English

• Cucurbit[n]uril (Q[n], n=5-8), as a kind of macrocyclic host, has played an important role in the field of supramolecular chemistry. Due to its structural characteristics, namely, two negatively charged carbonyl ports, a positively charged outer wall, and a weakly negatively charged cavity (Fig.1a). Q[n] can be used as a ligand for metal ions to form Q[n]-M complexes through M—O coordination bonds (Fig.1d). In addition, Q[n] can also interact with ammonium ions through dipoles, hydrogen bonds, etc., to form supramolecular compounds with port interactions (Fig.1e). Q[n] and guests can also form supramolecular outer-wall interaction compounds through non-covalent interactions (Fig.1c). This outer-wall effect becomes the main driving force for the construction of 2D and 3D structures of Q[n]-based systems. More importantly, Q[n] can also use different volumes of cavities to identify and encapsulate guest molecules to form host-guest supramolecular entities (Fig.1b). Whether Q[n]-based complexes or supramolecular entities with outer-wall and host-guest interactions, they have shown broad application prospects in many fields^[1-7]. In particular, Q[n]-based complexes have shown broad application potential in electrode materials^[8], oxidation and reduction catalysts^[9-13], separation^[14], fluorescence imaging^[15], adsorption^[16], fluorescent probes^[17], and other fields.

  Figure 1

  

  Figure 1.  (a) Single crystal structure of Q[6]; (b) Crystal structure of Q[6]-guest inclusion complex; (c) Q[6]-Q[6] and Q[6]-guest interactions; (d) Single crystal structure of CyB₅Q[5]-Ca and guest; (e) Crystal structure of CyB₅Q[5] interacting with the port of the guest

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  Tao Zhu′s group of Guizhou University has done a lot of basic work on Q[n]-based metal complexes^[14], especially in all-alkyl substituted and partially alkyl substituted five-membered cucurbit[5]urils (SQ[5]), and in the field of single crystal synthesis of these Q[n]. They have proposed structural inducers and Q[n] outer wall interactions. Their work has led to the development of Q[n] coordination chemistry^[18-23]. However, how to directionally synthesize cucurbit[n]uril-based metal-organic frameworks(CMOFS) has always been a challenge.

  The new type of Q[n] series cyclobutanocucurbit[n]uril (CyB_nQ[n])^[24] reported in 2017 is a series with a relatively complete structure except ordinary Q[n] (such as methyl substituted Q[n] only has one kind, cyclopentyl has three kinds, cyclohexyl has two kinds). This series has n=5-8 structure types, and solubility is good in aqueous solution. However, apart from the synthesis of CyB_nQ[n] reported by the Anthony team in Australia, only three papers in our laboratory have reported their different types of crystal structures^[25-27]. Especially in the field of using inorganic salts with the same cation and different anions to synthesize complexes with Q[n], no in-depth and systematic research has been carried out. Therefore, the research on the structure, properties, and application prospects of CyB_nQ[n] and its complexes and host-guest entities needs to be improved and developed.

  The synthesis of Q[n]-based complexes and their use as materials for separation, adsorption, fluorescence/phosphorescence probes, and catalysis are the main purposes for expanding the application prospects of Q[n]-based complexes as supramolecular entities. However, how to directionally synthesize Q[n]-based supramolecular entities with certain cavities or cavities and apply these entities to specific scenarios is still a challenge. This is mainly due to the lack of a large number of empirical materials for the synthesis of Q[n]-based complexes, and it is difficult to summarize the general rules used to guide the synthesis of these complexes. Herein, we report the synthesis examples and crystal structures of four CyB₅Q[5]-based complexes, and provide empirical materials for finding the law of directional synthesis of them. The four complexes have similar structures to the reported complexes, and complex 4 has its own characteristics.

