Supramolecular polyhedrons and preparation thereof

Abstract

Disclosed is a supramolecular polyhedron comprising 12 identical macrocyclic molecules wherein the macrocyclic molecules interact via 144 C-H hydrogen bonds, including 24 [C-H... F], 48 [C-H... O], and 72 [C-H... Pi]. A supramolecular assembly, a composite system, a crystalline material, and a porous material are also disclosed. The invention further discloses application of the supramolecular polyhedron, the supramolecular assembly and the composite system. Further, the invention discloses a preparation method.

Description

Technical Field

[0001] This invention relates generally to the field of supramolecular technology, and more specifically to supramolecular polyhedra, supramolecular assemblies, composite systems containing supramolecular polyhedra / assemblies, materials, and methods for their preparation. Background Technology

[0002] Spherical biological encapsulations based on supramolecular polyhedra, such as viral capsid proteins 1 and ferritin 2 They typically have a clear stereochemistry. 5 Dynamic superstructure 6 and multi-component binding properties 7 All these properties of biological encapsulations are essential for performing their functions, such as engulfing and protecting genetic material in living systems. 1 Transporting iron ions 2 and regulating virus-cell interactions 8 They are indispensable, according to many chemists. Unsurprisingly, numerous chemists... 9-15 and materials scientists 16，17 Attracted by the design and non-covalent synthesis of artificial polyhedra. (Literature) 18-24 The text details many artificial supramolecular polyhedra with different shapes and rich binding properties, demonstrating their applications in areas such as molecular separation. 17 , reaction catalysis 25 And protein stability 26 Applications in fields such as [unspecified fields]. However, synthesizing non-covalent enantiomeric supramolecular polyhedra with tunable mechanical properties and multi-component binding behavior remains challenging. Summary of the Invention

[0003] The inventors have conducted extensive research and developed supramolecular polyhedra with reversible photochromic behavior and light-controllable elasticity and hardness. They can also accommodate different small guest molecules simultaneously, thereby expanding the range of chiral superstructures, dynamic characteristics and binding properties of artificial supramolecular assemblies that simulate spherical biomacromolecules, and establishing a new scheme for constructing crystalline materials with light-controllable mechanical properties.

[0004] The present invention provides a supramolecular polyhedron comprising 12 identical macrocyclic molecules that interact through 144 CH hydrogen bonds, including 24 [CH…F], 48 [CH…O] and 72 [CH…π].

[0005] The present invention also provides a supramolecular assembly comprising the above-mentioned supramolecular polyhedra as building units.

[0006] The present invention also provides a composite system comprising the above-described supramolecular assembly and a guest molecule.

[0007] The present invention also provides a crystal material comprising the above-mentioned supramolecular polyhedron, supramolecular assembly, or composite system.

[0008] The present invention also provides a porous material comprising the above-mentioned supramolecular polyhedron, supramolecular assembly, or composite system.

[0009] Furthermore, the present invention provides the use of the above-mentioned supramolecular polyhedron, supramolecular assembly, or composite system in the preparation of materials with photochromic properties.

[0010] Furthermore, the present invention provides the use of the above-mentioned supramolecular polyhedron, or supramolecular assembly, or composite system in the preparation of materials with adjustable elasticity and / or hardness.

[0011] Furthermore, the present invention provides a preparation method, comprising:

[0012] (1) Provides a closed form of a diarylethene compound having an R conformation in two carbons in a diarylethene unit ((2R)-CE);

[0013] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units;

[0014] (3) React (2R)-CE and (4R)Cy-NDIDA in a 1:1 molar ratio to produce the macrocyclic molecule (8R)Cy-(4R)CE-TM; and

[0015] (4) To allow iPr2O to diffuse into the CHCl3 solution of the macrocyclic molecule.

[0016] Furthermore, the present invention also provides a preparation method, comprising:

[0017] (1) Provides a closed form of a diarylethene compound having an S conformation in two carbons in a diarylethene unit ((2S)-CE);

[0018] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units;

[0019] (3) React (2S)-CE and (4S)Cy-NDIDA in a 1:1 molar ratio to produce the macrocyclic molecule (8S)Cy-(4S)CE-TM; and

[0020] (4) To allow iPr2O to diffuse into the CHCl3 solution of the macrocyclic molecule.

[0021] Furthermore, the present invention also provides a preparation method, comprising:

[0022] (1) Provides a closed-form diarylethylene compound (CE);

[0023] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units;

[0024] (3) Equimolar amounts of (4R)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8R)Cy-(4R)CE-TM, (8R)Cy-(4S)CE-TM, (8R)Cy-(2R2S)CE-TM, and (8R)Cy-(2S2R)CE-TM; and

[0025] (4) Allow iPr2O to diffuse into the CHCl3 solution of the mixture.

[0026] Furthermore, the present invention also provides a preparation method, comprising:

[0027] (1) Provides a closed-form diarylethylene compound (CE);

[0028] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units;

[0029] (3) Equimolar amounts of (4S)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8S)Cy-(4R)CE-TM, (8S)Cy-(4S)CE-TM, (8S)Cy-(2R2S)CE-TM, and (8S)Cy-(2S2R)CE-TM; and

[0030] (4) Allow iPr2O to diffuse into the CHCl3 of the mixture.

[0031] Furthermore, the present invention also provides a method for preparing a material having photochromic properties and / or adjustable elasticity / hardness, comprising:

[0032] (1) Provides a chiral molecule containing a photoresponsive moiety, wherein all stereocenters of the chiral molecule have an R or S conformation; and

[0033] (2) Assemble supramolecular structures from chiral molecules. Attached Figure Description

[0034] Figure 1Illustrations of left-handed and right-handed supramolecular polyhedra (SSCs) are shown, along with an exemplary synthetic assembly of right-handed SSCs and their NMR spectra.

[0035] Figure 2 The configuration of solid-state SSCs and the stereo-oriented assembly of left-handed and right-handed SSCs are shown.

[0036] Figure 3 The stacking mode of solid right-handed SSC is shown.

[0037] Figure 4 A hierarchical porous framework for solid-state right-handed SSC is shown.

[0038] Figure 5 The complex system of dextrorotatory SCC with guest molecules is shown.

[0039] Figure 6 The complex system of levorotatory SSC with guest molecules is shown.

[0040] Figure 7 The photochromic behavior and photomechanical properties of SCC are shown.

[0041] Figure 8 An exemplary preparation scheme for dextrorotatory SSCs using diastereoselective crystallization is shown.

[0042] Figure 9 The driving force used to form the SSC is shown. Detailed Implementation

[0043] In this application, unless otherwise expressly stated, the use of the singular includes the plural and the use of the plural includes the singular.

[0044] In this invention, the terms "comprising," "including," and "containing" are not intended to limit the invention by excluding any changes or additions.

