32.334(7) 7.4008(15) 30.729(2) 90 95.78(3) 90 7316(3) 4 1.477 1.753 26568(7465)
31.122(2) 7.3333(4) 31.148(2) 90 98.783(2) 90 7025.4(7) 4 1.477 1.932 69865(17276)
7.053(4) 16.007(9) 29.493(17) 74.31(3) 88.89(2) 89.365(16) 3205(3) 2 1.684 10.808 27550(7459)
0.0548 98.0
0.0439 99.9
0.0690 99.1
0.0381 99.5
0.0444 97.6
0.122 95.3
4630/0/257
6896/43/418
6522/0/617
7465/48/444
17276/7/712
7496/131/815
1.045
1.055
1.044
1.192
1.046
1.031
0.0627, 0.1563
0.0425, 0.0643
0.0699, 0.1882
0.0510,0.1215
0.0408,0.0955
0.0762,0.1884
P 21/n P -1 0.40x0.10x0.10 0.15x0.05x0.05
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> 2σ(I)] R1 and wR2 indices (all data)
0.0892,0.1700
0.1030, 0.1204
0.0913, 0.2005
0.0677,0.1309
0.0595,0.1028
0.0894,0.2041
ASSOCIATED CONTENT Supporting Information. The following files are available free of charge: experimental details, materials and methods, single crystal X-ray analyses, data collection parameters, supplementary figures S1-S7 (PDF), and X-ray structural details (cif).
AUTHOR INFORMATION Corresponding Author *
[email protected] Present Addresses †CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Industrial Estate P O, Pappanamcode, Thiruvananthapuram 695019, India Author Contributions The manuscript was written through contributions of all authors. All authors have approved the final version of the manuscript. ‡These authors contributed equally. ACKNOWLEDGMENT This research was supported by the Helen and Martin Kimmel Center for Molecular Design and the Israel Science Foundation (ISF). M.E.vdB. is the incumbent of the Bruce A. Pearlman Professorial Chair in Synthetic Organic Chemistry.
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REFERENCES 1. 2. 3. 4. 5. 6. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26.
Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673–674 and other articles in this themed issue. Zhou, H.-C. J.; Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5415–5418 and other articles in this themed issue. Levason, B.; Bradshaw, D. (Eds.), Coord. Chem. Rev. 2016, 307, 105–424. Dinga, S. Y.; Wang, W. Chem. Soc. Rev. 2013, 42, 548–568. Waller, P. J.; Gándara, F.; Yaghi, O. M.; Acc. Chem. Res. 2015, 48, 3053–3063. Cote, A.; Benin, A. Ockwig, N.; O'Keefe, M.; Matzger, A.; Yaghi, O. Science 2005, 310, 1166–1170. Davis, M. E. Nature, 2002, 417, 813–821. Das, S.; Heasman, P.; Ben, T.; Qiu, S. Chem. Rev., 2017, 117, 1515–1563. James H. R.; Abbie, T.; Andrew C. I. Nat. Chem. 2010, 2, 915–920. Cooper, A. I. ACS Cent. Sci., 2017, 3, 544–553. Horike, H.; Shimomura, S.; Kitagawa, S. Nat. Chem. 2009, 1, 695–704. McKeown, N. B. J. Mater. Chem. 2010, 20, 10588–10597. Huang, L.; Yang, X.; Cao, D. J. Phys. Chem. C 2015, 119, 3260–3267. Mahadevi, S. A.; Sastry, G. N. Chem. Rev. 2016, 116, 2775–2825. Hifsudheen, M.; Mishra, R. K.; Vedhanarayanan, B.; Praveen, V. K.; Ajayaghosh, A. Angew. Chem. Int. Ed. 2017, 10.1002/anie.201707392. Mahmudov, K. T. Kopylovich, M. N.; da Silva, M. F. C. G.; Pombeiro, A. J. L. Coord. Chem. Rev. 2017, 345, 54–72. van Esch, J. H. Nature 2010, 466, 193–194. Schmuck, C. Nat. Nanotechnol. 