  1.   Experimental

  1.1   Main reagents

  Perchloric acid (40%), zinc chloride (anhydrous), sodium tetraborate, potassium thiocyanate, sodium bromide, potassium chloride, and hydrochloric acid (35%) were purchased from Xiya Reagents in China. All commercially available analytical-purity reagents are used directly without treatment. CyB₅Q[5] was synthesized and purified in our laboratory according to the literature^[24].

  1.2   Preparation of the complexes

  1.2.1   Preparation of complex [Na(CyB₅Q[5])(H₂O)₂]ClO₄·8H₂O (1)

  CyB₅Q[5] (22 mg, 0.02 mmol) and sodium tetraborate (38 mg, 0.19 mmol) were dissolved in 2 mL of distilled water to obtain solution A and solution B, respectively. ZnCl₂ (17 mg, 0.12 mmol) was dissolved in 1 mL of distilled water, and 0.05 mL of 3 mol·L^-1 hydrochloric acid was added to obtain solution C. Solution B was added slowly to solution C. Then, 0.05 mL perchloric acid (12 mol·L^-1) was added to obtain solution D. Finally, solution D was slowly added to solution A. After heating at 80 ℃ for 10 min, the solution was cooled and placed at room temperature for 9 d to obtain crystals that can be used for single-crystal X-ray diffraction.

  1.2.2   Preparation of complex [K₄(CyB₅Q[5])₂(H₂O)₄](SCN)₄·5H₂O (2)

  CyB₅Q[5] (20 mg, 0.02 mmol) and potassium thiocyanate (6 mg, 0.06 mmol) were dissolved in 2 mL of distilled water to obtain solution A and solution B, respectively. Solution B was added slowly dropwise to solution A to obtain solution C. Solution C was heated at 80 ℃ for 10 min, then cooled and placed at room temperature for 10 d to obtain crystals suitable for single-crystal X-ray diffraction.

  1.2.3   Preparation of complex [Na₂(CyB₅Q[5])(H₂O)]ClBr (3)

  CyB₅Q[5] (20 mg, 0.02 mmol) and sodium bromide (10 mg, 0.06 mmol) were dissolved in 2 mL of distilled water to obtain solution A and solution B, respectively. The mixture of solutions A and B was heated to 80 ℃ for 10 min, cooled, and left at room temperature for 10 d to obtain crystals suitable for single-crystal X-ray diffraction.

  1.2.4   Preparation of complex [K₂(CyB₅Q[5])(μ-H₂O)₃(H₂O)][ZnCl₄]·7H₂O (4)

  CyB₅Q[5] (20 mg, 0.02 mmol) and potassium chloride (5 mg, 0.06 mmol) were dissolved in 2 mL of distilled water to obtain solution A and solution B, respectively. ZnCl₂ (11 mg, 0.08 mmol) was dissolved in 1 mL of distilled water, and 0.05 mL of 3 mol·L^-1 hydrochloric acid was added to obtain solution C. Solution B was added dropwise to solution C to obtain solution D. Finally, solution D was added dropwise to solution A. The solution was heated at 80 ℃ for 10 min, cooled, and allowed to stand at room temperature for 15 d to obtain crystals suitable for single-crystal X-ray diffraction.

  1.3   Determination of single crystal structure

  Single-crystal X-ray diffraction data for complexes 1-4 were collected on a Rigaku Oxford Diffraction Supernova Dual Source (Oxford Diffraction Ltd., Abingdon, England) Cu at zero equipped with an AtlasS2 CCD using Mo Kα (2) or Cu Kα (1, 3, and 4) radiation. Lorentz polarization and absorption corrections were applied. The structure was solved by direct methods using the SHELXL-14 program^[28] and refined with SHELXL-14 by full matrix least-squares techniques on F². Non-hydrogen atoms were refined anisotropically, while the hydrogen atoms were located geometrically and refined isotropically. A summary of the crystallographic data, collection conditions, and refinement parameters for complexes 1-4 is listed in Table 1.