[0045] In this application, unless otherwise expressly stated, the use of "or" means "and / or", even if "and / or" may be explicitly used in certain circumstances.

[0046] As described above, the present invention provides a supramolecular polyhedron comprising 12 identical macrocyclic molecules that interact through 144 CH hydrogen bonds, including 24 [CH…F], 48 [CH…O], and 72 [CH…π].

[0047] As used herein, a "supramolecular polyhedron" refers to a superstructure with a polyhedral geometry formed by molecules or atoms through non-covalent interactions. The supramolecular polyhedron may have a twisted cube configuration. In this document, the supramolecular polyhedron may also be referred to as a "supramolecular twisted cube (SSC)".

[0048] In the SSC according to the invention, the macrocyclic molecules are held together by weak non-covalent interactions, i.e., intermolecular CH hydrogen bonds, without any other strong interactions. These weak non-covalent interactions hold multiple macrocyclic molecules together, resulting in a stable SSC. Suitably, the supramolecular polyhedron can consist of 12 macrocyclic molecules. Suitably, the supramolecular polyhedron can contain 2712 atoms.

[0049] In the SSC according to the invention, the CH hydrogen bond involves [CH…F], [CH…O], and [CH…π] interactions. The primary driving force can be the concerted [CH…π] interaction, supplemented by multiple [CH…F] and [CH…O] interactions.

[0050] In the SSC according to the invention, the macrocyclic molecule may have a C2-symmetric figure-eight configuration. Hereinafter, the macrocyclic molecule may also be referred to as a “twisted macrocycle.” Suitably, each pair of adjacent macrocyclic molecules may interact via 1 [CH…F], 2 [CH…O], or 3 [CH…π].

[0051] The twisted ring may contain a three-dimensional center. The three-dimensional center may have an R and / or S conformation.

[0052] In some embodiments, the three-dimensional centers contained in the twisted ring may all have an R conformation, and the SSC according to the invention may be a right-handed structure.

[0053] In some embodiments, the three-dimensional centers contained in the twisted ring may all have an S-conformation, and the SSC according to the present invention may be a left-handed structure.

[0054] Suitablely, the twisted macrocycle may include a cyclohexane unit. The cyclohexane unit refers to a substituted or unsubstituted cyclohexane structure. For example, the cyclohexane unit may include an aminocyclohexane structure.

[0055] Suitably, the twisted macrocycle may include a photoresponsive portion. Suitably, the photoresponsive portion in the twisted macrocycle may be derived from a diarylethylene compound. For example, the twisted macrocycle may be prepared from a material comprising a diarylethylene compound and a diaminocyclohexane-functionalized naphthalenediimide. Suitably, the molar ratio of the diarylethylene compound to the diaminocyclohexane-functionalized naphthalenediimide may be 1:1. Suitably, the diarylethylene compound may be in a closed form. For example, the diarylethylene compound may include a closed-form diarylvinyldialdehyde compound.

[0056] In some embodiments, the diarylethene compound may be a closed form with two carbons having an R conformation in the diarylethene unit ((2R)-CE); the diaminocyclohexane-functionalized naphthalenediimide may be a four-carbon compound with an R conformation in the two cyclohexane units ((4R)Cy-NDIDA); the reaction of (2R)-CE and (4R)Cy-NDIDA in a 2:2 molar ratio produces a twisted macrocycle (8R)Cy-(4R)CE-TM, which is subsequently assembled into a dextrorotatory SSC.

[0057] In some embodiments, the diarylethene compound may be a closed form with two carbons having an S conformation in the diarylethene unit ((2S)-CE); the diaminocyclohexane-functionalized naphthalenediimide may be a four-carbon compound having an S conformation in the two cyclohexane units ((4S)Cy-NDIDA); the reaction of (2S)-CE and (4S)Cy-NDIDA in a 2:2 molar ratio produces a twisted macrocycle (8S)Cy-(4S)CE-TM, which is subsequently assembled into a levorotatory SSC.

[0058] In the SSC according to the invention, the twisted ring can be assembled into first, second, and third pieces on the surface of a twisted cube. Suitably, the first piece can be a square with C4 symmetry. Suitably, the second piece can be an equilateral triangle with C3 symmetry. Suitably, the third piece can be an scalene triangle with C2 symmetry. The SSC according to the invention can contain 6 first pieces, 8 second pieces, and 24 third pieces.

[0059] Suitablely, in the first assembly, four cyclohexane units are incorporated within the cavity. Suitablely, in the second assembly, three hexafluorocyclopentane units occupy the center of the assembly. Suitablely, in the third assembly, a twisted macrocycle is located around the double axis.

[0060] The SSC according to the present invention can have 60 edges, 38 faces and 24 vertices.

[0061] The SSC according to the present invention can have an outer diameter of 5.1 nm.

[0062] The SSC according to the present invention may contain a cavity. The cavity may have a diameter of 2.3 nm. The cavity may have... The volume of the cavity.

[0063] Figure 1Illustrations of left-handed and right-handed supramolecular polyhedra (SSCs), an exemplary synthetic assembly of a right-handed SSC, and NMR spectra are shown. a) Illustrations of left-handed and right-handed SSCs, highlighting their topological chirality. Each SSC contains 6 squares (red) and 32 triangles (yellow and blue), with 60 sides and 24 vertices. b) Synthesis of the twisted macrocyclic (8R)Cy-(4R)CE-TM is shown, involving the [2+2]imine condensation of (2R)-CE with (4R)Cy-NDIDA in CHCl3 (70 °C, 2 days). Red asterisks (*) mark all stereocenters. c) Capped-Stick plot of solid-state (8R)Cy-(4R)CE-TM, showing its twisted figure-eight configuration. d. Illustration of a dextrorotatory SSC, which is assembled from 12 twisted macrocyclic (8R)Cy-(4R)CE-TM, wherein the twisted configuration is obtained by connecting the cyclohexane on the outer periphery of the structure, the gold bars represent the edges, and the gold spheres represent the vertices. e, f. (e) (8R)Cy-(4R)CE-TM and (f) SSC assemblies containing trace amounts of (8R)Cy-(4R)CE-TM. 1 The 1H NMR spectra (600 MHz, CDCl3, 298 K) show that the chemical shifts of H1 and H2 have shifted to higher fields (Δδ = -0.10 and -0.11 ppm, respectively), while the chemical shift of H5 has shifted to lower fields (Δδ = 0.07 ppm). Figure 1 (f) shows the spectrum originating from the large supramolecular structure, with a diffusion coefficient of 1.38 × 10⁻⁶. 6 cm 2 s 1 According to Stokes-Einstein-Sutherland calculations, the hydrodynamic radius of the supramolecular structure is 2.92 nm.