2011, 6, 136–137. Fyfe, M. C. T.; Stoddart, J. F. Acc. Chem. Res. 1997, 30, 393–401. Wang, H.; Li, B.; Wu, H. Hu, T.-L.; Yao, Z.; Zhou, W.; Xiang, S.; Chen, B. J. Am. Chem. Soc., 2015, 137, 9963–9970. Luo, X.-Z.; Jia, X.-J.; Deng, J.-H.; Zhong, J.-L.; Liu, H.-J.; Wang, K.-J.; Zhong, D.-C. J. Am. Chem. Soc. 2013, 135, 11684–11687. Li, P.; He, Y.; Guang, J.; Weng, J.; Zhao, J. C.-G.; Xiang, S.; Chen, B. J. Am. Chem. Soc., 2014, 136, 547–549. Gilday, L. C.; Robinson, S. W.; Barendt, T. A.; Langton, M. J.; Mullaney, B. R.; Beer, P. D. Chem. Rev. 2015, 115, 7118–7195. Politzer, P.; Murray, J. S. ChemPhysChem 2013, 14, 278–294. Politzer, P.; Murray, J. S.; Clark, T. Phys. Chem. Chem. Phys. 2010, 12, 7748–7757. Erdelyi, M. Chem. Soc. Rev. 2012, 41, 3547–3557. Berger, G.; Soubhyea, J.; Meyer, F. Polym. Chem. 2015, 6, 3559–3580.
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27. Cavallo, G.; Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.; Terraneo, G. Chem. Rev., 2016, 116, 2478–2601. 28. Priimagi, A.; Cavallo, G.; Metrangolo, P.; Resnati, G. Acc. Chem. Res. 2013, 46, 2686– 2695. 29. Schmidt, G. Pure Appl. Chem. 1971, 27, 647–678. 30. Erdelyi, M. Nat. Chem. 2014, 6, 762–764. 31. Metrangolo, P.; Neukirch, H.; Pilati, T.; Resnati, G. Acc. Chem. Res. 2005, 38, 386–395. 32. Metrangolo, P.; Meyer, F.; Pilati, T.; Resnati, G.; Terraneo, G. Angew. Chem. Int. Ed. 2008, 47, 6114–6127. 33. Mukherjee, A.; Tothadi, S.; Desiraju, G. R. Acc. Chem. Res. 2014, 47, 2514–2524. 34. Meazza, L.; Foster, J. A.; Fucke, K.; Metrangolo, P.; Resnati, G.; Steed, J. W. Nat. Chem. 2013, 5, 42–47. 35. Meyer, F.; Dubois, P. CrystEngComm 2013, 15, 3058–3071. 36. Zhu, W.; Zheng, R.; Zhen, Y.; Yu, Z.; Dong, H.; Fu, H.; Shi, Q.; Hu, W. J. Am. Chem. Soc. 2015, 137, 11038–11046. 37. Lu, Y.; Shi, T.; Wang, Y.; Yang, H.; Yan, X.; Luo, X.; Jiang, H.; Zhu, W. J. Med. Chem. 2009, 52, 2854–2862. 38. Wilcken, R.; Liu, X.; Zimmermann, M. O.; Rutherford, T. J.; Fersht, A. R.; Joerger, A. C.; Boeckler, F. M. J. Am. Chem. Soc.2012, 134, 6810–6818. 39. Wilcken, R.; Zimmermann, M. O.; Lange, A.; Joerger, A. C.; Boeckler, F. M. J. Med. Chem. 2013, 56, 1363–1388. 40. M. R. Scholfield, C. M. Zanden, M. Carter, P. S. Ho, Protein Sci. 2013, 22, 139-152. 41. Kitagawa, S.; Uemura, K. Chem. Soc. Rev. 2005, 34, 109–119. 42. Raatikainen, K.; Rissanen, K. Chem Sci 2012, 3, 1235–1239. 