  Table 1

  

  Table 1.  Crystallographic data and structural refinement parameters for complexes 1-4

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  Parameter	1	2	3	4
  Formula	C40H60ClN20NaO244	C42H46K2N22O13S2	C40H42BrClN20Na2O11	C40H46Cl4K2N20O13Zn
  Formula weight	1 263.52	1 209.33	1 140.27	1 300.34
  λ / nm	0.154 184	0.071 073	0.154 184	0.154 184
  Temperature / K	120.01(10)	200.00(10)	220(2)	99.99(13)
  Crystal system	Orthorhombic	Monoclinic	Orthorhombic	Triclinic
  Space group	Pnma	P21/n	Pnma	P1
  a / nm	3.113 79(4)	1.616 33(6)	2.937 87(5)	1.165 75(2)
  b / nm	1.534 48(2)	1.509 62(5)	1.157 84(2)	1.407 81(3)
  c / nm	1.128 75(10)	2.127 30(10)	1.491 25(3)	1.763 10(3)
  α / (°)				88.077(2)
  β / (°)		99.688(4)		82.669 0(10)
  γ / (°)				81.942
  V / nm3	5.393 22(11)	5.116 7(4)	5.072 61(16)	2.841 17(9)
  Z	4	4	4	2
  Dc / (g·cm-3)	1.537	1.570	1.493	1.520
  Goodness-of-fit on F 2	1.002	1.025	1.023	1.067
  R1a [I > 2σ(I)]	0.090 2	0.079 7	0.098 3	0.062 8
  wR2b [I > 2σ(I)]	0.250 0	0.249 8	0.283 2	0.175 8
  R1 (all data)	0.094 8	0.110 6	0.103 3	0.065 7
  wR2 (all data)	0.247 3	0.221 4	0.290 6	0.174 0
  a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=|∑w(|Fo|2-|Fc|2)|/∑|w(Fo)2|1/2, where w=1/[σ2(Fo2)+(aP)2+bP], P=(Fo2+2Fc2)/3.

  2.   Results and discussion

  The crystal structures of complexes 1-4 are shown in Fig.2. Although in the synthesis of complex 1, in addition to CyB₅Q[5], hydrochloric acid and sodium tetraborate, zinc chloride, and perchloric acid were added to the mixed solution, [B₄O₇]^2- and [ZnCl₄]^2- were not found in the crystal structure of 1, only Cl^- and ClO₄^- were involved in the formation of crystals. The sodium ion (Na1) coordinates with five oxygen atoms (O1, O2, O3, O2^ⅰ, and O3^ⅰ) at one port of CyB₅Q[5], and also coordinates with the oxygen atoms (O13, O12) of a water molecule inside and outside the CyB₅Q[5] to form a Na—O coordinated seven-ligand molecular bowl (Fig.2a). The parameters of these coordination bonds are shown in Table S1 (Supporting information). These molecular bowls form a 1D molecular chain through hydrogen bonds between the O12 of the water molecule and the port O4 of another CyB₅Q[5] (Fig.3d). The 1D molecular chains are constructed into 1D supramolecular aggregates through a series of non-covalent interactions between water molecules, perchlorate ions and the outer wall of CyB₅Q[5] (Fig.3a-3c)

  Figure 2

  

  Figure 2.  Coordination bond details of complexes 1 (a), 2 (b), 3 (c), and 4 (d)

  Water molecules, chloride ions, and other anions are omitted for clarity; Symmetry codes: ^ⅰ x, 3/2-y, z for 1; ^ⅰ x, 1/2-y, z for 3.