[0064] Figure 2 The solid-state SSC and its surface configuration are shown, along with the stereo-oriented assembly of left-handed and right-handed SSCs. a) Capped-Stick diagram of the solid-state superstructure of the right-handed SSC, with an outer diameter of 5.1 nm and an internal structure having a diameter of 2.3 nm and a volume of... a) Spherical cavity (orange). b) Right-handed SSC, where gold bars represent sides and gold spheres represent vertices. c) Right-handed SSC, its surface comprising a mosaic of 6 squares (red), 8 equilateral triangles (blue), and 24 scalene triangles (yellow). d) The first mosaic of squares (red) is shown, surrounded by four twisted macrorings, with four cyclohexane units incorporated within the cavity of the twisted macrorings. The squares of the first mosaic are rotated 25.9 degrees counterclockwise relative to the c-axis, giving the polyhedron chirality. e) The second mosaic of equilateral triangles (blue) is shown, surrounded by three twisted macrorings, with three hexafluorocyclopentanes occupying the center of the mosaic. f) The third mosaic of scalene triangles (yellow) is shown, surrounded by three twisted macrorings, with one twisted macroring located around the double axis. g) Left-handed SSC assembled from 12 helical twisted macrorings (8S)Cy-(4S)CE-TM. h, a right-handed SSC is assembled from 12 helical twisted macrorings (8R)Cy-(4R)CE-TM. According to X-ray crystallography, (8R)Cy-(4R)CE-TM crystallizes into a chiral space group (P432), with a unit cell volume of h. In solid-state SSC, 6 first-piece blocks, 8 second-piece blocks, and 24 third-piece blocks form a supramolecular polyhedron with 4-3-2 symmetry.

[0065] The SSC according to the present invention can be used to construct the next level of assembly. The present invention also provides a supramolecular assembly comprising supramolecular polyhedra as building blocks.

[0066] In the supramolecular assembly according to the invention, adjacent supramolecular polyhedra can interact via [π...π] stacking in at least one direction. Suitably, adjacent supramolecular polyhedra can be stabilized via [π...π] stacking interactions of naphthalenediimide units.

[0067] In the supramolecular assembly according to the present invention, a distance of 3.4 nm may exist between adjacent supramolecular polyhedra.

[0068] In the supramolecular assembly according to the invention, adjacent supramolecular polyhedra can be rotated relative to each other to provide a helical assembly. Suitably, the angle of rotation of adjacent supramolecular polyhedra relative to each other can be 32.6 degrees.

[0069] Figure 3 The stacking pattern of solid-state right-handed SSCs is shown. Figure a shows two stacked adjacent SSCs, indicating [π…π] stacking of naphthalene diimide (NDI) units in adjacent SSCs. Stable. The supramolecular square has a pore with a diameter of 0.8 nm at its center. b, A schematic diagram of two adjacent SSC stacks shows that the stacking planes of the adjacent squares are rotated 32.6 degrees relative to each other. c, d, show the stacking pattern of four adjacent SSCs.

[0070] The supramolecular assembly according to the invention may further comprise a second supramolecular structure. The second supramolecular structure may differ from the SSC described above. Suitably, the second supramolecular structure may consist of 24 identical twisted macrocycles. The twisted macrocycles may have any of the characteristics of the twisted macrocycles described above. Suitably, the second supramolecular structure may have an outer diameter of 6.6 nm. Suitably, the second supramolecular structure may have... The gap.

[0071] The supramolecular assemblies according to the present invention can construct porous frameworks. The assemblies according to the present invention can contain at least two different cavities, forming independent porous networks. For example, the assemblies according to the present invention can include SSC cavities to form one type of porous network. For example, the assemblies according to the present invention can include a second supramolecular cavity to form another type of porous network.

[0072] Figure 4 A hierarchical porous framework for right-handed SSCs is shown. a) A truncated octahedron (purple) is shown at the center of a cubic structure of eight right-handed SSCs. b) This truncated octahedron (purple) is a supramolecular polyhedron with a diameter of 6.6 nm, located in the cavity of the assembly, and is composed of 24 twisted macrocycles (8R)Cy-(4R)CE-TM. c) Each truncated octahedron is connected to its adjacent SSC polyhedrons through six pores with a diameter of 1.7 nm. The total volume of the truncated octahedron is... d, The hierarchical porous superstructure of right-handed SSCs, denoted by Capped-stick, comprises two distinct cavities (orange and purple spheres) and two sets (e and f) of independent porous networks. e, One set of porous networks consists of the internal cavities (orange spheres) of the right-handed SSCs, which are interconnected by six pores with a diameter of 0.8 nm. f, The other set of porous networks is formed by truncated octahedrons (purple), which are interconnected by six pores with a diameter of 1.7 nm.

[0073] The supramolecular assembly according to the invention comprises cavities that enclose guest molecules. The supramolecular assembly according to the invention may contain at least two separate compartments. The supramolecular assembly according to the invention may contain at least two different guest molecules. The compartments may be located within the inner cavity of the SSC, within the outer pocket of the SSC (e.g., within the inner cavity of the second supramolecular structure), and / or in the middle of the twisted macrocycle.

[0074] The present invention also relates to a composite system comprising a supramolecular assembly and a guest molecule. Suitably, the guest molecule may comprise different molecules, such as first and second guest molecules. The guest molecule may be housed in the internal cavity of the SSC, in the external pocket of the SSC, and / or in the middle of a twisted macrocycle. Suitable guest molecules may include one or more of the following: p-carborane, benzene, m-carborane, cyclohexane, and any combination thereof.

[0075] In some implementations, the SSC is a left-handed structure, with the first guest molecule housed in the internal cavity of the structure and the second guest molecule housed in the external pocket of the structure.

[0076] In some implementations, the SSC is a right-handed structure, with the first guest molecule housed in the internal cavity of the structure and the second guest molecule housed in the external pocket of the structure.

[0077] In some implementations, the SSC is a right-handed structure, with the first guest molecule housed in the twisted macrocycle of the structure and the second guest molecule housed in the internal cavity and / or external pocket of the structure.

[0078] Figure 5 The diagram illustrates a complex system of dextrorotatory SCCs with guest molecules. a, b, different views of the crystal superstructure of a dextrorotatory SCC simultaneously accommodating p-carborane and cyclohexane molecules. Capped-sticks and space-filling represent the dextrorotatory SCC and guest molecules (p-carborane and cyclohexane), respectively. c, disordered p-carborane molecules (red) are present in the inner compartments of the second equilateral triangular assembly, while cyclohexane molecules (green) are located in the outer pockets of the second equilateral triangular assembly. d, e, different views of the crystal superstructure of a dextrorotatory SCC simultaneously accommodating benzene and cyclohexane molecules. Capped-sticks and space-filling represent the dextrorotatory SCC and guest molecules (benzene and cyclohexane), respectively. f, disordered benzene molecules (magenta) are located in the center of a distorted macrocycle, while cyclohexane molecules (gold and green) are located in the inner compartments and outer pockets of the second equilateral triangular assembly.