43. Turunen, L.; Beyeh, N. K.; Pan, F.; Valkonen, A.; Rissanen, K. Chem. Commun. 2014, 50, 15920–15923. 44. Zang, S. Q.; Fan, Y. J.; Li, J. B.; Hou, H. W.; Mak, T. C. W. Cryst. Growth Des. 2011, 11, 3395–3405. 45. Metrangolo, P.; Meyer, F.; Pilati, T.; Proserpio, D. M.; Resnati, G. Chem. Eur. J. 2007, 13, 5765–5772. 46. Syssa-Magalé, J.-L.; Boubekeur, K.; Leroy, J.; Chamoreau, L.-M.; Fave, C.; Schöllhorn, B. CrystEngComm 2014, 16, 10380–10384. 47. Roques, N.; Mouchaham, G.; Duhayon, C.; Brands, S.; Tachon, A.; Weber, G.; Bellat, J. P.; Sutter, J.-P. Chem. Eur. J. 2014, 20, 11690–11694. 48. Martí-Rujas, J.; Colombo, L.; Lü, J.; Dey, A.; Terraneo, G.; Metrangolo, P.; Pilati, T.; Resnati, G. Chem. Commun. 2012, 48, 8207–8209. 49. Pigge, F. C.; Vangala, V. R.; Kapadia, P. P.; Swensona, D. C.; Rathb, N. P. Chem. Commun. 2008, 4726–4728. 50. Pfrunder, M. C.; Micallef, A. S.; Rintoul, L.; Arnold, D. P.; Davy, K. J. P.; McMurtrie, J. Cryst. Growth Des. 2014, 14, 6041−6047. 51. Li, B.; Zang, S-Q.; Wang, L-Y.; Mak, T. C. W. Coord. Chem. Rev. 2016, 308, 1-21. 52. Spek, A. L. Acta Cryst. 2015, C71, 9–18. 53. Spek, A. L. Acta Cryst. 2009, 65, 148–155. 54. Metrangolo, P.; Carcenac, Y.; Lahtinen, M.; Pilati, T.; Rissanen, K.; Vij, A.; Resnati, G. Science 2009, 323, 1461–1464.
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55. Lucassen, A. C. B.; Karton, A.; Leitus, G.; Shimon, L. J. W.; Martin, J. M. L.; van der Boom, M. E. Cryst. Growth Des. 2007, 7, 386–392. 56. Turunen, L.; Pan, F.; Beyeh, N. K.; Trant, J. F.; Ras, R. H. A.; Rissanen, K. Cryst. Growth Des., 2018, 18, 513–520. 57. Thompson, A. M. W. C.; Hock, J.; McCleverty, J. A.; Ward, M. D. Inorg. Chim. Acta 1997, 256, 331–334. 58. Wenk, H. H.; Sander, W. Eur. J. Org. Chem. 2002, 3927–3935. 59. Sharifa, M.; Maalika, A.; Reimanna, S.; Iqbal, J.; Patonay, T.; Spannenberg, A.; Villinger, A.; Langer, P. Tetrahedron 2013, 69, 174–183. 60. Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Germany, 1996. 61. Sheldrick, G. M. SHELXS-2013, Program for Solution of Crystal Refinement, 2013. 62. Sheldrick, G. M. Acta Cryst. 2015, A71, 3–8. 63. Sheldrick, G. M. Acta Cryst. 2015, C71, 3–8.
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For Table of Contents Use Only manuscript title Directed Molecular Structure Variations of Three-Dimensional Halogen-Bonded Organic Frameworks (XBOFs)
author list Sreejith Shankar, Olga Chovnik, Linda J. W. Shimon, Michal Lahav, and Milko E. van der Boom
TOC graphic
Synopsis
Halogen-Bonded Co-crystal Networks: Crystal packing variations in halogen-bonded (XB) cocrystals studied via systematic modifications in the molecular structure of XB donors. 3D supramolecular networks with extended channels have been demonstrated.
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