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  Figure 3

  

  Figure 3.  Stacking diagram and 1D molecular chain of complex 1: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules, chloride ions, and perchlorate ions are omitted for clarity)

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  The crystal structure of complex 2 is shown in Fig.2b. The two port oxygen atoms of CyB₅Q[5] are coordinated by two potassium ions (K1, K2), and K1, K2 are also coordinated with the oxygen atoms of two water molecules (O12, O13), forming two six-coordinated molecular capsules. The parameters of the coordination bonds are shown in Table S1. These molecular capsules form 1D molecular chains (Fig.4d) through a variety of non-covalent interactions, and the molecular chains are further constructed into a 2D planar layered structure (Fig.4a-4c).

  Figure 4

  

  Figure 4.  Stacking diagram and 1D molecular chain of complex 2: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules and chloride ions are omitted for clarity)

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  The crystal structure of complex 3 is shown in Fig.2c. It can be seen that complex 3 uses the carbonyl oxygen atoms (O1-O5 and O1^ⅰ-O5^ⅰ) of the two ports of the CyB₅Q[5] to coordinate with two sodium ions (Na1 and Na1^ⅰ). At the same time, the two Na1 are also coordinated with the oxygen atoms (O1W and O1W^ⅰ) of the water molecules in the cavity of the two CyB₅Q[5] molecules, forming a 6-coordinated molecular capsule. The parameters of these coordination bonds are shown in Table S1. In addition, there is a chloride ion in the cavity of CyB₅Q[5] (the chloride ion is disordered in the crystal) connected to two OW1 atoms by dipole interaction. Through the dipole interaction of Na1, the molecular capsules are connected into 1D molecular chains (Fig.5d). These 1D molecular chains are further constructed into supramolecular aggregates by water molecules and bromide ions (Fig.5a-5c).

  Figure 5

  

  Figure 5.  Stacking diagram and 1D molecular chain of complex 3: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules and bromide ions are omitted for clarity)

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  The crystal structure of complex 4 is shown in Fig.2d. It can be seen that the carbonyl oxygen atoms of the two ports of CyB₅Q[5] are coordinated by K ions, forming a molecular capsule sealed at both ends. Its special molecular structure lies in the fact that K1 is coordinated with the oxygen atoms (O1-O5) of one port of CyB₅Q[5], and also coordinated with the oxygen atoms (O11-O13) of three water molecules to form an eight-ligand coordination geometry. At the other end of the CyB₅Q[5], K2 is coordinated with five oxygen atoms (O6-O10) at the port of CyB₅Q[5]. At the same time, K2 also coordinates with the oxygen atom (O11-O13) of three water molecules and the oxygen atom (O18) of one water molecule in the CyB₅Q[5] cavity to form a nine-ligand coordination geometry. The parameters of these coordination bonds are shown in Table S1. Such a complex is then connected to another identical complex by three oxygen bridges (O11-O13) to form a 1D molecular chain (Fig.6a). The 1D molecular chain is constructed into a 2D layered structure through the interaction of [ZnCl₄]^2- ions, water molecules and various non-covalent bonds between CyB₅Q[5] and CyB₅Q[5], and further constructed into a 3D stacked structure (Fig.6b). Such a structure already has the characteristics of a MOF structure (Fig.6b-6e). All the coordinate bond data are shown in Table S1.

  Figure 6

  

  Figure 6.  Stacking diagram and 1D molecular chain of complex 4: (a) 1D molecular chain (along b-axis); stacking diagram along (b) a-axis, (d) b-axis, and (e) c-axis, respectively; (c, f) details of the noncovalent interaction between CyB₅Q[5] and [ZnCl₄]^2- (water molecules and chlorine ions are omitted for clarity Cl^-)

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  3.   Conclusions

  Two kinds of inorganic salts with the same cations and different anions were used to react with CyB₅Q[5] to obtain four different types of CyB₅Q[5]-based complexes. The 1D molecular chain formed by the coordination bond was only obtained in the ZnCl₂ medium, which provides an imaginary space for further directional synthesis of Q[n]-based MOF materials. It is well known that the directional synthesis of Q[n]-based MOFs has not been systematically studied so far, which restricts the further application of Q[n]. Here, we propose the following assumptions: (1) whether ZnCl₂ or analogues are necessary conditions for the synthesis of Q[n]-based MOFs; (2) whether the concentration of Q[n] or metal ions affects the synthesis of Q[n]-based MOFs. Next, we will conduct in-depth research on these two issues.