[0079] Figure 6The composite system of levorotatory SSCs and guest molecules is shown. a) Capped-stick and space filling represent (8S)Cy-(4S)CE-TM (magenta) and m-carborane molecules (red), respectively, indicating that the m-carborane molecule is located in the inner compartment of the second equilateral triangular assembly. b) Capped-stick and space filling represent (8S)Cy-(4S)CE-TM (magenta) and cyclohexane molecules (green), respectively, indicating that the cyclohexane molecule is located in the outer pocket of the second equilateral triangular assembly. c) The relative positions of m-carborane and cyclohexane are shown. d) In the superstructure of solid SSCs, disordered m-carborane molecules (red) are located in the inner cavity of the levorotatory SSC, while cyclohexane molecules (green) are located in the outer pocket of the levorotatory SSC. e) The m-carborane (red) and cyclohexane (green) guest molecules are accommodated in different compartments of the porous framework composed of levorotatory SSCs.

[0080] The present invention also relates to crystalline materials comprising the above-mentioned supramolecular polyhedra, supramolecular assemblies, or composite systems.

[0081] The present invention also relates to porous materials, which include the above-mentioned supramolecular polyhedra, supramolecular assemblies, or composite systems.

[0082] The supramolecular polyhedra, assemblies containing supramolecular polyhedra, and / or composite systems according to the present invention exhibit reversible phototransformation behavior. Upon irradiation with light, the molecular structure of the supramolecular structure changes, and different structures exhibit different appearances and / or mechanical properties, such as color, transparency, hardness, elasticity, etc., thus displaying different behaviors.

[0083] Figure 7The photoinduced conversion behavior and photomechanical properties of SSC are shown. a, The change in the structure of right-handed SSC under alternating visible and ultraviolet light irradiation, showing that the closed diarylethene unit in the twisted macrocyclic (8R)Cy-(4R)CE-TM undergoes ring opening upon visible light irradiation and then ring closure upon ultraviolet light irradiation. bd, The color of the right-handed SSC crystal changes from deep blue to colorless upon visible light irradiation (b→c), and then recovers from colorless to deep blue upon exposure to ultraviolet light (c→d). e, Scanning electron microscopy (SEM) image of the right-handed SSC crystal, showing its truncated octahedral morphology. f, Solid-state UV-Vis-NIR absorption spectra of right-handed SSC before (blue) and after (red) visible light irradiation. g, Partial Raman spectra of right-handed SSC before (blue) and after (red) visible light irradiation, and the recovered SSC (green) obtained by irradiating the colorless SSC with ultraviolet light. h, Schematic diagram of probing the photocontrollable mechanical properties of SSC crystals by nanoindentation experiments on the crystal surface using a Berkovich tip. i, Comparison between representative load depth curves of nanoindentations performed on the SSC crystal surface before irradiation (blue), after irradiation with visible light (red), and then after irradiation with ultraviolet light (green). j, Scatter plot data of indentation tests performed on the SSC crystal after three alternating cycles of irradiation: before irradiation (square), after irradiation with visible light (circle), and after irradiation with ultraviolet light (triangle). Red, green, and magenta symbols (circle and triangle) represent data from the first, second, and third irradiation cycles, respectively. It can be seen that the mechanical properties of SSC crystals can be reversibly tuned between soft and hard states using light.

[0084] Furthermore, the present invention relates to the use of the above-mentioned supramolecular polyhedra, supramolecular assemblies, or composite systems in the preparation of materials with photochromic properties.

[0085] Furthermore, the present invention also relates to the use of the above-mentioned supramolecular polyhedra, or supramolecular assemblies, or composite systems in the preparation of materials with adjustable elasticity and / or hardness.

[0086] Furthermore, the present invention also relates to a preparation method, comprising:

[0087] (1) Provides a closed form of a diarylethene compound having an R conformation in two carbons in a diarylethene unit ((2R)-CE);

[0088] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units;

[0089] (3) React (2R)-CE and (4R)Cy-NDIDA in a 1:1 molar ratio to produce the macrocyclic molecule (8R)Cy-(4R)CE-TM; and

[0090] (4) To allow iPr2O to diffuse into the CHCl3 solution of the macrocyclic molecule.

[0091] Suitablely, step (1) may include:

[0092] (a) Provides diarylethene compounds (OE) in open form;

[0093] (b) Irradiating the OE solution with ultraviolet light to produce a closed form of diarylethene compound (CE);

[0094] and

[0095] (c) Separate (2R)-CE from a diarylethene compound ((2S)-CE) having two carbons in the S conformation of a closed diarylethene unit.

[0096] Suitablely, step (3) may include:

[0097] (2R)-CE and (4R)Cy-NDIDA were refluxed in CDCl3 for 2 days in a 2:2 molar ratio.

[0098] The supramolecular structure obtained by this method may include dextrorotatory SSC. Alternatively, the supramolecular structure may be prepared by diastereoselective crystallization.

[0099] This invention also relates to a preparation method, comprising:

[0100] (1) Provides a closed-form diarylethylene compound (CE);

[0101] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units;

[0102] (3) Equimolar amounts of (4R)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8R)Cy-(4R)CE-TM, (8R)Cy-(4S)CE-TM, (8R)Cy-(2R2S)CE-TM, and (8R)Cy-(2S2R)CE-TM; and

[0103] (4) iPr2O diffuses into the CHCl3 solution of the mixture.

[0104] Suitablely, step (3) may include:

[0105] Equimolar amounts of (4R)Cy-NDIDA and CE were convectioned and reacted at 70°C for 2 days to produce a mixture containing four macrocyclic molecules.

[0106] Based on single-crystal X-ray derivatization analysis, dextrorotatory SSCs can be assembled using diastereoselective crystallization.

[0107] Figure 8 Assembly of dextrorotatory SSCs using diastereoselective crystallization is illustrated. a) A mixture of four diastereomeric mixtures of [2+2] macrocycles was synthesized starting from racemic CE and (4R)Cy-NDIDA. This mixture contained 25% (8R)Cy-(4R)CE-TM and 25% (8R)Cy-(4S)CE-TM, while the remaining 50% could be two other twisted macrocycles, (8R)Cy-(2R2S)CE-TM and (8R)Cy-(2S2R)CE-TM. b) In the diastereomeric mixture of (8R)Cy-(4R)CE-TM, (8R)Cy-(4S)CE-TM, (8R)Cy-(2R2S)CE-TM, and (8R)Cy-(2S2R)CE-TM, diastereoselective crystallization of (8R)Cy-(4R)CE-TM yielded dextrorotatory SSCs.

[0108] Furthermore, the present invention also relates to a preparation method, comprising:

[0109] (1) Provides a closed form of a diarylethene compound having an S conformation in two carbons in a diarylethene unit ((2S)-CE);

[0110] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units;

[0111] (3) Reacting (2S)-CE and (4S)Cy-NDIDA in a 2:2 molar ratio to produce a twisted macrocyclic (8S)Cy-(4S)CE-TM; and

[0112] (4) Allow iPr2O to diffuse into the CHCl3 solution of the twisted macrocycle.

[0113] Suitablely, step (1) may include:

[0114] (a) Provides diarylethene compounds (OE) in open form;

[0115] (b) Irradiating an OE solution with ultraviolet light to produce a closed-form diarylethylene compound (CE); and

[0116] (c) Separate (2S)-CE from a diarylethene compound ((2S)-CE) having two carbons in the S conformation of a closed diarylethene unit.

[0117] Suitablely, step (3) may include:

[0118] (2S)-CE and (4S)Cy-NDIDA were refluxed in CDCl3 for 2 days in a 2:2 molar ratio.

[0119] The supramolecular structure obtained by this method may include levorotatory SSC. Alternatively, the supramolecular structure may be prepared by diastereoselective crystallization.

[0120] This invention also relates to a preparation method, comprising:

[0121] (1) Provides a closed-form diarylethylene compound (CE);

[0122] (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units;

[0123] (3) Equimolar amounts of (4S)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8S)Cy-(4R)CE-TM, (8S)Cy-(4S)CE-TM, (8S)Cy-(2R2S)CE-TM, and (8S)Cy-(2S2R)CE-TM; and

[0124] (4) Allow iPr2O to diffuse into the CHCl3 solution of the mixture.

[0125] Suitablely, step (3) may include:

[0126] Equimolar amounts of (4S)Cy-NDIDA and CE were convectioned and reacted at 70°C for 2 days to produce a mixture containing four macrocyclic molecules.

[0127] Furthermore, the present invention relates to a method for preparing a material having photochromic properties and / or adjustable elasticity / hardness, comprising:

[0128] (1) Provides a chiral molecule containing a photoresponsive moiety, wherein all stereocenters of the chiral molecule have an R or S conformation; and

[0129] (2) Assemble supramolecular structures from chiral molecules.

[0130] The chiral molecules exhibit different properties in different conformations, thereby obtaining materials with photoconvertible properties.

[0131] Example

[0132] Synthesis of open-form diarylethene (OE): Butyllithium (0.50 g, 7.76 mmol) was added dropwise at -78 °C under N2 to a solution of 2-(4-(4-bromo-5-methylthiophen-2-yl)phenyl)-1,3-dioxolane (2.50 g, 7.72 mmol) in anhydrous THF (80 mL). After stirring at -78 °C for 1 hour, octafluorocyclopentene (0.78 g, 3.66 mmol) in anhydrous THF (10 mL) was added dropwise. The mixture was stirred at -78 °C for 6 hours and then heated to room temperature. A saturated aqueous solution of NH4Cl (50 mL) was slowly added to quench the reaction. The mixture was extracted with CH2Cl2 and brine, dried (Na2SO4), and evaporated. The resulting yellow solid was separated by silica gel column chromatography (hexane:CH2Cl2 = 10:1). The photochromic component (1.79 g, 2.70 mmol) was dissolved in a mixture of Me₂CO and H₂O (120 mL, 5:1) containing pyridinium tosylate (2.51 g, 10.0 mmol). After heating under reflux for 2 days, an aqueous solution of NaHCO₃ (100 mL) was added, and the mixture was extracted with Et₂O and washed with brine. The combined organic phases were dried (Na₂SO₄) and concentrated under vacuum. The residue was purified by silica gel column chromatography (hexane:CH₂Cl₂ = 2:1) to give OE as a light green solid (yield: 65%). 1 H NMR (600MHz, CDCl3) δ10.01 (s, 2H), 7.90 (d, J=7.0Hz, 4H), 7.70 (d, J=7.1Hz, 4H), 7.42 (s, 2H), 2.02 (s, 6H); 13 C NMR (150MHz, CDCl3) δ191.4, 143.5, 141.0, 138.9, 135.7, 130.7, 126.4, 126.0, 124.5, 14.9; 19 F NMR (564MHz, CDCl3) δ 110.1 (t, J = 5.3Hz, 4H), -131.9 (q, J = 5.1Hz, 2H). HRMS-ESI of OE; C 29 H 18 The calculated value of F6NaO2S2 is: m / z = 599.0550[M + Na] + The measured value was 599.0551 [M+Na]. + .

[0133]

[0134] Synthesis of closed-form diarylethylene (CE): A solution of open-form diarylethylene (2.88 mg, 0.005 mmol) in CDCl3 (0.5 mL) was irradiated with ultraviolet light (370 nm) for several minutes, and the CE was synthesized by... 1 The blue solution obtained by H NMR spectroscopy showed a racemic CE yield of ~95%. 1 H NMR (600MHz, CDCl3) δ10.06 (s, 2H), 7.93 (d, J=8.4Hz, 4H), 7.73 (d, J=8.4Hz, 4H), 6.81 (s, 2H), 2.22 (s, 6H); 13 C NMR (150MHz, CDCl3) δ191.2, 156.7, 149.5, 138.3, 137.4, 130.2, 127.6, 116.3, 66.4, 25.4; 19 F NMR (564MHz, CDCl3) δ -112.1 (dd, J=256, 6.3Hz, 2H), -113.8 (dd, J=257, 5.9Hz, 2H), -133.4 (p, J=6.2Hz, 2H).

[0135]

[0136] Enantiomers (2R)-CE and (2S)-CE: A blue solution of racemic CE was passed through a semi-preparative chiral polysaccharide column (Lux 5μmi-Amylose-1LC column, 250×10 mm). 2 Separation was performed using hexane and isopropanol (9:1) as eluents. After 30 minutes, the fraction containing the desired compound was collected, and the solvent was removed under vacuum to obtain deep blue (2R)-CE and (2S)-CE solids. It is important to note that the separation should be performed in the dark. The NMR spectra of (2R)-CE and (2S)-CE were identical. 1 H NMR (600MHz, CDCl3) δ10.06 (s, 2H), 7.93 (d, J=8.4Hz, 4H), 7.73 (d, J=8.4Hz, 4H), 6.80 (s, 2H), 2.22 (s, 6H); 13 C NMR (125MHz, CDCl3) δ191.3, 156.7, 149.5, 138.3, 137.3, 130.2, 127.6, 116.3, 66.3, 25.4; 19FNMR (564MHz, CDCl3) δ 112.1 (dd, J=257, 5.9Hz, 2H), 113.8 (dd, J=257, 5.9Hz, 2H), 133.4 (p, J=6.1Hz, 2H). HRMS-ESI of (2S)-CE; C 30 H 21 The calculated value of F6O3S2 is: m / z = 607.0836 [M + MeO] - The measured value is 607.0846 [M+MeO]. - .