  
  Supporting information is available at http://www.wjhxxb.cn
  
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• 

  Figure 1  (a) Single crystal structure of Q[6]; (b) Crystal structure of Q[6]-guest inclusion complex; (c) Q[6]-Q[6] and Q[6]-guest interactions; (d) Single crystal structure of CyB₅Q[5]-Ca and guest; (e) Crystal structure of CyB₅Q[5] interacting with the port of the guest

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  Figure 2  Coordination bond details of complexes 1 (a), 2 (b), 3 (c), and 4 (d)

  Water molecules, chloride ions, and other anions are omitted for clarity; Symmetry codes: ^ⅰ x, 3/2-y, z for 1; ^ⅰ x, 1/2-y, z for 3.

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  Figure 3  Stacking diagram and 1D molecular chain of complex 1: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules, chloride ions, and perchlorate ions are omitted for clarity)

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  Figure 4  Stacking diagram and 1D molecular chain of complex 2: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules and chloride ions are omitted for clarity)

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  Figure 5  Stacking diagram and 1D molecular chain of complex 3: stacking diagram along (a) a-axis, (b) b-axis, and (c) c-axis, respectively; (d) 1D molecular chain (water molecules and bromide ions are omitted for clarity)

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  Figure 6  Stacking diagram and 1D molecular chain of complex 4: (a) 1D molecular chain (along b-axis); stacking diagram along (b) a-axis, (d) b-axis, and (e) c-axis, respectively; (c, f) details of the noncovalent interaction between CyB₅Q[5] and [ZnCl₄]^2- (water molecules and chlorine ions are omitted for clarity Cl^-)

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  Table 1.  Crystallographic data and structural refinement parameters for complexes 1-4

  Parameter	1	2	3	4
  Formula	C40H60ClN20NaO244	C42H46K2N22O13S2	C40H42BrClN20Na2O11	C40H46Cl4K2N20O13Zn
  Formula weight	1 263.52	1 209.33	1 140.27	1 300.34
  λ / nm	0.154 184	0.071 073	0.154 184	0.154 184
  Temperature / K	120.01(10)	200.00(10)	220(2)	99.99(13)
  Crystal system	Orthorhombic	Monoclinic	Orthorhombic	Triclinic
  Space group	Pnma	P21/n	Pnma	P1
  a / nm	3.113 79(4)	1.616 33(6)	2.937 87(5)	1.165 75(2)
  b / nm	1.534 48(2)	1.509 62(5)	1.157 84(2)	1.407 81(3)
  c / nm	1.128 75(10)	2.127 30(10)	1.491 25(3)	1.763 10(3)
  α / (°)				88.077(2)
  β / (°)		99.688(4)		82.669 0(10)
  γ / (°)				81.942
  V / nm3	5.393 22(11)	5.116 7(4)	5.072 61(16)	2.841 17(9)
  Z	4	4	4	2
  Dc / (g·cm-3)	1.537	1.570	1.493	1.520
  Goodness-of-fit on F 2	1.002	1.025	1.023	1.067
  R1a [I > 2σ(I)]	0.090 2	0.079 7	0.098 3	0.062 8
  wR2b [I > 2σ(I)]	0.250 0	0.249 8	0.283 2	0.175 8
  R1 (all data)	0.094 8	0.110 6	0.103 3	0.065 7
  wR2 (all data)	0.247 3	0.221 4	0.290 6	0.174 0
  a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=|∑w(|Fo|2-|Fc|2)|/∑|w(Fo)2|1/2, where w=1/[σ2(Fo2)+(aP)2+bP], P=(Fo2+2Fc2)/3.

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