[0137]

[0138] (4R)Cy-NDIDA: The synthesis scheme followed the literature procedure. 27 The procedure was performed, but with slight modifications. Naphthalenetetracarboxylic dianhydride (NDA, 1.34 g, 5.0 mmol), (RR)-trans-1,2-cyclohexanediamine ((2R)Cy-DA, 1.14 g, 10.0 mmol), and p-toluenesulfonic acid monohydrate (1.90 g, 10.0 mmol) were dissolved in anhydrous DMF (20 mL) at room temperature. The reaction mixture was stirred at 125 °C until a homogeneous solution was obtained, and then stirred for 2 h to form a suspension. The reaction mixture was cooled to room temperature, and DMF was removed under vacuum. The pink solid was washed with MeOH and PhMe to obtain the xylenesulfonate of (4R)Cy-NDIDA, which was a yellow solid. The xylenesulfonate of (4R)Cy-NDIDA was suspended in CH2Cl2 (200 mL), and saturated NaHCO3 solution (50 mL) was added. The resulting solution was stirred at room temperature for 2 h. The organic layer was separated and extracted with CH2Cl2 (3 × 100 mL) and H2O. The combined organic layers were dried (Na2SO4) and concentrated under vacuum to give pure (4R)Cy-NDIDA as a pale yellow solid (yield: 65%). 1 H NMR (600MHz, CDCl3) δ8.72 (s, 4H), 4.79-4.74 (m, 2H), 3.76-3.71 (m, 2H), 2.53-2.46 (m, 2H), 2 .10-2.07(m, 2H), 1.89-1.88(m, 2H), 1.83-1.80(m, 4H), 1.56-1.40(m, 6H), 1.32-1.24(m, 4H). 13 C NMR (125MHz, CDCl3) δ164.5, 163.3, 131.5, 130.8, 127.3, 126.9, 126.6, 61.4, 50.5, 38.0, 28.9, 26.2, 25.5. (4R)HRMS-ESI of Cy-NDIDA; C26 H 29 The calculated value of N4O4 is: m / z = 461.2189 [M+H] + The actual measured value is: 461.2192 [M+H] + .

[0139]

[0140] (4S)Cy-NDIDA: Enantiomerically pure (4S)Cy-NDIDA was obtained in 60% yield from naphthalenetetracarboxylic dianhydride (NDA, 1.34 g, 5.0 mmol) and (SS)-trans-1,2-cyclohexanediamine ((2S)Cy-DA, 1.14 g, 10 mmol) following the same procedure as described above for the preparation of (4R)Cy-NDIDA. Its NMR spectral data were identical to those obtained from (4R)Cy-NDIDA. HRMS-ESI of (4S)Cy-NDIDA; C 26 H 29 The calculated value of N4O4 is: m / z = 461.2189 [M+H] + The actual measured value is: 461.2198 [M+H] + .

[0141]

[0142] (8R)Cy-(4R)CE-TM: (4R)Cy-NDIDA (2.30 mg, 0.005 mmol) and (2R)-CE (2.88 mg, 0.005 mmol) were dissolved in CDCl3 (0.5 mL) in an NMR tube. The NMR tube was wrapped with aluminum foil and heated to 70 °C in an oil bath. According to... 1 According to the results of H NMR spectroscopy and HRMS, after heating and reflux for 2 days, all reactants were exhausted and converted to [2+2](8R)Cy-(4R)CE-TM (yield: >99%). 1 H NMR (600MHz, CDCl3) 68.63 (d, J=7.7Hz, 4H), 8.56 (d, J=7.7Hz, 4H), 8.08 (s, 4H), 7.48 (d, J=8.5Hz, 8H), 7.33 (d, J=8.4Hz, 8H), 6.64 (s, 4H), 5.41-5.35 (m, 4H), 4.30 (td, J=10.3, 4.8Hz, 4H), 2.64-2.55 (m, 4H), 2.10 (s, 12H), 1.97-1.76 (m, 20H), 1.62-1.51 (m, 8H); 13C NMR (150MHz, CDCl3) δ163.4, 163.2, 159.0, 157.0, 149.1, 138.0, 134.7, 131.3, 130.7, 12 8.5, 127.0, 126.9, 126.7, 126.2, 114.8, 69.0, 66.0, 58.6, 34.7, 27.8, 26.0, 25.5, 24.4; 19 F NMR (564MHz, CDCl3) δ-112.0 (dd, J=256, 6.1Hz, 4H), -113.7 (dd, J=256, 6.0 Hz, 4H), -133.4 (p, J=6.1Hz, 4H); HRMS-ESI of (8R) Cy-(4R)CE-TM; C 110 H 85 F 12 The N8O8S4 is calculated as: m / z = 2002.5207 [M+H] + The actual measurement is: 2002.5186 [M+H] + .

[0143]

[0144] (8S)Cy-(4S)CE-TM: Using the same synthetic protocol, with (4S)Cy-NDIDA (2.30 mg, 0.005 mmol) and (2S)-CE (2.88 mg, 0.005 mmol) as precursors, (8S)Cy-(4S)CE-TM was obtained almost quantitatively. (8S)Cy-(4S)CE-TM exhibited the same NMR spectrum as (8R)Cy-(4R)CE-TM. HRMMS-ESI of (8S)Cy-(4S)CE-TM; C 110 H 85 F 12 The N8O8S4 is calculated as: m / z = 2002.5207 [M+H] + The actual measurement was: 2002.5198 [M+H] + .

[0145]

[0146] Right-handed SSC

[0147] Preparation: A 2 mM solution of enantiomeric pure [2+2](8R)Cy-(4R)CE-TM in CHCl3 was passed through a 0.45 μm filter and added to two 1 mL tubes, with volumes of 0.20 mL and 0.45 mL, respectively. These tubes were then placed together into a 20 mL vial containing ~3 mL of iPr2O, and the vial was capped. The capped vial was wrapped in aluminum foil and stored away from light. Over a week, iPr2O slowly diffused into the (8R)Cy-(4R)CE-TM CHCl3 solution, producing deep blue single crystals.

[0148] Left-handed SSC

[0149] Preparation: An enantiomeric pure [2+2](8S)Cy-(4S)CE-TM (2 mM) CHCl3 solution was passed through a 0.45 μm filter and added to two 1 mL tubes, with volumes of 0.20 mL and 0.45 mL respectively. These tubes were then placed together into a 20 mL vial containing ~3 mL of iPr2O, and the vial was capped. The capped vial was wrapped in aluminum foil and stored away from light. Over a week, iPr2O slowly diffused into the (8S)Cy-(4S)CE-TM CHCl3 solution, producing deep blue single crystals.

[0150] Dextrorotatory SSCs were obtained by diastereoselective crystallization.

[0151] A mixture of diastereomers of [2+2](8R)Cy-CE-TM synthesized from (4R)Cy-NDIDA and racemic CE was diluted from 10 mM to 2 mM using CHCl3. The solution was passed through a 0.45 μm filter and added to two 1 mL tubes, with volumes of 0.20 mL and 0.45 mL, respectively. These tubes were then placed together into a 20 mL vial containing ~3 mL of iPr2O and capped. The capped vial was wrapped in aluminum foil and stored away from light. Over a week, iPr2O slowly diffused into the CHCl3 solution of [2+2](8R)Cy-CE-TM, yielding deep blue single crystals with an average yield of ~17%.

[0152] Levorotatory SSCs were obtained by diastereoselective crystallization.

[0153] A mixture of diastereomers of (8S)Cy-CE-TM synthesized from (4S)Cy-NDIDA and racemic CE was diluted from 10 mM to 2 mM using CHCl3. The solution was passed through a 0.45 μm filter and added to two 1 mL tubes, with volumes of 0.20 mL and 0.45 mL, respectively. These tubes were then placed together into a 20 mL vial containing ~3 mL of iPr2O and capped. The capped vial was wrapped in aluminum foil and stored away from light. Over a week, iPr2O slowly diffused into the CHCl3 solution of (8S)Cy-CE-TM, yielding deep blue single crystals with an average yield of ~17%.

[0154] Visualization of non-covalent interactions

[0155] Independent gradient model (IGM) analysis is a method for identifying and separating intermolecular interactions based on pre-molecular density (electronic density model before molecule formation). 28 Strong polar attraction and van der Waals contact are visualized as blue and green isosurfaces, respectively. A single-crystal superstructure was used as the input file. The visualization was generated using the Multiwfn 3.6 program. 29 The binding surface was calculated using function 20 (Visualization of Weak Interactions) and Chimera software. 30 Visualize it.

[0156] Figure 9 The driving forces for SSC formation are illustrated. a) Non-covalent interactions between two adjacent twisted macrocycles in a right-handed SSC are shown: stabilization occurs through one [CH…F] (red line), two [CH…O] (green line), and three [CH…π] (magenta line) interactions. b) Independent gradient model (IGM) analysis shows the isosurfaces of intermolecular interactions between the two adjacent twisted macrocycles. c) Independent gradient model (IGM) analysis of non-covalent interactions within the right-handed SSC, illustrating the isosurfaces of intermolecular interactions. The right-handed SSC is stabilized by 144 weak hydrogen bonds of CH, including 24 [CH…F], 48 [CH…O], and 72 [CH…π] interactions. Δκinter(ρ) = 0.003au. Isosurfaces are colored in the range -0.05 < sign(λ2)ρ < +0.05au according to the BGR scheme.

[0157] The influence of the configuration of the diarylethylene unit on SSC assembly

[0158] To elucidate the influence of the configuration of the diarylethene unit on the stereooriented assembly of SSCs, we attempted to synthesize an open-form [2+2] twisted macrocycle, namely (8R)Cy-OE-TM. Refluxing a mixture of (4R)Cy-NDIDA and OE in CDCl3 for two days resulted only in the formation of a [1+1](4R)Cy-OE-triangle, rather than the open-form [2+2] twisted macrocycle. These observations suggest that the rigid configuration of the closed-form diarylethene is crucial for the formation of the [2+2] twisted macrocycle. Fortunately, (8R)Cy-OE-TM was obtained by irradiating a solution of (8R)Cy-(4R)CE-TM with visible light. However, after trying various crystallization methods, we found that (8R)Cy-OE-TM was difficult to crystallize, indicating that the rigid configuration of the closed-form [2+2] twisted macrocycle exhibits a significant influence on SSC formation.

[0159] The influence of the solid center in the NDI unit on the twisted macro-helix helix

[0160] To evaluate the influence of the stereocenter in the NDI unit on the helicity of the [2+2] twisted macrocycle, various conditions were tried for the crystallization of (8R)Cy-(4S)CE-TM. Only amorphous powders were obtained. Fortunately, single crystals of (8R)Cy-(4S)CE-TM and its enantiomers were obtained after three weeks of slow diffusion of cyclohexane into its CHCl3 solution. (8R)Cy-(4S)CE-TM exhibited a helicity similar to that of (8R)Cy-(4R)CE-TM in the solid-state superstructure. The overall helicity of the twisted macrocycle (8S)Cy-(4R)CE-TM was also similar to that of (8S)Cy-(4S)CE-TM. These observations suggest that the stereocenter in the NDI unit plays a crucial role in determining the overall helicity of the macrocycle.

[0161] SSC surface nanoindentation test

[0162] All nanoindentation tests were performed on Hysitron 950 / 980 Triboindenters equipped with a Berkovich indenter (150 nm radius). Single crystals of SSCs were immersed in Paratone oil and cooled to -20°C to avoid thermal decomposition during irradiation. The single crystals were washed with a small amount of hexane before and after visible and ultraviolet irradiation to remove the Paratone oil. Subsequently, the crystals were mounted on coverslips using Araldite adhesive, and the coverslips were then bonded to the top of a steel disk. For all measurements, loading and unloading rates were maintained at approximately 100 μN / s, with the indenter held at a constant load (500 μN) for 2 s before unloading. Elastic modulus (E) and hardness (H) values ​​were determined using standard Olive and Pharr analyses. For each sample type, several crystals were measured, and they were indented 10 times. The reported values ​​for each sample type are the average of all measurements.

[0163] After nanoindentation was performed on the surfaces of pristine SSC crystals and colorless SSC, significant changes in mechanical properties were clearly observed from their load-displacement curves. Figure 7 i). The original SSC crystal exhibits ( Figure 7 i) Under a peak load of 500 μN, the indenter produced a representative displacement of ~570 nm, while colorless SSC exhibited a representative displacement of ~2080 nm under the same conditions. Representative load depth curves of the recovered SSC ( Figure 7 i) The loading depth curve is significantly closer to that of the original SSC crystal. The results confirm that the elasticity and hardness of the SSC crystal can be reversibly tuned by light.

[0164] Although specific aspects of the invention have been shown and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, the appended claims are intended to cover all such changes and modifications falling within the scope of the invention.

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Claims

1. A supramolecular polyhedron comprising 12 identical macrocyclic molecules, wherein the macrocyclic molecules interact through 144 CH hydrogen bonds, the CH hydrogen bonds comprising 24 [CH···F], 48 [CH···O] and 72 [CH···π].

2. The supramolecular polyhedron of claim 1, wherein the macrocycle has a C2-symmetric figure-eight configuration.

3. The supramolecular polyhedron as described in claim 1 or 2, wherein the supramolecular polyhedron comprises a first piece, a second piece, and a third piece on its surface.

4. The supramolecular polyhedron as described in claim 3, wherein the first piece is a square with C4 symmetry.

5. The supramolecular polyhedron as described in claim 3 or 4, wherein the second piece is an equilateral triangle with C3 symmetry.

6. The supramolecular polyhedron according to any one of claims 3-5, wherein the third piece is an scalene triangle with C2 symmetry.

7. The supramolecular polyhedron according to any one of claims 1-6, wherein the supramolecular polyhedron has The volume of the cavity.

8. The supramolecular polyhedron according to any one of claims 1-7, wherein the supramolecular polyhedron has a right-handed structure and each macrocyclic molecule contains a stereocenter with an R conformation.

9. The supramolecular polyhedron according to any one of claims 1-8, wherein the supramolecular polyhedron has a left-handed structure and each macrocyclic molecule contains a stereocenter with an S conformation.

10. The supramolecular polyhedron according to any one of claims 1-9, wherein the macrocyclic molecule includes a photoresponsive portion.

11. The supramolecular polyhedron according to any one of claims 1-10, wherein the macrocyclic molecule is prepared from a material comprising a diarylethylene compound and a diaminocyclohexane-functionalized naphthalimide.

12. The supramolecular polyhedron of claim 11, wherein the molar ratio of the diarylethene compound to the diaminocyclohexane-functionalized naphthalimide is 1:

1.

13. A supramolecular assembly comprising a supramolecular polyhedron as any one of claims 1-12 as a building block.

14. The supramolecular assembly of claim 13, wherein adjacent supramolecular polyhedra interact through [π...π] stacking.

15. The supramolecular assembly of claim 13 or 14, further comprising a second supramolecular polyhedron, the second supramolecular structure comprising 24 identical macrocyclic molecules, said macrocyclic molecules being the same as those used in the supramolecular structure of any one of claims 1-13.

16. The supramolecular assembly according to any one of claims 13-15, comprising at least two independent compartments.

17. The supramolecular assembly of claim 16, wherein the compartment is located in the internal cavity of the supramolecular polyhedron, in the external pocket of the supramolecular polyhedron, and / or in the middle of the macrocyclic molecule.

18. A composite system comprising a supramolecular assembly and a guest molecule as described in any one of claims 13-17.

19. The composite system of claim 18, wherein the guest molecule comprises different first guest molecules and second guest molecules.

20. The composite system of claim 18 or 19, wherein the guest molecule is contained in the internal cavity of the supramolecular polyhedron, in the external pocket of the supramolecular polyhedron, and / or in the middle of the macrocyclic molecule.

21. The composite system according to any one of claims 18-20, wherein the guest molecule comprises one or more of the following: p-carborane, benzene, m-carborane, cyclohexane, and any combination thereof.

22. A crystalline material comprising a supramolecular polyhedron as described in any one of claims 1-12, a supramolecular assembly as described in any one of claims 13-17, or a composite system as described in any one of claims 18-21.

23. A porous material comprising a supramolecular polyhedron as described in any one of claims 1-12, a supramolecular assembly as described in any one of claims 13-17, or a composite system as described in any one of claims 18-21.

24. Use of the supramolecular polyhedron as described in any one of claims 1-12, or the supramolecular assembly as described in any one of claims 13-17, or the composite system as described in any one of claims 18-21 in the preparation of materials with photochromic properties.

25. Use of the supramolecular polyhedron as claimed in any one of claims 1-12, or the supramolecular assembly as claimed in any one of claims 13-17, or the composite system as claimed in any one of claims 18-21 in the preparation of a material having adjustable elasticity / hardness.

26. A preparation method, comprising: (1) Provides a closed form of a diarylethene compound having an R conformation in two carbons in a diarylethene unit ((2R)-CE); (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units; (3) React (2R)-CE and (4R)Cy-NDIDA in a 1:1 molar ratio to produce the macrocyclic molecule (8R)Cy-(4R)CE-TM; and (4) To allow iPr2O to diffuse into the CHCl3 solution of the macrocyclic molecule.

27. The preparation method according to claim 26, wherein step (1) comprises: (a) Provides diarylethene compounds (OE) in open form; (b) Irradiating OE with ultraviolet light to produce a closed-form diarylethylene compound (CE); and (c) Separate (2R)-CE from a closed form of a diarylethene compound ((2S)-CE) having an S conformation in a diarylethene unit with two carbons.

28. A preparation method, comprising: (1) Provides a closed form of a diarylethene compound having an S conformation in two carbons in a diarylethene unit ((2S)-CE); (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units; (3) React (2S)-CE and (4S)Cy-NDIDA in a 1:1 molar ratio to produce the macrocyclic molecule (8S)Cy-(4S)CE-TM; and (4) To allow iPr2O to diffuse into the CHCl3 solution of the macrocyclic molecule.

29. The preparation method according to claim 28, wherein step (1) comprises: (a) Provides diarylethene compounds (OE) in open form; (b) Irradiating OE with ultraviolet light to produce a closed-form diarylethylene compound (CE); and (c) Separate (2R)-CE from a closed form of a diarylethene compound ((2S)-CE) having an S conformation in a diarylethene unit with two carbons.

30. A preparation method, comprising: (1) Provides a closed-form diarylethylene compound (CE); (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4R)Cy-NDIDA) having an R conformation in two cyclohexane units; (3) Equimolar amounts of (4R)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8R)Cy-(4R)CE-TM, (8R)Cy-(4S)CE-TM, (8R)Cy-(2R2S)CE-TM, and (8R)Cy-(2S2R)CE-TM; and (4) Allow iPr2O to diffuse into the CHCl3 solution of the mixture.

31. A preparation method, comprising: (1) Provides a closed-form diarylethylene compound (CE); (2) Provides a four-carbon diaminocyclohexane-functionalized naphthalenediimide ((4S)Cy-NDIDA) having an S conformation in two cyclohexane units; (3) Equimolar amounts of (4S)Cy-NDIDA and CE are reacted to produce a mixture containing four macrocyclic molecules: (8S)Cy-(4R)CE-TM, (8S)Cy-(4S)CE-TM, (8S)Cy-(2R2S)CE-TM, and (8S)Cy-(2S2R)CE-TM; and (4) Allow iPr2O to diffuse into the CHCl3 solution of the mixture.

32. A method for preparing a material having photochromic properties and / or adjustable elasticity / hardness, comprising: (1) Provide a chiral molecule containing a photoresponsive part, wherein all stereocenters of the chiral molecule have an R or S conformation; and (2) Assemble supramolecular structures from chiral molecules.

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